[Title 40 CFR ]
[Code of Federal Regulations (annual edition) - July 1, 2005 Edition]
[From the U.S. Government Printing Office]
[[Page i]]
40
Parts 136 to 149
Revised as of July 1, 2005
Protection of Environment
________________________
Containing a codification of documents of general
applicability and future effect
As of July 1, 2005
With Ancillaries
Published by
Office of the Federal Register
National Archives and Records
Administration
A Special Edition of the Federal Register
[[Page ii]]
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[[Page iii]]
Table of Contents
Page
Explanation................................................. v
Title 40:
Chapter I--Environmental Protection Agency
(Continued) 3
Finding Aids:
Material Approved for Incorporation by Reference........ 845
Table of CFR Titles and Chapters........................ 867
Alphabetical List of Agencies Appearing in the CFR...... 885
List of CFR Sections Affected........................... 895
[[Page iv]]
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Cite this Code: CFR
To cite the regulations in
this volume use title,
part and section number.
Thus, 40 CFR 136.1 refers
to title 40, part 136,
section 1.
----------------------------
[[Page v]]
EXPLANATION
The Code of Federal Regulations is a codification of the general and
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Each volume of the Code is revised at least once each calendar year
and issued on a quarterly basis approximately as follows:
Title 1 through Title 16.................................as of January 1
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[[Page vi]]
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the revision dates of the 50 CFR titles.
[[Page vii]]
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July 1, 2005.
[[Page ix]]
THIS TITLE
Title 40--Protection of Environment is composed of thirty-one
volumes. The parts in these volumes are arranged in the following order:
parts 1-49, parts 50-51, part 52 (52.01-52.1018), part 52 (52.1019-End),
parts 53-59, part 60 (60.1-End), part 60 (Appendices), parts 61-62, part
63 (63.1-63.599), part 63 (63.600-63.1199), part 63 (63.1200-63.1439),
part 63 (63.1440-63.6175), part 63 (63.6580-63.8830), part 63 (63.8980-
End) parts 64-71, parts 72-80, parts 81-85, part 86 (86.1-86.599-99)
part 86 (86.600-1-End), parts 87-99, parts 100-135, parts 136-149, parts
150-189, parts 190-259, parts 260-265, parts 266-299, parts 300-399,
parts 400-424, parts 425-699, parts 700-789, and part 790 to End. The
contents of these volumes represent all current regulations codified
under this title of the CFR as of July 1, 2005.
Chapter I--Environmental Protection Agency appears in all thirty-one
volumes. An alphabetical Listing of Pesticide Chemicals Index appears in
parts 150-189. Regulations issued by the Council on Environmental
Quality appear in the volume containing part 790 to End. The OMB control
numbers for title 40 appear in Sec. 9.1 of this chapter.
For this volume, Cheryl E. Sirofchuck was Chief Editor. The Code of
Federal Regulations publication program is under the direction of
Frances D. McDonald, assisted by Alomha S. Morris.
[[Page 1]]
TITLE 40--PROTECTION OF ENVIRONMENT
(This book contains parts 136 to 149)
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Part
chapter i--Environmental Protection Agency (Continued)...... 136
[[Page 3]]
CHAPTER I--ENVIRONMENTAL PROTECTION AGENCY (CONTINUED)
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Editorial Note: Nomenclature changes to chapter I appear at 65 FR
47324, 47325, Aug. 2, 2000, and at 66 FR 34375, 34376, June 28, 2001.
SUBCHAPTER D--WATER PROGRAMS (CONTINUED)
Part Page
136 Guidelines establishing test procedures for
the analysis of pollutants.............. 5
140 Marine sanitation device standard........... 339
141 National primary drinking water regulations. 343
142 National primary drinking water regulations
implementation.......................... 560
143 National secondary drinking water
regulations............................. 614
144 Underground injection control program....... 616
145 State UIC program requirements.............. 683
146 Underground injection control program:
Criteria and standards.................. 696
147 State underground injection control programs 727
148 Hazardous waste injection restrictions...... 827
149 Sole source aquifers........................ 836
[[Page 5]]
SUBCHAPTER D_WATER PROGRAMS (CONTINUED)
PART 136_GUIDELINES ESTABLISHING TEST PROCEDURES FOR THE ANALYSIS OF
POLLUTANTS--Table of Contents
Sec.
136.1 Applicability.
136.2 Definitions.
136.3 Identification of test procedures.
136.4 Application for alternate test procedures.
136.5 Approval of alternate test procedures.
Appendix A to Part 136--Methods for Organic Chemical Analysis of
Municipal and Industrial Wastewater
Appendix B to Part 136--Definition and Procedure for the Determination
of the Method Detection Limit--Revision 1.11
Appendix C to Part 136--Inductively Coupled Plasma--Atomic Emission
Spectrometric Method for Trace Element Analysis of Water and
Wastes Method 200.7
Appendix D to Part 136--Precision and Recovery Statements for Methods
for Measuring Metals
Authority: Secs. 301, 304(h), 307 and 501(a), Pub. L. 95-217, 91
Stat. 1566, et seq. (33 U.S.C. 1251, et seq.) (the Federal Water
Pollution Control Act Amendments of 1972 as amended by the Clean Water
Act of 1977).
Sec. 136.1 Applicability.
The procedures prescribed herein shall, except as noted in Sec.
136.5, be used to perform the measurements indicated whenever the waste
constituent specified is required to be measured for:
(a) An application submitted to the Administrator, or to a State
having an approved NPDES program for a permit under section 402 of the
Clean Water Act of 1977, as amended (CWA), and/or to reports required to
be submitted under NPDES permits or other requests for quantitative or
qualitative effluent data under parts 122 to 125 of title 40, and,
(b) Reports required to be submitted by discharges under the NPDES
established by parts 124 and 125 of this chapter, and,
(c) Certifications issued by States pursuant to section 401 of the
CWA, as amended.
[38 FR 28758, Oct. 16, 1973, as amended at 49 FR 43250, Oct. 26, 1984]
Sec. 136.2 Definitions.
As used in this part, the term:
(a) Act means the Clean Water Act of 1977, Pub. L. 95-217, 91 Stat.
1566, et seq. (33 U.S.C. 1251 et seq.) (The Federal Water Pollution
Control Act Amendments of 1972 as amended by the Clean Water Act of
1977).
(b) Administrator means the Administrator of the U.S. Environmental
Protection Agency.
(c) Regional Administrator means one of the EPA Regional
Administrators.
(d) Director means the Director of the State Agency authorized to
carry out an approved National Pollutant Discharge Elimination System
Program under section 402 of the Act.
(e) National Pollutant Discharge Elimination System (NPDES) means
the national system for the issuance of permits under section 402 of the
Act and includes any State or interstate program which has been approved
by the Administrator, in whole or in part, pursuant to section 402 of
the Act.
(f) Detection limit means the minimum concentration of an analyte
(substance) that can be measured and reported with a 99% confidence that
the analyte concentration is greater than zero as determined by the
procedure set forth at appendix B of this part.
[38 FR 28758, Oct. 16, 1973, as amended at 49 FR 43250, Oct. 26, 1984]
Sec. 136.3 Identification of test procedures.
(a) Parameters or pollutants, for which methods are approved, are
listed together with test procedure descriptions and references in
Tables IA, IB, IC, ID, IE, and IF. The full text of the referenced test
procedures are incorporated by reference into Tables IA, IB, IC, ID, IE,
and IF. The incorporation by reference of these documents, as specified
in paragraph (b) of this section, was approved by the Director of the
Federal Register in accordance with 5 U.S.C. 552(a) and 1 CFR part 51.
Copies of the documents may be obtained from the sources listed in
paragraph (b) of
[[Page 6]]
this section. Information regarding obtaining these documents can be
obtained from the EPA Office of Water Statistics and Analytical Support
Branch at 202-566-1000. Documents may be inspected at EPA's Water
Docket, EPA West, 1301 Constitution Avenue, NW., Room B135, Washington,
DC (Telephone: 202-566-2426); or at the National Archives and Records
Administration (NARA). For information on the availability of this
material at NARA, call 202-741-6030, or go to: http://www.archives.gov/
federal--register/code--of--federal--regulations/ibr--locations.html.
These test procedures are incorporated as they exist on the day of
approval and a notice of anys change in these test procedures will be
published in the Federal Register. The discharge parameter values for
which reports are required must be determined by one of the standard
analytical test procedures incorporated by reference and described in
Tables IA, IB, IC, IE, and IF, or by any alternate test procedure which
has been approved by the Administrator under the provisions of paragraph
(d) of this section and Sec. Sec. 136.4 and 136.5. Under certain
circumstances (paragraph (b) or (c) of this section or 40 CFR 401.13)
other test procedures may be more advantageous when such other test
procedures have been previously approved by the Regional Administrator
of the Region in which the discharge will occur, and providing the
Director of the State in which such discharge will occur does not object
to the use of such alternate test procedure.
[[Page 7]]
Table IA--List of Approved Biological Methods
--------------------------------------------------------------------------------------------------------------------------------------------------------
Standard methods 18th,
Parameter and units Method \1\ EPA 19th, 20th Ed. ASTM AOAC USGS Other
--------------------------------------------------------------------------------------------------------------------------------------------------------
Bacteria:
1. Coliform (fecal), number Most Probable Number p. 132 9221C E \4\
per 100 mL. (MPN), 5 tube 3 \3\
dilution, or
Membrane filter (MF) p. 124 9222D \4\ ........... ........... B-0050-85
\2\, single step. \3\ \5\
2. Coliform (fecal) in MPN, 5 tube, 3 p. 132 9221C E \4\ ........... ........... ...........
presence of chlorine, number dilution, or \3\
per 100 mL.
MF, single step \6\. p. 124 9222D \4\ ........... ........... ........... ....................
\3\
3. Coliform (total), number MPN, 5 tube, 3 p. 114 9221B \4\
per 100 mL. dilution, or \3\
MF \2\, single step p. 108 9222B \4\ ........... ........... B-0025-85 ....................
or two step. \3\ \5\
4. Coliform (total), in MPN, 5 tube, 3 p. 114 9221B \4\ ........... ........... ........... ....................
presence of chlorine, number dilution, or \3\
per 100 mL.
MF \2\ with p. 111 9222(B+B.5c) \4\
enrichment. \3\
5. E. coli, number per 100 mL MPN \7,9,15\, ......... 9221B.1/9221F \4,12,14\
\28\. multiple tube,.
multiple tube/ ......... 9223B \4,13\ ........... 991.15 \11\ ........... Colilert [reg]
multiple well, \13,17\
Colilert-18 [reg]
\13,16,17\
MF \2,6,7,8,9\ two ......... 9222B/9222G \4,19\
step, or
1103.1 9213D \4\ D5392-93
\20\ \10\
single step......... 1603 \21\
1604 \22\
......... ....................... ........... ........... ........... mColiBue 24 \18\
6. Fecal streptococci, number MPN, 5 tube, 3 p. 139 9230B \4\, 9230C \4\
per 100 mL. dilution, \3\
MF \2\, or.......... p. 136 ....................... ........... B-0055-85
\3\ \5\
Plate count......... p. 143
\4\
7. Enterococci, number per MPN \7, 9\ multiple ......... 9230B \4\
100 mL. tube.
multiple tube/ ......... ....................... D6503-99 ........... ........... Enterolert
multiple well. \10\ [reg]\13,23\
MF \2,6,7,8,9\ two 1106.1 9230C \4\ D5259-92
step. \24\ \10\
single step, or..... 1600 \25\
Plate count......... p. 143
\3\
Protozoa:
8. Cryptosporidium \28\...... Filtration/IMS/FA... 1622 \26\
1623 \27\
9. Giardia \28\.............. Filtration/IMS/FA... 1623 \27\
Aquatic Toxicity:
10. Toxicity, acute, fresh Ceriodaphnia dubia 2002.0
water organisms, LC50, acute. \29\
percent effluent.
[[Page 8]]
Daphnia puplex and 2021.0
Daphnia magna acute. \29\
Fathead Minnow, 2000.0
Pimephales \29\
promelas, and
Bannerfin shiner,
Cyprinella leedsi,
acute.
Rainbow Trout, 2019.0
Oncorhynchus \29\
mykiss, and brook
trout, Salvelinus
fontinalis, acute.
11. Toxicity, acute, Mysid, Mysidopsis 2007.0
estuarine and marine bahia, acute. \29\
organisms of the Atlantic
Ocean and Gulf of Mexico,
LC50, percent effluent.
Sheepshead Minnow, 2004.0
Cyprinodon \29\
variegatus, acute.
Silverside, Menidia 2006.0
beryllina, Menidia \29\
menidia, and
Menidia peninsulae,
acute.
12. Toxicity, chronic, fresh Fathead minnow, 1000.0
water organisms, NOEC or Pimephales \30\
IC25, percent effluent. promelas,
larvalsurvival and
growth.
Fathead minnow, 1001.0
Pimephales \30\
promelas, embryo-
larval survival and
teratogenicity.
Daphnia, 1002.0
Ceriodaphnia dubia, \30\
survival and
reproduction.
Green alga, 1003.0
Selenastrum \30\
capricornutum,
growth.
13. Toxicity, chronic, Sheepshead minnow, 1004.0
estuarine and marine Cyprinodon \31\
organisms of the Atlantic variegatus,larval
Ocean and Gulf of Mexico, survival and growth.
NOEC or IC25, percent
effluent.
Sheepshead minnow, 1005.0
Cyprinodon \31\
variegatus,embryo-
larval survival and
teratogenicity.
Inland silverside, 1006.0
Menidia beryllina, \31\
larval survival and
growth.
Mysid, Mysidopsis 1007.0
bahia, survival, \31\
growth,and
fecundity.
[[Page 9]]
Sea urchin, Arbacia 1008.0
punctulata, \31\
fertilization.
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Notes to Table IA:
\1\ The method must be specified when results are reported.
\2\ A 0.45 [micro]m membrane filter (MF) or other pore size certified by the manufacturer to fully retain organisms to be cultivated and to be free of
extractables which could interfere with their growth.
\3\ USEPA. 1978. Microbiological Methods for Monitoring the Environment, Water, and Wastes. Environmental Monitoring and Support Laboratory, U.S.
Environmental Protection Agency, Cincinnati, Ohio. EPA/600/8-78/017.
\4\ APHA. 1998, 1995, 1992. Standard Methods for the Examination of Water and Wastewater. American Public Health Association. 20th, 19th, and 18th
Editions. Amer. Publ. Hlth. Assoc., Washington, D.C.
\5\ USGS. 1989. U.S. Geological Survey Techniques of Water-Resource Investigations, Book 5, Laboratory Analysis, Chapter A4, Methods for Collection and
Analysis of Aquatic Biological and Microbiological Samples, U.S. Geological Survey, U.S. Department of Interior, Reston, Virginia.
\6\ Because the MF technique usually yields low and variable recovery from chlorinated wastewaters, the Most Probable Number method will be required to
resolve any controversies.
\7\ Tests must be conducted to provide organism enumeration (density). Select the appropriate configuration of tubes/filtrations and dilutions/volumes
to account for the quality, character, consistency, and anticipated organism density of the water sample.
\8\ When the MF method has not been used previously to test ambient waters with high turbidity, large number of noncoliform bacteria, or samples that
may contain organisms stressed by chlorine, a parallel test should be conducted with a multiple-tube technique to demonstrate applicability and
comparability of results.
\9\ To assess the comparability of results obtained with individual methods, it is suggested that side-by-side tests be conducted across seasons of the
year with the water samples routinely tested in accordance with the most current Standard Methods for the Examination of Water and Wastewater or EPA
alternate test procedure (ATP) guidelines.
\10\ ASTM. 2000, 1999, 1996. Annual Book of ASTM Standards--Water and Environmental Technology. Section 11.02. American Society for Testing and
Materials. 100 Barr Harbor Drive, West Conshohocken, PA 19428.
\11\ AOAC. 1995. Official Methods of Analysis of AOAC International, 16th Edition, Volume I, Chapter 17. Association of Official Analytical Chemists
International. 481 North Frederick Avenue, Suite 500, Gaithersburg, Maryland 20877-2417.
\12\ The multiple-tube fermentation test is used in 9221B.1. Lactose broth may be used in lieu of lauryl tryptose broth (LTB), if at least 25 parallel
tests are conducted between this broth and LTB using the water samples normally tested, and this comparison demonstrates that the false-positive rate
and false-negative rate for total coliform using lactose broth is less than 10 percent. No requirement exists to run the completed phase on 10 percent
of all total coliform-positive tubes on a seasonal basis.
\13\ These tests are collectively known as defined enzyme substrate tests, where, for example, a substrate is used to detect the enzyme [beta]-
glucuronidase produced by E. coli.
\14\ After prior enrichment in a presumptive medium for total coliform using 9221B.1, all presumptive tubes or bottles showing any amount of gas, growth
or acidity within 48 h 3 h of incubation shall be submitted to 9221F. Commercially available EC-MUG media or EC media
supplemented in the laboratory with 50 [micro]g/mL of MUG may be used.
\15\ Samples shall be enumerated by the multiple-tube or multiple-well procedure. Using multiple-tube procedures, employ an appropriate tube and
dilution configuration of the sample as needed and report the Most Probable Number (MPN). Samples tested with Colilert [reg] may be enumerated with
the multiple-well procedures, Quanti-Tray [reg] or Quanti-Tray [reg] 2000, and the MPN calculated from the table provided by the manufacturer.
\16\ Colilert-18 [reg] is an optimized formulation of the Colilert [reg] for the determination of total coliforms and E. coli that provides results
within 18 h of incubation at 35 [deg]C rather than the 24 h required for the Colilert [reg] test and is recommended for marine water samples.
\17\ Descriptions of the Colilert [reg], Colilert-18 [reg], Quanti-Tray [reg], and Quanti-Tray [reg]/2000 may be obtained from IDEXX Laboratories, Inc.,
One IDEXX Drive, Westbrook, Maine 04092.
\18\ A description of the mColiBlue24'' test, Total Coliforms and E. coli, is available from Hach Company, 100 Dayton Ave., Ames, IA 50010.
\19\ Subject total coliform positive samples determined by 9222B or other membrane filter procedure to 9222G using NA-MUG media.
\20\ USEPA. 2002. Method 1103.1: Escherichia coli (E. coli) In Water By Membrane Filtration Using membrane-Thermotolerant Escherichia coli Agar (mTEC).
U.S. Environmental Protection Agency, Office of Water, Washington D.C. EPA-821-R-02-020.
\21\ USEPA. 2002. Method 1603: Escherichia coli (E. coli) In Water By Membrane Filtration Using Modified membrane-Thermotolerant Escherichia coli Agar (
modified mTEC). U.S. Environmental Protection Agency, Office of Water, Washington D.C. EPA-821-R-02-023.
\22\ Preparation and use of MI agar with a standard membrane filter procedure is set forth in the article, Brenner et al. 1993. ``New Medium for the
Simultaneous Detection of Total Coliform and Escherichia coli in Water.'' Appl. Environ. Microbiol. 59:3534-3544 and in USEPA. 2002. Method 1604:
Total Coliforms and Escherichia coli (E. coli) in Water by Membrane Filtration by Using a Simultaneous Detection Technique (MI Medium). U.S.
Environmental Protection Agency, Office of Water, Washington DC. EPA 821-R-02-024.
\23\ A description of the Enterolert [reg] test may be obtained from IDEXX Laboratories, Inc., One IDEXX Drive, Westbrook, Maine 04092.
\24\ USEPA. 2002. Method 1106.1: Enterococci In Water By Membrane Filtration Using membrane-Enterococcus-Esculin Iron Agar (mE-EIA). U.S. Environmental
Protection Agency, Office of Water, Washington DC. EPA-821-R-02-021.
\25\ USEPA. 2002. Method 1600: Enterococci in Water by Membrane Filtration Using membrane-Enterococcus Indoxyl-[beta]-D-Glucoside Agar (mEI). U.S.
Environmental Protection Agency, Office of Water, Washington, DC. EPA-821-R-02-022.
\26\ Method 1622 uses filtration, concentration, immunomagnetic separation of oocysts from captured material, immunofluorescence assay to determine
concentrations, and confirmation through vital dye staining and differential interference contrast microscopy for the detection of Cryptosporidium.
USEPA. 2001. Method 1622: Cryptosporidium in Water by Filtration/IMS/FA. U.S. Environmental Protection Agency, Office of Water, Washington DC. EPA-821-
R-01-026.
\27\ Method 1623 uses filtration, concentration, immunomagnetic separation of oocysts and cysts from captured material, immunofluorescence assay to
determine concentrations, and confirmation through vital dye staining and differential interference contrast microscopy for the simultaneous detection
of Cryptosporidium and Giardia oocysts and cysts. USEPA. 2001. Method 1623. Cryptosporidium and Giardia in Water by Filtration/IMS/FA. U.S.
Environmental Protection Agency, Office of Water, Washington DC. EPA-821-R-01-025.
\28\ Recommended for enumeration of target organism in ambient water only.
[[Page 10]]
\29\ USEPA. October 2002. Methods for Measuring the Acute Toxicity of Effluents and Receiving Waters to Freshwater and Marine Organisms. Fifth Edition.
U.S. Environmental Protection Agency, Office of Water, Washington DC. EPA/821/R-02/012.
\30\ USEPA. October 2002. Short-term Methods for Estimating the Chronic Toxicity of Effluents and Receiving Waters to Freshwater Organisms. Fourth
Edition. U.S. Environmental Protection Agency, Office of Water, Washington DC. EPA/821/R-02/013.
\31\ USEPA. October 2002. Short-term Methods for Estimating the Chronic Toxicity of Effluents and Receiving Waters to Marine and Estuarine Organisms.
Third Edition. U.S. Environmental Protection Agency, Office of Water, Washington DC. EPA/821/R-02/014.
Table IB--List of Approved Inorganic Test Procedures
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
Reference (method number or page)
Parameter, units and method --------------------------------------------------------------------------------------------------------------------------------------------------------------
EPA 1, 35 Standard Methods [Edition(s)] ASTM USGS \2\ Other
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
1. Acidity, as CaCO3, mg/L:
Electrometric endpoint or 305.1......................... 2310 B(4a) [18th, 19th, 20th]. D1067-92...................... I-1020-85
phenolphthalein endpoint.
I-2030-85
2. Alkalinity, as CaCO3, mg/L:
Electrometric of Colorimetric 310.1......................... 2320 B [18th, 19th, 20th]..... D1067-92...................... I-1030-85..................... 973.43 \3\
titration to pH 4.5, manual .............................. .............................. .............................. ..............................
or automatic. 310.2......................... .............................. I-2030-85.....................
3. Aluminium--Total,\4\ mg/L;
Digestion \4\ followed by:
AA direct aspiration \36\.... 202.1......................... 3111 D [18th, 19th]........... .............................. I-3051-85
AA furnace................... 202.2......................... 3113 B [18th, 19th]...........
Inductively Coupled Plasma/ 200.7 \5\..................... 3120 B [18th, 19th, 20th]..... .............................. I-4471-97 \50\ .............................
Atomic Emission Spectrometry
(ICP/AES) \36\.
Direct Current Plasma (DCP) .............................. .............................. D4190-94...................... .............................. Note 34.
\36\.
Colorimetric (Eriochrome .............................. 3500-Al B [20th] and 3500-Al D
cyanine R). [18th, 19th].
4. Ammonia (as N), mg/L:
Manual, distillation (at pH 350.2......................... 4500-NH3 B [18th, 19th, 20th]. .............................. .............................. 973.49 \3\
9.5) \6\ followed by.
Nesslerization............... 350.2......................... 4500-NH3 C [18th]............. D1426-98(A)................... I-3520-85..................... 973.49 \3\
Titration.................... 350.2......................... 4500-NH3 C [19th, 20th] and
4500-NH3 E [18th].
Electrode.................... 350.3......................... 4500-NH3 D or E [19th, 20th] D1426-98(B)...................
and 4500-NH3 F or G [18th].
Automated phenate, or........ 350.1......................... 4500-NH3 G [19th, 20th] and .............................. I-4523-85 .............................
4500-NH3 H [18th].
Automated electrode.......... .............................. .............................. .............................. .............................. Note 7.
5. Antimony-Total,\4\ mg/L;
Digestion \4\ followed by:
AA direct aspiration \36\.... 204.1......................... 3111 B [18th, 19th]
AA furnace................... 204.2......................... 3113 B [18th, 19th]...........
ICP/AES \36\................. 200.7 \5\..................... 3120 B [18th, 19th, 20th].....
6. Arsenic-Total\4\ mg/L:
[[Page 11]]
Digestion \4\ followed by.... 206.5.........................
AA gaseous hydride........... 206.3......................... 3114 B 4.d [18th, 19th]....... D2972-97(B) I-3062-85
AA furnace................... 206.2......................... 3113 B [18th, 19th]........... D2972-97(C) I-4063-98 \49\ .............................
ICP/AES \36\ or.............. 200.7 \5\..................... 3120 B [18th, 19th, 20th].....
Colorimetric (SDDC).......... 206.4......................... 3500-As B [20th] and 3500-As C D2972-97(A) I-3060-85 .............................
[18th, 19th].
7. Barium-Total,\4\ mg/L;
Digestion \4\ followed by:
AA direct aspiration \14\.... 208.1......................... 3111 D [18th, 19th]........... .............................. I-3084-85 .............................
AA furnace................... 208.2......................... 3113 B [18th, 19th]........... D4382-95
ICP/AES \14\................. 200.7 \5\..................... 3120 B [18th, 19th, 20th].....
DCP \14\..................... .............................. .............................. .............................. .............................. Note 34.
8. Beryllium-Total,\4\ mg/L;
Digestion \4\ followed by:
AA direct aspiration......... 210.1......................... 3111 D [18th, 19th]........... D3645-93(88)(A)............... I-3095-85 .............................
AA furnace................... 210.2......................... 3113 B [18th, 19th]........... D3645-93(88)(B) .............................
ICP/AES...................... 200.7 \5\..................... 3120 B [18th, 19th, 20th]..... .............................. I-4471-97 \50\ .............................
DCP, or...................... .............................. .............................. D4190-94...................... .............................. Note 34.
Colorimetric (aluminon....... .............................. 3500-Be D [18th, 19th]........
9. Biochemical oxygen demand
(BOD5), mg/L:
Dissolved Oxygen Depletion... 405.1......................... 5210 B [18th, 19th, 20th]..... .............................. I-1578-78 \8\................. 973.44,\3\ p. 17 \9\
10. Boron \37\-Total, mg/L:
Colorimetric (curcumin)...... 212.3......................... 4500-B B [18th, 19th, 20th]... .............................. I-3112-85
ICP/AES, or.................. 200.7 \5\..................... 3120 B [18th, 19th, 20th]..... .............................. I-4471-97 \50\ .............................
DCP.......................... .............................. .............................. D4190-94...................... .............................. Note 34.
11. Bromide, mg/L:
Titrimetric.................. 320.1......................... .............................. D1246-95(C)................... I-1125-85..................... p. S44 \10\
12. Cadmium--Total,\4\ mg/L;
Digestion \4\ followed by:
AA direct aspiration \36\.... 213.1......................... 3111 B or C [18th, 19th]...... D3557-95 (A or B)............. I-3135-85 or I-3136-85........ 974.27,\3\ p. 37 \9\
AA furnace................... 213.2......................... 3113 B [18th, 19th]........... D3557-95(D)................... I-4138-89 \51\
ICP/AES \36\................. 200.7 \5\..................... 3120 B [18th, 19th, 20th]..... .............................. I-1472-85 or I-4471-97 \50\
DCP \36\..................... .............................. .............................. D4190-94...................... .............................. Note 34.
Voltametry \11\, or.......... .............................. .............................. D3557-95(C)...................
Colorimetric (Dithizone)..... .............................. 3500-Cd D [18th, 19th]........
13. Calcium--Total,\4\ mg/L;
Digestion \4\ followed by:
AA direct aspiration......... 215.1......................... 3111 B [18th, 19th]........... D511-93(B).................... I-3152-85
ICP/AES...................... 200.7 \5\..................... 3120 B [18th, 19th, 20th]..... .............................. I-4471-97 \50\
DCP, or...................... .............................. .............................. .............................. .............................. Note 34.
Titrimetric (EDTA)........... 215.2......................... 3500-Ca B [20th] and 3500-Ca D D511-93(A)....................
[18th, 19th].
14. Carbonaceous biochemical
oxygen demand (CBOD 3), mg/
L\12\:
Dissolved Oxygen Depletion .............................. 5210 B [18th, 19th, 20th].....
with nitrification inhibitor.
15. Chemical oxygen demand (COD), 410.1......................... 5220 C [18th, 19th, 20th]..... D1252-95(A)................... I-3560-85..................... 973.46,\3\ p. 17 \9\
mg/L; Titrimetric
or........................... 410.2......................... .............................. .............................. I-3562-85
[[Page 12]]
410.3.........................
Spectrophotometric, manual or 410.4......................... 5220 D [18th, 19th, 20th]..... D1252-95(B)................... I-3561-85..................... Notes 13, 14.
automatic.
16. Chloride, mg/L:
Titrimetric (silver nitrate) .............................. 4500-Cl-B [18th, 19th, 20th].. D512-89(B).................... I-1183-85
or.
(Mercuric nitrate)........... 325.3......................... 4500-Cl-C [18th, 19th, 20th].. D512-89(A).................... I-1184-85..................... 973.51 \3\
Colorimetric, manual or...... .............................. .............................. .............................. I-1187-85
Automated (Ferricyanide)..... 325.1 or 325.2................ 4500-Cl-E [18th, 19th, 20th].. .............................. I-2187-85
17. Chlorine--Total residual, mg/
L; Titrimetric:
Amperometric direct.......... 330.1......................... 4500-Cl D [18th, 19th, 20th].. D1253-86(92)..................
Iodometric direct............ 330.3......................... 4500-Cl B [18th, 19th, 20th]..
Back titration ether end- 330.2......................... 4500-Cl C [18th, 19th, 20th]..
point \15\ or.
DPD-FAS...................... 330.4......................... 4500-Cl F [18th, 19th, 20th]..
Spectrophotometric, DPD...... 330.5......................... 4500-Cl G [18th, 19th, 20th]..
Or Electrode................. .............................. .............................. .............................. .............................. Note 16.
18. Chromium VI dissolved, mg/L;
0.45 micron filtration followed
by:
AA chelation-extraction or... 218.4......................... 3111 C [18th, 19th]........... .............................. I-1232-85
Colorimetric .............................. 3500-Cr B [20th] and 3500-Cr D D1687-92(A)................... I-1230-85
(Diphenylcarbazide). [18th, 19th].
19. Chromium-Total,\4\ mg/L;
Digestion \4\ followed by:
AA direct aspiration \36\.... 218.1......................... 3111 B [18th, 19th]........... D1687-92(B)................... I-3236-85..................... 974.27 \3\
AA chelation-extraction...... 218.3......................... 3111 C [18th, 19th]...........
AA furnace................... 218.2......................... 3113 B [18th, 19th]........... D1687-92(C)................... I-3233-93 \46\................
ICP/AES \36\................. 200.7 \5\..................... 3120 B [18th, 19th, 20th].....
DCP \36\ or.................. .............................. .............................. D4190-94...................... .............................. Note 34.
Colorimetric .............................. 3500-Cr B [20th] and 3500-Cr D
(Diphenylcarbazide). [18th, 19th].
20. Cobalt--Total,\4\ mg/L;
Digestion \4\ followed by:
AA direct aspiration......... 219.1......................... 3111 B or C [18th, 19th]...... D3558-94(A or B).............. I-3239-85..................... p. 37 \9\
AA furnace................... 219.2......................... 3113 B [18th, 19th]........... D3558-94(C)................... I-4243-89 \51\................
ICP/AES...................... 200.7 \5\..................... 3120 B [18th, 19th, 20th]..... .............................. I-4471-97 \50\................
[[Page 13]]
DCP.......................... .............................. .............................. D4190-94...................... .............................. Note 34.
21. Color platinum cobalt units
or dominant wavelength, hue,
luminance purity:
Colorimetric (ADMI), or......
(Platinum cobalt), or........ 110.1......................... 2120 E [18th, 19th, 20th]..... .............................. .............................. Note 18.
Spectrophotometric........... 110.2......................... 2120 B [18th, 19th, 20th]..... .............................. I-1250-85
110.3......................... 2120 C [18th, 19th, 20th].....
22. Copper--Total,4 mg/L;
Digestion 4 followed by:
AA direct aspiration 36...... 220.1......................... 3111 B or C [18th, 19th]...... D1688-95(A or B).............. I-3270-85 or I-3271-85........ 974.27 3 p. 37 9
AA furnace................... 220.2......................... 3113 B [18th, 19th]........... D1688-95(C)................... I-4274-89 51
ICP/AES 36................... 200.7 5....................... 3120 B [18th, 19th, 20th]..... .............................. I--4471--97 50
DCP 36 or.................... .............................. .............................. D4190-94...................... .............................. Note 34.
Colorimetric (Neocuproine) or .............................. 3500-Cu B [20th] and 3500-Cu D
[18th, 19th].
(Bicinchoninate)............. .............................. 3500-Cu C [20th] and 3500-As B .............................. .............................. Note 19.
[18th, 19th].
23. Cyanide--Total, mg/L:
Manual distillation with .............................. 4500-CN C [18th, 19th, 20th].. D2036-98(A)
MgCl2 followed by..
Titrimetric, or.............. .............................. 4500-CN D [18th, 19th, 20th].. .............................. .............................. p. 22 9
Spectrophotometric, manual or 335.2 31...................... 4500-CN E [18th, 19th, 20th].. D2036-98(A)................... I-3300-85
Automated 20................. 335.3 31...................... .............................. .............................. I-4302-85
24. Available Cyanide, mg/L:
Manual distillation with 335.1......................... 4500-CN G [18th, 19th, 20th].. D2036-98(B)
MgCl2 followed by
titrimetric or
Spectrophotometric.
Flow injection and ligand .............................. .............................. .............................. .............................. OIA-1677 44
exchange, followed by
amperometry.
25. Fluoride--Total, mg/L:
Manual distillation 6 .............................. 4500-F B [18th, 19th, 20th]...
followed by.
Electrode, manual or......... 340.2......................... 4500-F C [18th, 19th, 20th]... D1179-93(B)
Automated.................... .............................. .............................. .............................. I-4327-85 .............................
Colorimetric (SPADNS)........ 340.1......................... 4500-F D [18th, 19th, 20th]... D1179-93(A)
Or Automated complexone...... 340.3......................... 4500-F E [18th, 19th, 20th]...
26. Gold--Total,4 mg/L; Digestion
4 followed by:
AA direct aspiration......... 231.1......................... 3111 B [18th, 19th]...........
AA furnace, or............... 231.2
DCP.......................... .............................. .............................. .............................. .............................. Note 34.
27. Hardness--Total, as CaCO3, mg/
L:
Automated colorimetric,...... 130.1
[[Page 14]]
Titrimetric (EDTA), or Ca 130.2......................... 2340 B or C [18th, 19th, 20th] D1126-86(92).................. I-1338-85..................... 973.52B 3
plus Mg as their carbonates,
by inductively coupled
plasma or AA direct
aspiration (See Parameters
13 and 33).
28. Hydrogen ion (pH), pH units:
Electrometric measurement, or 150.1......................... 4500-H+ B [18th, 19th, 20th].. D1293-84 (90)(A or B)......... I-1586-85..................... 973.41 3
Automated electrode.......... .............................. .............................. .............................. I-2587-85..................... Note 21.
29. Iridium--Total,4 mg/L;
Digestion 4 followed by:
AA direct aspiration or...... 235.1......................... 3111 B [18th, 19th]...........
AA furnace................... 235.2
30. Iron--Total,4 mg/L; Digestion
4 followed by:
AA direct aspiration 36...... 236.1......................... 3111 B or C [18th, 19th]...... D1068-96(A or B).............. I-3381-85..................... 974.27 3
AA furnace................... 236.2......................... 3113 B [18th, 19th]........... D1068-96(C)
ICP/AES 36................... 200.7 5....................... 3120 B [18th, 19th, 20th]..... .............................. I-4471-97 50
DCP 36 or.................... .............................. .............................. D4190-94...................... .............................. Note 34.
Colorimetric (Phenanthroline) .............................. 3500-Fe B [20th] and 3500-Fe D D1068-96(D)................... .............................. Note 22.
[18th, 19th].
31. Kjeldahl Nitrogen--Total, (as
N), mg/L:
Digestion and distillation 351.3......................... 4500-Norg B or C and 4500-NH3 D3590-89(A)
followed by. B [18th, 19th, 20th].
Titration.................... 351.3......................... .............................. D3590-89(A)................... .............................. 973.48 \3\
Nesslerization............... 351.3......................... 4500-NH3 C [18th]............. D3590-89(A)...................
Electrode.................... 351.3......................... 4500-NH3 C [19th, 20th] and
4500-NH3 E [18th].
Automated phenate colorimetric... 351.1......................... .............................. .............................. I-4551-78\8\
Semi-automated block digestor 351.2......................... .............................. D3590-89(B)................... I-4515-91 \45\................
colorimetric.
Manual or block digestor 351.4......................... .............................. D3590-89(A)
potentiometric.
Block digester, followed by Auto .............................. .............................. .............................. .............................. Note 39.
distillation and Titration, or.
Nesslerization, or............... .............................. .............................. .............................. .............................. Note 40.
Flow injection gas diffusion..... .............................. .............................. .............................. .............................. Note 41.
32. Lead--Total,\4\ mg/L;
Digestion \4\ followed by:
AA direct aspiration \36\.... 239.1......................... 3111 B or C [18th, 19th]...... D3559-96(A or B).............. I-3399-85..................... 974.27 \3\
[[Page 15]]
AA furnace................... 239.2......................... 3113 B [18th, 19th]........... D3559-96(D)................... I-4403-89 \51\
ICP/AES \36\................. 200.7 \5\..................... 3120 B [18th, 19th, 20th]..... .............................. I-4471-97 \50\
DCP 36....................... .............................. .............................. D4190-94...................... .............................. Note 34.
Voltametry \11\ or........... D3559-96(C)...................
Colorimetric (Dithizone)..... 3500-Pb B [ 20th] and 3500-Pb
D [18th, 19th].
33. Magnesium--Total,\4\ mg/L;
Digestion \4\ followed by:
AA direct aspiration......... 242.1......................... 3111 B [18th, 19th]........... D511-93(B).................... I-3447-85..................... 974.27 \3\
ICP/AES...................... 200.7 \5\..................... 3120 B [18th, 19th, 20th]..... .............................. I-4471-97 \50\
DCP or....................... .............................. .............................. .............................. .............................. Note 34.
Gravimetric.................. .............................. 3500-Mg D [18th, 19th]........
34. Manganese-Total,\4\ mg/L;
Digestion \4\ followed by:
AA direct aspiration \36\.... 243.1......................... 3111 B [18th, 19th]........... D858-95(A or B)............... I-3454-85..................... 974.27 \3\
AA furnace................... 243.2......................... 3113 B [18th, 19th]........... D858-95(C)
ICP/AES \36\................. 200.7 \5\..................... 3120 B [18th, 19th, 20th]..... .............................. I-4471-97 \50\
DCP \36\, or................. .............................. .............................. D4190-94...................... .............................. Note 34
Colorimetric (Persulfate), or .............................. 3500-Mn B [20th] and 3500-Mn D .............................. .............................. 920.203 \3\
[18th, 19th].
(Periodate).................. .............................. .............................. .............................. .............................. Note 23.
35. Mercury--Total,\4\ mg/L:
Cold vapor, manual or........ 245.1......................... 3112 B [18th, 19th]........... D3223-91...................... I-3462-85..................... 977.22 \3\
Automated.................... 245.2
Oxidation, purge and trap, 1631E \43\
and cold vapor atomic
fluorescence spectrometry
(ng/L).
36. Molybdenum--Total \4\, mg/L;
Digestion \4\ followed by:
AA direct aspiration......... 246.1......................... 3111 D [18th, 19th]........... .............................. I-3490-85
AA furnace................... 246.2......................... 3113 B [18th, 19th]........... .............................. I-3492-96 \47\
ICP/AES...................... 200.7 \5\..................... 3120 B [18th, 19th, 20th]..... .............................. I-4471-97 \50\
DCP.......................... .............................. .............................. .............................. .............................. Note 34.
37. Nickel--Total,\4\ mg/L;
Digestion \4\ followed by:
AA direct aspiration \36\.... 249.1......................... 3111 B or C [18th, 19th]...... D1886-90(A or B).............. I-3499-85.....................
AA furnace................... 249.2......................... 3113 B [18th, 19th]........... D1886-90(C)................... I-4503-89 \51\................
ICP/AES \36\................. 200.7 \5\..................... 3120 B [18th, 19th, 20th]..... .............................. I-4471-97 \50\................
DCP \36\, or................. .............................. .............................. D4190-94...................... .............................. Note 34.
Colorimetric (heptoxime)..... .............................. 3500-Ni D [17th]..............
38. Nitrate (as N), mg/L:
Colorimetric (Brucine 352.1......................... .............................. .............................. .............................. 973.50,\3\ 419D,\17\ p. 28
sulfate), orNitrate-nitrite \9\
N minus Nitrite N (See
parameters 39 and 40).
39. Nitrate-nitrite (as N),
mg/L:
Cadmium reduction, Manual or. 353.3......................... 4500-NO3-E [18th, 19th, 20th]. D3867-99(B)...................
[[Page 16]]
Automated, or................ 353.2......................... 4500-NO3-F [18th, 19th, 20th]. D3867-99(A)................... I-4545-85.....................
Automated hydrazine.......... 353.1......................... 4500-NO3-H [18th, 19th, 20th].
40. Nitrite (as N), mg/L;
Spectrophotometric:
Manual or.................... 354.1......................... 4500-NO2-B [18th, 19th, 20th]. .............................. .............................. Note 25.
Automated (Diazotization).... .............................. .............................. .............................. I-4540-85.....................
41. Oil and grease--Total
recoverable, mg/L:
Gravimetric (extraction)..... 413.1......................... 5520B [18th, 19th, 20th] \38\.
Oil and grease and non-polar 1664A \42\.................... 5520B [18th, 19th, 20th] \38\.
material, mg/L: Hexane
extractable material (HEM):
n-Hexane extraction and
gravimetry.
Silica gel treated HEM (SGT- 1664A \42\....................
HEM):Silica gel treatment
and gravimetry.
42. Organic carbon--Total (TOC),
mg/L:
Combustion or oxidation...... 415.1......................... 5310 B, C, or D [18th, 19th, D2579-93 (A or B)............. .............................. 973.47,\3\ p. 14 \24\
20th].
43. Organic nitrogen (as N), mg/
L:
Total Kjeldahl N (Parameter
31) minus ammonia N
(Parameter 4).
44. Orthophosphate (as P), mg/L;
Ascorbic acid method:
Automated, or................ 365.1......................... 4500-P F [18th, 19th, 20th]... .............................. I-4601-85..................... 973.56 \3\
Manual single reagent........ 365.2......................... 4500-P E [18th, 19th, 20th]... D515-88(A).................... .............................. 973.55 \3\
Manual two reagent........... 365.3.........................
45. Osmium--Total \4\, mg/L;
Digestion \4\ followed by:
AA direct aspiration, or..... 252.1......................... 3111 D [18th, 19th]...........
AA furnace................... 252.2.........................
46. Oxygen, dissolved,mg/L:
Winkler (Azide modification), 360.2......................... 4500-O C [18th, 19th, 20th]... D888-92(A).................... I-1575-78 \8\................. 973.45B \3\
or.
Electrode.................... 360.1......................... 4500-O G [18th, 19th, 20th]... D888-92(B).................... I-1576-78 \8\.................
[[Page 17]]
47. Palladium--Total,\4\ mg/L;
Digestion \4\ followed by:
AA direct aspiration, or..... 253.1......................... 3111 B [18th, 19th]........... .............................. .............................. p. S27 \10\
AA furnace................... 253.2......................... .............................. .............................. .............................. p. S28 \10\
DCP.......................... .............................. .............................. .............................. .............................. Note 34.
48. Phenols, mg/L:
Manual distillation \26\..... 420.1......................... .............................. .............................. .............................. Note 27.
Followed by:.................
Colorimetric (4AAP) 420.1......................... .............................. .............................. .............................. Note 27.
manual, or.
Automated \19\........... 420.2.........................
49. Phosphorus (elemental), mg/L:
Gas-liquid chromatography.... .............................. .............................. .............................. .............................. Note 28.
50. Phosphorus--Total, mg/L:
Persulfate digestion followed 365.2......................... 4500-P B, 5 [18th, 19th, 20th] .............................. .............................. 973.55 \3\
by.
Manual or.................... 365.2 or 365.3................ 4500-P E [18th, 19th, 20th]... D515-88(A)
Automated ascorbic acid 365.1......................... 4500-P F [18th, 19th, 20th]... .............................. I-4600-85..................... 973.56 \3\
reduction.
Semi-automated block digestor 365.4......................... .............................. D515-88(B).................... I-4610-91 \48\................
51. Platinum--Total,\4\ mg/L:
Digestion \4\ followed by:
AA direct aspiration......... 255.1......................... 3111 B [18th, 19th]...........
AA furnace................... 255.2.........................
DCP.......................... .............................. .............................. .............................. .............................. Note 34
52. Potassium--Total,\4\ mg/L:
Digestion \4\ followed by:
AA direct aspiration......... 258.1......................... 3111 B [18th, 19th]........... .............................. I-3630-85..................... 973.53 \3\
ICP/AES...................... 200.7 \5\..................... 3120 B [18th, 19th, 20th].....
Flame photometric, or........ .............................. 3500-K B [20th] and 3500-K D
[18th, 19th].
Colorimetric................. .............................. .............................. .............................. .............................. 317 B \17\
53. Residue--Total, mg/L:
Gravimetric, 103-105[deg].... 160.3......................... 2540 B [18th, 19th, 20th]..... .............................. I-3750-85.....................
54. Residue--filterable, mg/L:
Gravimetric, 180[deg]........ 160.1......................... 2540 C [18th, 19th, 20th]..... .............................. I-1750-85.....................
55. Residue--nonfilterable (TSS),
mg/L:
Gravimetric, 103-105[deg] 160.2......................... 2540 D [18th, 19th, 20th]..... .............................. I-3765-85.....................
post washing of residue.
56. Residue--settleable, mg/L:
Volumetric, (Imhoff cone), or 160.5......................... 2540 F [18th, 19th, 20th].....
gravimetric.
57. Residue--Volatile, mg/L:
Gravimetric, 550[deg]........ 160.4......................... .............................. .............................. I-3753-85.....................
58. Rhodium-Total,\4\ mg/L;
Digestion \4\ followed by:
AA direct aspiration, or..... 265.1......................... 3111 B [18th, 19th]...........
[[Page 18]]
AA furnace................... 265.2.........................
59. Ruthenium--Total,\4\ mg/L;
Digestion \4\ followed by:
AA direct aspiration, or..... 267.1......................... 3111 B [18th, 19th]...........
AA furnace................... 267.2.........................
60. Selenium--Total,\4\ mg/L;
Digestion \4\ followed by:
AA furnace................... 270.2......................... 3113 B [18th, 19th]........... D3859-98(B)................... I-4668-98 \49\................
ICP/AES,\36\ or.............. 200.7 \5\..................... 3120 B [18th, 19th, 20th].....
AA gaseous hydride........... .............................. 3114 B [18th, 19th]........... D3859-98(A)................... I-3667-85.....................
61. Silica \37\--Dissolved, mg/L;
0.45 micron filtration followed
by:
Colorimetric, Manual or...... 370.1......................... 4500-SiO2 C [20th] and 4500-Si D859-94....................... I-1700-85.....................
D [18th, 19th].
Automated (Molybdosilicate), .............................. .............................. .............................. I-2700-85.....................
or.
ICP.......................... 200.7 \5\..................... 3120 B [18th, 19th, 20th]..... .............................. I-4471-97 \50\................
62. Silver--Total,\4\ mg/L:
Digestion 4 29 followed by:
AA direct aspiration......... 272.1......................... 3111 B or C [18th, 19th]...... .............................. I-3720-85..................... 974.27,\3\ p. 37 \9\
AA furnace................... 272.2......................... 3113 B [18th, 19th]........... .............................. I-4724-89 \51\
ICP/AES...................... 200.7 \5\..................... 3120 B [18th, 19th, 20th]..... .............................. I-4471-97 \50\
DCP.......................... .............................. .............................. .............................. .............................. Note 34.
63. Sodium--Total,\4\ mg/L;
Digestion \4\ followed by:
AA direct aspiration......... 273.1......................... 3111 B [18th, 19th]........... .............................. I-3735-85..................... 973.54 \3\
ICP/AES...................... 200.7 \5\..................... 3120 B [18th, 19th, 20th]..... .............................. I-4471-97 \50\
DCP, or...................... .............................. .............................. .............................. .............................. Note 34.
Flame photometric............ .............................. 3500 Na B [20th] and 3500 Na D
[18th, 19th].
64. Specific conductance,
micromhos/cm at 25 [deg]C:
Wheatstone bridge............ 120.1......................... 2510 B [18th, 19th, 20th]..... D1125-95(A)................... I-2781-85..................... 973.40 \3\
65. Sulfate (as SO4), mg/L:
Automated colorimetric 375.1.........................
(barium chloranilate).
Gravimetric.................. 375.3......................... 4500-SO4-\2\C or D [18th, .............................. .............................. 925.54 \3\
19th, 20th].
Turbidimetric................ 375.4......................... .............................. D516-90....................... .............................. 426C \30\
66. Sulfide (as S), mg/L:
Titrimetric (iodine), or..... 376.1......................... 4500-S-\2\F [19th, 20th] or .............................. I-3840-85.....................
4500-S-\2\E [18th].
[[Page 19]]
Colorimetric (methylene blue) 376.2......................... 4500-S-\2\D [18th, 19th, 20th]
67. Sulfite (as SO3), mg/L:
Titrimetric (iodine-iodate).. 377.1......................... 4500-SO3-\2\B [18th, 19th,
20th].
68. Surfactants, mg/L:
Colorimetric (methylene blue) 425.1......................... 5540 C [18th, 19th, 20th]..... D2330-88......................
69. Temperature, [deg]C:
Thermometric................. 170.1......................... 2550 B [18th, 19th, 20th]..... .............................. .............................. Note 32.
70. Thallium--Total,\4\ mg/L;
Digestion \4\ followed by:
AA direct aspiration......... 279.1......................... 3111 B [18th, 19th]...........
AA furnace................... 279.2.........................
ICP/AES...................... 200.7 \5\..................... 3120 B [18th, 19th, 20th].....
71. Tin--Total,\4\ mg/L;
Digestion \4\ followed by:
AA direct aspiration......... 282.1......................... 3111 B [18th, 19th]........... .............................. I-3850-78 \8\.................
AA furnace, or............... 282.2......................... 3113 B [18th, 19th]...........
ICP/AES...................... 200.7 \5\.....................
72. Titanium--Total,\4\ mg/L;
Digestion \4\ followed by:
AA direct aspiration......... 283.1......................... 3111 D [18th, 19th]...........
AA furnace................... 283.2.........................
DCP.......................... .............................. .............................. .............................. .............................. Note 34.
73. Turbidity, NTU:
Nephelometric................ 180.1......................... 2130 B [18th, 19th, 20th]..... D1889-94(A)................... I-3860-85.....................
74. Vanadium--Total,\4\ mg/L;
Digestion \4\ followed by:
AA direct aspiration......... 286.1......................... 3111 D [18th, 19th]...........
AA furnace................... 286.2......................... .............................. D3373-93......................
ICP/AES...................... 200.7 \5\..................... 3120 B [18th, 19th, 20th]..... .............................. I-4471-97 \50\................
DCP, or...................... .............................. .............................. D4190-94...................... .............................. Note 34.
Colorimetric (Gallic Acid)... .............................. 3500-V B [20th] and 3500-V D
[18th, 19th].
75. Zinc--Total,\4\ mg/L;
Digestion \4\ followed by:
AA direct aspiration \36\.... 289.1......................... 3111 B or C [18th, 19th]...... D1691-95(A or B).............. I-3900-85..................... 974.27,\3\ p. 37 \9\
AA furnace................... 289.2.........................
ICP/AES \36\................. 200.7 \5\..................... 3120 B [18th, 19th, 20th]..... .............................. I-4471-97 \50\................
DCP,\36\ or.................. .............................. .............................. D4190-94...................... .............................. Note 34.
Colorimetric (Dithizone) or.. .............................. 3500-Zn E [18th, 19th]........
(Zincon)..................... .............................. 3500-Zn B [20th] and 3500-Zn F .............................. .............................. Note 33.
[18th, 19th].
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
Table 1B Notes:
\1\ ``Methods for Chemical Analysis of Water and Wastes,'' Environmental Protection Agency, Environmental Monitoring Systems Laboratory--Cincinnati (EMSL-CI), EPA-600/4-79-020, Revised March
1983 and 1979 where applicable.
\2\ Fishman, M.J., et al. ``Methods for Analysis of Inorganic Substances in Water and Fluvial Sediments, ''U.S. Department of the Interior, Techniques of Water-Resource Investigations of the
U.S. Geological Survey, Denver, CO, Revised 1989, unless otherwise stated.
\3\ ``Official Methods of Analysis of the Association of Official Analytical Chemists,'' methods manual, 15th ed. (1990).
[[Page 20]]
\4\ For the determination of total metals the sample is not filtered before processing. A digestion procedure is required to solubilize suspended material and to destroy possible organic-metal
complexes. Two digestion procedures are given in ``Methods for Chemical Analysis of Water and Wastes, 1979 and 1983''. One (Section 4.1.3), is a vigorous digestion using nitric acid. A less
vigorous digestion using nitric and hydrochloric acids (Section 4.1.4) is preferred; however, the analyst should be cautioned that this mild digestion may not suffice for all samples types.
Particularly, if a colorimetric procedure is to be employed, it is necessary to ensure that all organo-metallic bonds be broken so that the metal is in a reactive state. In those situations,
the vigorous digestion is to be preferred making certain that at no time does the sample go to dryness. Samples containing large amounts of organic materials may also benefit by this
vigorous digestion, however, vigorous digestion with concentrated nitric acid will convert antimony and tin to insoluble oxides and render them unavailable for analysis. Use of ICP/AES as
well as determinations for certain elements such as antimony, arsenic, the noble metals, mercury, selenium, silver, tin, and titanium require a modified sample digestion procedure and in all
cases the method write-up should be consulted for specific instructions and/or cautions.
Note to Table 1B Note 4: If the digestion procedure for direct aspiration AA included in one of the other approved references is different than the above, the EPA procedure must be used.
Dissolved metals are defined as those constituents which will pass through a 0.45 micron membrane filter. Following filtration of the sample, the referenced procedure for total metals must
be followed. Sample digestion of the filtrate for dissolved metals (or digestion of the original sample solution for total metals) may be omitted for AA (direct aspiration or graphite
furnace) and ICP analyses, provided the sample solution to be analyzed meets the following criteria:
a. has a low COD (<20)
b. is visibly transparent with a turbidity measurement of 1 NTU or less
c. is colorless with no perceptible odor, and
d. is of one liquid phase and free of particulate or suspended matter following acidification.
\5\ The full text of Method 200.7, ``Inductively Coupled Plasma Atomic Emission Spectrometric Method for Trace Element Analysis of Water and Wastes,'' is given at Appendix C of this Part 136.
\6\ Manual distillation is not required if comparability data on representative effluent samples are on company file to show that this preliminary distillation step is not necessary: however,
manual distillation will be required to resolve any controversies.
\7\ Ammonia, Automated Electrode Method, Industrial Method Number 379-75 WE, dated February 19, 1976, Bran & Luebbe (Technicon) Auto Analyzer II, Bran & Luebbe Analyzing Technologies, Inc.,
Elmsford, NY 10523.
\8\ The approved method is that cited in ``Methods for Determination of Inorganic Substances in Water and Fluvial Sediments'', USGS TWRI, Book 5, Chapter A1 (1979).
\9\ American National Standard on Photographic Processing Effluents, Apr. 2, 1975. Available from ANSI, 25 West 43rd Street, New York, NY 10036.
\10\ ``Selected Analytical Methods Approved and Cited by the United States Environmental Protection Agency'', Supplement to the Fifteenth Edition of Standard Methods for the Examination of
Water and Wastewater (1981).
\11\ The use of normal and differential pulse voltage ramps to increase sensitivity and resolution is acceptable.
\12\ Carbonaceous biochemical oxygen demand (CBOD5) must not be confused with the traditional BOD5 test method which measures ``total BOD''. The addition of the nitrification inhibitor is not
a procedural option, but must be included to report the CBOD5 parameter. A discharger whose permit requires reporting the traditional BOD5 may not use a nitrification inhibitor in the
procedure for reporting the results. Only when a discharger's permit specifically states CBOD5 is required can the permittee report data using a nitrification inhibitor.
\13\ OIC Chemical Oxygen Demand Method, Oceanography International Corporation, 1978, 512 West Loop, PO Box 2980, College Station, TX 77840.
\14\ Chemical Oxygen Demand, Method 8000, Hach Handbook of Water Analysis, 1979, Hach Chemical Company, PO Box 389, Loveland, CO 80537.
\15\ The back titration method will be used to resolve controversy.
\16\ Orion Research Instruction Manual, Residual Chlorine Electrode Model 97-70, 1977, Orion Research Incorporated, 840 Memorial Drive, Cambridge, MA 02138. The calibration graph for the Orion
residual chlorine method must be derived using a reagent blank and three standard solutions, containing 0.2, 1.0, and 5.0 mL 0.00281 N potassium iodate/100 mL solution, respectively.
\17\ The approved method is that cited in Standard Methods for the Examination of Water and Wastewater, 14th Edition, 1976.
\18\ National Council of the Paper Industry for Air and Stream Improvement, Inc. Technical Bulletin 253, December 1971.
\19\ Copper, Biocinchoinate Method, Method 8506, Hach Handbook of Water Analysis, 1979, Hach Chemical Company, PO Box 389, Loveland, CO 80537.
\20\ After the manual distillation is completed, the autoanalyzer manifolds in EPA Methods 335.3 (cyanide) or 420.2 (phenols) are simplified by connecting the re-sample line directly to the
sampler. When using the manifold setup shown in Method 335.3, the buffer 6.2 should be replaced with the buffer 7.6 found in Method 335.2.
\21\ Hydrogen ion (pH) Automated Electrode Method, Industrial Method Number 378-75WA, October 1976, Bran & Luebbe (Technicon) Autoanalyzer II. Bran & Luebbe Analyzing Technologies, Inc.,
Elmsford, NY 10523.
\22\ Iron, 1,10-Phenanthroline Method, Method 8008, 1980, Hach Chemical Company, PO Box 389, Loveland, CO 80537.
\23\ Manganese, Periodate Oxidation Method, Method 8034, Hach Handbook of Wastewater Analysis, 1979, pages 2-113 and 2-117, Hach Chemical Company, Loveland, CO 80537.
\24\ Wershaw, R.L., et al, ``Methods for Analysis of Organic Substances in Water,'' Techniques of Water-Resources Investigation of the U.S. Geological Survey, Book 5, Chapter A3, (1972 Revised
1987) p. 14.
\25\ Nitrogen, Nitrite, Method 8507, Hach Chemical Company, PO Box 389, Loveland, CO 80537.
\26\ Just prior to distillation, adjust the sulfuric-acid-preserved sample to pH 4 with 1 + 9 NaOH.
\27\ The approved method is cited in Standard Methods for the Examination of Water and Wastewater, 14th Edition. The colorimetric reaction is conducted at a pH of 10.00.2. The approved methods are given on pp 576-81 of the 14th Edition: Method 510A for distillation, Method 510B for the manual colorimetric procedure, or Method 510C for the manual
spectrometric procedure.
\28\ R.F. Addison and R.G. Ackman, ``Direct Determination of Elemental Phosphorus by Gas-Liquid Chromatography,'' Journal of Chromatography, Vol. 47, No. 3, pp. 421-426, 1970.
\29\ Approved methods for the analysis of silver in industrial wastewaters at concentrations of 1 mg/L and above are inadequate where silver exists as an inorganic halide. Silver halides such
as the bromide and chloride are relatively insoluble in reagents such as nitric acid but are readily soluble in an aqueous buffer of sodium thiosulfate and sodium hydroxide to pH of 12.
Therefore, for levels of silver above 1 mg/L, 20 mL of sample should be diluted to 100 mL by adding 40 mL each of 2 M Na2S2O3 and NaOH. Standards should be prepared in the same manner. For
levels of silver below 1 mg/L the approved method is satisfactory.
\30\ The approved method is that cited in Standard Methods for the Examination of Water and Wastewater, 15th Edition.
[[Page 21]]
\31\ EPA Methods 335.2 and 335.3 require the NaOH absorber solution final concentration to be adjusted to 0.25 N before colorimetric determination of total cyanide.
\32\ Stevens, H.H., Ficke, J.F., and Smoot, G.F., ``Water Temperature--Influential Factors, Field Measurement and Data Presentation,'' Techniques of Water-Resources Investigations of the U.S.
Geological Survey, Book 1, Chapter D1, 1975.
\33\ Zinc, Zincon Method, Method 8009, Hach Handbook of Water Analysis, 1979, pages 2-231 and 2-333, Hach Chemical Company, Loveland, CO 80537.
\34\ ``Direct Current Plasma (DCP) Optical Emission Spectrometric Method for Trace Elemental Analysis of Water and Wastes, Method AES0029,'' 1986--Revised 1991, Thermo Jarrell Ash Corporation,
27 Forge Parkway, Franklin, MA 02038.
\35\ Precision and recovery statements for the atomic absorption direct aspiration and graphite furnace methods, and for the spectrophotometric SDDC method for arsenic are provided in Appendix
D of this part titled, ``Precision and Recovery Statements for Methods for Measuring Metals''.
\36\ ``Closed Vessel Microwave Digestion of Wastewater Samples for Determination of Metals'', CEM Corporation, PO Box 200, Matthews, NC 28106-0200, April 16, 1992. Available from the CEM
Corporation.
\37\ When determining boron and silica, only plastic, PTFE, or quartz laboratory ware may be used from start until completion of analysis.
\38\ Only use Trichlorotrifluorethane (1,1,2-trichloro-1,2,2-trifluoroethane; CFC-113) extraction solvent when determining Total Recoverable Oil and Grease (analogous to EPA Method 413.1).
Only use n-hexane extraction solvent when determining Hexane Extractable Material (analogous to EPA Method 1664A). Use of other extraction solvents is strictly prohibited.
\39\ Nitrogen, Total Kjeldahl, Method PAI-DK01 (Block Digestion, Steam Distillation, Titrimetric Detection), revised 12/22/94, OI Analytical/ALPKEM, PO Box 9010, College Station, TX 77842.
\40\ Nitrogen, Total Kjeldahl, Method PAI-DK02 (Block Digestion, Steam Distillation, Colorimetric Detection), revised 12/22/94, OI Analytical/ALPKEM, PO Box 9010, College Station, TX 77842.
\41\ Nitrogen, Total Kjeldahl, Method PAI-DK03 (Block Digestion, Automated FIA Gas Diffusion), revised 12/22/94, OI Analytical/ALPKEM, PO Box 9010, College Station, TX 77842.
\42\ Method 1664, Revision A ``n-Hexane Extractable Material (HEM; Oil and Grease) and Silica Gel Treated n-Hexane Extractable Material (SGT-HEM; Non-polar Material) by Extraction and
Gravimetry'' EPA-821-R-98-002, February 1999. Available at NTIS, PB-121949, U.S. Department of Commerce, 5285 Port Royal, Springfield, Virginia 22161.
\43\ USEPA. 2002. Method 1631, Revision E, ``Mercury in Water by Oxidation, Purge and Trap, and Cold Vapor Atomic Fluorescence Spectrometry.'' September 2002. Office of Water, U.S.
Environmental Protection Agency (EPA-821-R-02-019). The application of clean techniques described in EPA's draft Method 1669: Sampling Ambient Water for Trace Metals at EPA Water Quality
Criteria Levels (EPA-821-R-96-011) are recommended to preclude contamination at low-level, trace metal determinations.
\44\ Available Cyanide, Method OIA-1677 (Available Cyanide by Flow Injection, Ligand Exchange, and Amperometry), ALPKEM, A Division of OI Analytical, PO Box 9010, College Station, TX 77842-
9010.
\45\ ``Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory--Determination of Ammonia Plus Organic Nitrogen by a Kjeldahl Digestion Method'', Open File Report
(OFR) 00-170.
\46\ ``Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory--Determination of Chromium in Water by Graphite Furnace Atomic Absorption Spectrophotometry'', Open
File Report (OFR) 93-449.
\47\ ''Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory--Determination of Molybdenum by Graphite Furnace Atomic Absorption Spectrophotometry'', Open File
Report (OFR) 97-198.
\48\ ''Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory--Determination of Total Phosphorus by Kjeldahl Digestion Method and an Automated Colorimetric Finish
That Includes Dialysis'' Open File Report (OFR) 92-146.
\49\ ``Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory--Determination of Arsenic and Selenium in Water and Sediment by Graphite Furnace-Atomic Absorption
Spectrometry'' Open File Report (OFR) 98-639.
\50\ ``Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory--Determination of Elements in Whole-water Digests Using Inductively Coupled Plasma-Optical Emission
Spectrometry and Inductively Coupled Plasma-Mass Spectrometry'', Open File Report (OFR) 98-165.
\51\ ``Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory--Determination of Inorganic and Organic Constituents in Water and Fluvial Sediment'', Open File
Report (OFR) 93-125.
Table IC--List of Approved Test Procedures for Non-Pesticide Organic Compounds
--------------------------------------------------------------------------------------------------------------------------------------------------------
EPA method number 2, 7 Other approved methods
------------------------------------------------------------------------------------------------------------------------
Parameter \1\ Standard Methods
GC GC/MS HPLC [Edition(s)] ASTM Other
--------------------------------------------------------------------------------------------------------------------------------------------------------
1. Acenaphthene................ 610................ 625, 1625B......... 610................ 6440 B [18th, D4657-92......... Note 9, p.27.
19th, 20th].
2. Acenaphthylene.............. 610................ 625, 1625B......... 610................ 6440 B, 6410 B D4657-92......... Note 9, p.27.
[18th, 19th,
20th].
3. Acrolein.................... 603................ 624\4\, 1624B...... .................
4. Acrylonitrile............... 603................ 624\4\, 1624B...... .................
5. Anthracene.................. 610................ 625, 1625B......... 610................ 6410 B, 6440 B D4657-92......... Note 9, p. 27.
[18th, 19th,
20th].
[[Page 22]]
6. Benzene..................... 602................ 624, 1624B......... ................... 6200 B [20th] and
6210 B [18th,
19th], 6200 C
[20th] and 6220 B
[18th, 19th].
7. Benzidine................... ................... 625\5\, 1625B...... 605................ .................. ................. Note 3, p.1.
8. Benzo(a)anthracene.......... 610................ 625, 1625B......... 610................ 6410 B, 6440 B D4657-92......... Note 9, p. 27.
[18th, 19th,
20th].
9. Benzo(a)pyrene.............. 610,............... 625, 1625B......... 610................ 6410 B, 6440 B D4657-92......... Note 9, p. 27.
[18th, 19th,
20th].
10. Benzo(b)fluoranthene....... 610................ 625, 1625B......... 610................ 6410 B, 6440 B D4657-92......... Note 9, p. 27.
[18th, 19th,
20th].
11. Benzo(g, h, i)perylene..... 610................ 625, 1625B......... 610................ 6410 B, 6440 B D4657-92......... Note 9, p. 27.
[18th, 19th,
20th].
12. Benzo(k)fluoranthene....... 610................ 625, 1625B......... 610................ 6410 B, 6440 B D4657-92......... Note 9, p. 27.
[18th, 19th,
20th].
13. Benzyl chloride............ ................... ................... ................... .................. ................. Note 3, p 130:
Note 6, p. S102.
14. Benzyl butyl phthalate..... 606................ 625, 1625B......... ................... 6410 B [18th, ................. Note 9, p. 27.
19th, 20th].
15. Bis(2-chloroethoxy) methane 611................ 625, 1625B......... ................... 6410 B [18th, ................. Note 9, p. 27.
19th, 20th].
16. Bis(2-chloroethyl) ether... 611................ 625, 1625B......... ................... 6410 B [18th, ................. Note 9, p. 27.
19th, 20th].
17. Bis(2-ethylhexyl) phthalate 606................ 625, 1625B......... ................... 6410 B [18th, ................. Note 9, p. 27.
19th, 20th].
18. Bromodichloromethane....... 601................ 624, 1624B......... ................... 6200 C [20th] and
6230 B [18th,
19th], 6200 B
[20th] and 6210 B
[18th, 19th].
19. Bromoform.................. 601................ 624, 1624B......... ................... 6200 C [20th] and
6230 B [18th,
19th], 6200 B
[20th] and 6210 B
[18th, 19th].
20. Bromomethane............... 601................ 624, 1624B......... ................... 6200 C [20th] and
6230 B [18th,
19th], 6200 B
[20th] and 6210 B
[18th, 19th].
21. 4-Bromophenylphenyl ether.. 611................ 625, 1625B......... ................... 6410 B [18th, ................. Note 9, p. 27.
19th, 20th].
22. Carbon tetrachloride....... 601................ 624, 1624B......... ................... 6200 C [20th] and ................. Note 3, p. 130.
6230 B [18th,
19th].
23. 4-Chloro-3-methylphenol.... 604................ 625,1625B.......... ................... 6410 B, 6420 B ................. Note 9, p. 27.
[18th, 19th,
20th].
[[Page 23]]
24. Chlorobenzene.............. 601, 602........... 624, 1624B......... ................... 6200 B [20th] and ................. Note 3, p. 130.
6210 B [18th,
19th], 6200 C
[20th] and 6220 B
[18th, 19th],
6200 C [20th] and
6230 B [18th,
19th],.
25. Chloroethane............... 601................ 624, 1624B......... ................... 6200 B [20th] and
6210 B [18th,
19th], 6200 C
[20th] and 6230 B
[18th, 19th].
26. 2-Chloroethylvinyl ether... 601................ 624, 1624B......... ................... 6200 B [20th] and .................
6210 B [18th,
19th], 6200 C
[20th] and 6230 B
[18th, 19th].
27. Chloroform:................ 601................ 624, 1624B......... ................... 6200 B [20th] and ................. Note 3, p 130.
6210 B [18th,
19th], 6200 C
[20th] and 6230 B
[18th, 19th].
28. Chloromethane.............. 601................ 624, 1624B......... ................... 6200 B [20th] and .................
6210 B [18th,
19th] 6200C
[20th] and 6230 B
[18th, 19th].
29. 2-Chloronaphthalene........ 612................ 625, 1625B......... ................... 6410 B [18th, ................. Note 9, p. 27.
19th, 20th].
30. 2-Chlorophenol............. 604................ 625, 1625B......... ................... 6410 B, 6420 B ................. Note 9, p. 27.
[18th, 19th,
20th].
31. 4-Chlorophenylphenyl ether. 611................ 625, 1625B......... ................... 6410 B, [18th, ................. Note 9, p. 27.
19th, 20th].
32. Chrysene................... 610................ 625, 1625B......... 610................ 6410 B, 6440 B D4657-92......... Note 9, p. 27.
[18th, 19th,
20th].
33. Dibenzo(a,h)anthracene..... 610................ 625, 1625B......... 610................ 6410 B, 6440 B D4657-92......... Note 9, p. 27.
[18th, 19th,
20th].
34. Dibromochloromethane....... 601................ 624, 1624B......... ................... 6200 B [20th] and .................
6210 B [18th,
19th] 6200 C
[20th] and 6230 B
[18th, 19th].
35. 1,2-Dichlorobenzene........ 601, 602, 612...... 624, 625, 1625B.... ................... 6200 C [20th] and ................. Note 9, p 27.
6220 B [18th,
19th], 6200 C
[20th] and 6230 B
[18th, 19th],
6410 B [18th,
19th, 20th].
36. 1,3-Dichlorobenzene........ 601, 602, 612...... 624, 625, 1625B.... ................... 6200 C [20th] and ................. Note 9, p. 27.
6220 B [18th,
19th], 6200 C
[20th] and 6230 B
[18th, 19th],
6410 B [18th,
19th, 20th].
[[Page 24]]
37. 1,4-Dichlorobenzene........ 601, 602, 612...... 624, 625, 1625B.... ................... 6200 C [20th] and ................. Note 9, p. 27.
6220 B [18th,
19th], 6200 C
[20th] and 6230 B
[18th, 19th],
6410 B [18th,
19th, 20th].
38. 3,3-Dichlorobenzidine...... ................... 625, 1625B......... 605................ 6410 B [18th, .................
19th, 20th].
39. Dichlorodifluoromethane.... 601................ ................... ................... 6200 C [20th] and .................
6230 B [18th,
19th].
40. 1,1-Dichloroethane......... 601................ 624, 1624B......... ................... 6200 B [20th] and .................
6210 B [18th,
19th], 6200 C
[20th] and 6230 B
[18th, 19th].
41. 1,2-Dichloroethane......... 601................ 624, 1624B......... ................... 6200 B [20th] and .................
6210 B [18th,
19th], 6200 C
[20th] and 6230 B
[18th, 19th].
42. 1,1-Dichloroethene......... 601................ 624, 1624B......... ................... 6200 B [20th] and .................
6210 B [18th,
19th], 6200 C
[20th] and 6230 B
[18th, 19th].
43. trans-1,2-Dichloroethene... 601................ 624, 1624B......... ................... 6200 B [20th] and .................
6210 B [18th,
19th], 6200 C
[20th] and 6230 B
[18th, 19th].
44. 2,4-Dichlorophenol......... 604................ 625, 1625B......... ................... 6410 B, 6420 B ................. Note 9, p. 27.
[18th, 19th,20th].
45. 1,2-Dichloropropane........ 601................ 624, 1624B......... ................... 6200 B [20th] and
6210 B [18th,
19th], 6200 C
[20th] and 6230 B
[18th, 19th].
46. cis-1,3-Dichloropropene.... 601................ 624, 1624B......... ................... 6200 B [20th] and
6210 B [18th,
19th], 6200 C
[20th] and 6230 B
[18th, 19th].
47. trans-1,3-Dichloropropene.. 601................ 624, 1624B......... ................... 6200 B [20th] and
6210 B [18th,
19th], 6200 C
[20th] and 6230 B
[18th, 19th].
48. Diethyl phthalate.......... 606................ 625, 1625B......... ................... 6410 B [18th, ................. Note 9, p. 27.
19th, 20th].
[[Page 25]]
49. 2,4-Dimethylphenol......... 604................ 625, 1625B......... ................... 6410 B, 6420 B ................. Note 9, p. 27.
[18th, 19th,20th].
50. Dimethyl phthalate......... 606................ 625, 1625B......... ................... 6410 B [18th, ................. Note 9, p. 27.
19th, 20th].
51. Di-n-butyl phthalate....... 606................ 625, 1625B......... ................... 6410 B [18th, ................. Note 9, p. 27.
19th, 20th].
52. Di-n-octyl phthalate....... 606................ 625, 1625B......... ................... 6410 B [18th, ................. Note 9, p. 27.
19th, 20th].
53. 2,3-Dinitrophenol.......... 604................ 625, 1625B......... ................... 6410 B, 6420 B
[18th, 19th,
20th].
54. 2,4-Dinitrotoluene......... 609................ 625, 1625B......... ................... 6410 B [18th, ................. Note 9, p. 27.
19th, 20th].
55. 2,6-Dinitrotoluene......... 609................ 625, 1625B......... ................... 6410 B [18th, ................. Note 9, p. 27.
19th, 20th].
56. Epichlorohydrin............ ................... ................... ................... .................. ................. Note 3, p. 130;
Note 6, p. S102.
57. Ethylbenzene............... 602................ 624, 1624B......... ................... 6200 B [20th] and
6210 B [18th,
19th], 6200 C
[20th] and 6220 B
[18th, 19th].
58. Fluoranthene............... 610................ 625, 1625B......... 610................ 6410 B, 6440 B D4657-92......... Note 9, p. 27.
[18th, 19th,
20th].
59. Fluorene................... 610................ 625, 1625B......... 610................ 6410 B, 6440 B D4657-92......... Note 9, p. 27.
[18th, 19th,
20th].
60. 1,2,3,4,6,7,8-Heptachloro- ................... 1613B
dibenzofuran.
61. 1,2,3,4,7,8,9-Heptachloro- ................... 1613B .................
dibenzofuran.
62. 1,2,3,4,6,7,8-Heptachloro- ................... 1613B .................
dibenzo-p-dioxin.
63. Hexachlorobenzene.......... 612................ 625, 1625B......... ................... 6410 B [18th, ................. Note 9, p. 27.
19th, 20th].
64. Hexachlorobutadiene........ 612................ 625, 1625B......... ................... 6410 B [18th, ................. Note 9, p. 27.
19th, 20th].
65. Hexachlorocyclopentadiene.. 612................ \5\625, 1625B..... ................... 6410 [18th, 19th, ................. Note 9, p. 27.
20th].
66. 1,2,3,4,7,8-Hexachloro- ................... 1613B..............
dibenzofuran.
67. 1,2,3,6,7,8-Hexachloro- ................... 1613B..............
dibenzofuran.
68. 1,2,3,7,8,9-Hexachloro- ................... 1613B..............
dibenzofuran.
69. 2,3,4,6,7,8-Hexachloro- ................... 1613B..............
dibenzofuran.
70. 1,2,3,4,7,8-Hexachloro- ................... 1613B..............
dibenzo-p-dioxin.
71. 1,2,3,6,7,8-Hexachloro- ................... 1613B..............
dibenzo-p-dioxin.
72. 1,2,3,7,8,9-Hexachloro- ................... 1613B..............
dibenzo-p-dioxin.
73. Hexachloroethane........... 616................ 625, 1625B......... ................... 6410 B [18th, ................. Note 9, p. 27.
19th, 20th].
74. Ideno(1,2,3-cd) pyrene..... 610................ 625, 1625B......... 610................ 6410 B, 6440 B D4657-92......... Note 9, p. 27.
[18th, 19th,
20th].
75. Isophorone................. 609................ 625, 1625B......... ................... 6410 B [18th, ................. Note 9, p. 27.
19th, 20th].
76. Methylene chloride......... 601................ 624, 1624B......... ................... 6200 C [20th] and ................. Note 3, p. 130.
6230 B [18th,
19th].
77. 2-Methyl-4,6-dinitrophenol. 604................ 625, 1625B......... ................... 6420 B, 6410 B ................. Note 9, p. 27.
[18th, 19th,
20th].
[[Page 26]]
78. Naphthalene................ 610................ 625, 1625B......... 610................ 6440 B, 6410 B ................. Note 9, p. 27.
[18th, 19th,
20th].
79. Nitrobenzene............... 609................ 625, 1625B......... ................... 6410 B [18th, D4657-92......... Note 9, p. 27.
19th, 20th].
80. 2-Nitrophenol.............. 604................ 625, 1625B......... ................... 6410 B, 6420 B ................. Note 9, p. 27
[18th, 19th,
20th].
81. 4-Nitrophenol.............. 604................ 625, 1625B......... ................... 6410 B, 6420 B ................. Note 9, p. 27
[18th, 19th,
20th].
82. N-Nitrosodimethylamine..... 607................ 625\5\, 1625B...... ................... 6410 B [18th, ................. Note 9, p. 27
19th, 20th].
83. N-Nitrosodi-n-propylamine.. 607................ 625, 1625B......... ................... 6410 B [18th, ................. Note 9, p. 27
19th, 20th].
84. N-Nitrosodiphenylamine..... 607................ 625\5\, 1625B...... ................... 6410 B [18th, ................. Note 9, p. 27
19th, 20th].
85. Octachlorodibenzofuran..... ................... 1613B..............
86. Octachlorodibenzo-p-dioxin. ................... 1613B..............
87. 2,2'-Oxybis(2- 611................ 625, 1625B......... ................... 6410 B [18th,
chloropropane) [also known as 19th, 20th].
bis(2-chloroisopropyl) ether].
88. PCB-1016................... 608................ 625................ ................... 6410 B [18th, ................. Note 3, p. 43
19th, 20th].
89. PCB-1221................... 608................ 625................ ................... 6410 B [18th, ................. Note 3, p. 43
19th, 20th].
90. PCB-1232................... 608................ 625................ ................... 6410 B [18th, ................. Note 3, p. 43
19th, 20th].
91. PCB-1242................... 608................ 625................ ................... 6410 B [18th, ................. Note 3, p. 43
19th, 20th].
92. PCB-1248................... 608................ 625................
93. PCB-1254................... 608................ 625................ ................... 6410 B [18th, ................. Note 3, p. 43
19th, 20th].
94. PCB-1260................... 608................ 625................ ................... 6410 B, 6630 B ................. Note 3, p. 43
[18th, 19th,
20th].
95. 1,2,3,7,8-Pentachloro- ................... 1613B..............
dibenzofuran.
96. 2,3,4,7,8-Pentachloro- ................... 1613B..............
dibenzofuran.
97. 1,2,3,7,8,- ................... 1613B..............
Pentachlorodibenzo-p-dioxin.
98. Pentachlorophenol.......... 604................ 625, 1625B......... ................... 6410 B, 6630 B ................. Note 3, p. 140;
[18th, 19th, Note 9, p. 27
20th].
99. Phenanthrene............... 610................ 625, 1625B......... 610................ 6410 B, 6440 B D4657-92......... Note 9, p. 27
[18th, 19th,
20th].
100. Phenol.................... 604................ 625, 1625B......... ................... 6420 B, 6410 B ................. Note 9, p. 27
[18th, 19th,
20th].
101. Pyrene.................... 610................ 625, 1625B......... 610................ 6440 B, 6410 B D4675-92......... Note 9, p. 27
D4675-92 [18th,
19th, 20th].
[[Page 27]]
102. 2,3,7,8-Tetrachloro- ................... 1613B..............
dibenzofuran.
103. 2,3,7,8-Tetrachlorodibenzo- ................... 613, 1613B.........
p-dioxin.
104. 1,1,2,2-Tetrachloroethane. 601................ 624, 1624B......... ................... 6200 B [20th] and ................. Note 3, p. 130
6210 B [18th,
19th], 6200 C
[20th] and 6230 B
[18th, 19th].
105. Tetrachloroethene......... 601................ 624, 1624B......... ................... 6200 B [20th] and ................. Note 3, p. 130
6210 B [18th,
19th], 6200 C
[20th] and 6230 B
[18th, 19th].
106. Toluene................... 602................ 624, 1624B......... ................... 6200 B [20th] and
6210 B [18th,
19th], 6200 C
[20th] and 6220 B
[18th, 19th].
107. 1,2,4-Trichlorobenzene.... 612................ 625, 1625B......... ................... 6410 B [18th, ................. Note 3, p. 130;
19th, 20th]. Note 9, p. 27.
108. 1,1,1-Trichloroethane..... 601................ 624, 1624B......... ................... 6200 B [20th] and
6210 B [18th,
19th], 6200 C
[20th] and 6230 B
[18th, 19th].
109. 1,1,2-Trichloroethane..... 601................ 624, 1624B......... ................... 6200 B [20th] and ................. Note 3, p. 130
6210 B [18th,
19th], 6200 C
[20th] and 6230 B
[18th, 19th].
110. Trichloroethene........... 601................ 624, 1624B......... ................... 6200 B [20th] and
6210 B [18th,
19th], 6200 C
[20th] and 6230 B
[18th, 19th].
111. Trichlorofluoromethane.... 601................ 624................ ................... 6200 B [20th] and
6210 B [18th,
19th], 6200 C
[20th] and 6230 B
[18th, 19th].
112. 2,4,6-Trichlorophenol..... 604................ 625, 1625B......... ................... 6420 B, 6410 B ................. Note 9, p. 27.
[18th, 19th,
20th].
113. Vinyl chloride............ 601................ 624, 1624B......... ................... 6200 B [20th] and
6210 B [18th,
19th], 6200 C
[20th] and 6230 B
[18th, 19th].
--------------------------------------------------------------------------------------------------------------------------------------------------------
Table IC notes:
\1\ All parameters are expressed in micrograms per liter ([micro]g/L) except for Method 1613B in which the parameters are expressed in picograms per
liter (pg/L).
\2\ The full text of Methods 601-613, 624, 625, 1624B, and 1625B, are given at Appendix A, ``Test Procedures for Analysis of Organic Pollutants,'' of
this Part 136. The full text of Method 1613B is incorporated by reference into this Part 136 and is available from the National Technical Information
Services as stock number PB95-104774. The standardized test procedure to be used to determine the method detection limit (MDL) for these test
procedures is given at Appendix B, ``Definition and Procedure for the Determination of the Method Detection Limit,'' of this Part 136.
\3\ ``Methods for Benzidine: Chlorinated Organic Compounds, Pentachlorophenol and Pesticides in Water and Wastewater,'' U.S. Environmental Protection
Agency, September, 1978.
\4\ Method 624 may be extended to screen samples for Acrolein and Acrylonitrile. However, when they are known to be present, the preferred method for
these two compounds is Method 603 or Method 1624B.
\5\ Method 625 may be extended to include benzidine, hexachlorocyclopentadiene, N-nitrosodimethylamine, and N-nitrosodiphenylamine. However, when they
are known to be present, Methods 605, 607, and 612, orMethod 1625B, are preferred methods for these compounds.
\6\ ``Selected Analytical Methods Approved and Cited by the United States Environmental Protection Agency,'' Supplement to the Fifteenth Edition of
Standard Methods for the Examination of Water and Wastewater (1981).
[[Page 28]]
\7\ Each Analyst must make an initial, one-time demonstration of their ability to generate acceptable precision and accuracy with Methods 601-603, 624,
625, 1624B, and 1625B (See Appendix A of this Part 136) in accordance with procedures each in Section 8.2 of each of these Methods. Additionally, each
laboratory, on an on-going basis must spike and analyze 10% (5% for Methods 624 and 625 and 100% for methods 1624B and 1625B) of all samples to
monitor and evaluate laboratory data quality in accordance with Sections 8.3 and 8.4 of these Methods. When the recovery of any parameter falls
outside the warning limits, the analytical results for that parameter in the unspiked sample are suspect and cannot be reported to demonstrate
regulatory compliance.
Note: These warning limits are promulgated as an ``interim final action with a request for comments.''
\8\ ``Organochlorine Pesticides and PCBs in Wastewater Using Empore TM Disk'' 3M Corporation Revised 10/28/94.
\9\ USGS Method 0-3116-87 from ``Methods of Analysis by U.S. Geological Survey National Water Quality Laboratory--Determination of Inorganic and Organic
Constituents in Water and Fluvial Sediments'' U.S. Geological Survey, Open File Report 93-125.
Table ID--List of Approved Test Procedures for Pesticides \1\
--------------------------------------------------------------------------------------------------------------------------------------------------------
Standard Methods
Parameter Method EPA 2, 7 18th, 19th, 20th Ed. ASTM Other
--------------------------------------------------------------------------------------------------------------------------------------------------------
1. Aldrin......................... GC.................... 608................... 6630 B & C............ D3086-90.............. Note 3, p. 7; Note
4, p. 27; Note 8.
GC/MS................. 625................... 6410 B
2. Ametryn........................ GC.................... ...................... ...................... ...................... Note 3, p. 83; Note
6, p S68.
3. Aminocarb...................... TLC................... ...................... ...................... ...................... Note 3, p. 94; Note
6, p. S16.
4. Atraton........................ GC.................... ...................... ...................... ...................... Note 3, p. 83; Note
6, p. S68.
5. Atrazine....................... GC.................... ...................... ...................... ...................... Note 3, p. 83; Note
6, p. S68; Note 9.
6. Azinphos methyl................ GC.................... ...................... ...................... ...................... Note 3, p. 25; Note
6, p. S51.
7. Barban......................... TLC................... ...................... ...................... ...................... Note 3, p. 104; Note
6, p. S64.
8. [alpha]-BHC.................... GC.................... 608................... 6630 B & C............ D3086-90.............. Note 3, p. 7; Note
8.
GC/MS................. 625 \5\............... 6410 B................
9. [beta]-BHC..................... GC.................... 608................... 6630 C................ D3086-90.............. Note 8.
GC/MS................. 625 \5\............... 6410 B................
10. [delta]-BHC................... GC.................... 608................... 6630 C................ D3086-90.............. Note 8.
GC/MS................. 625 \5\............... 6410 B................
11. [gamma]-BHC (Lindane)......... GC.................... 608................... 6630 B & C............ D3086-90.............. Note 3, p. 7; Note
4, p. 27; Note 8.
GC/MS................. 625................... 6410 B................
12. Captan........................ GC.................... ...................... 6630 B................ D3086-90.............. Note 3, p. 7.
13. Carbaryl...................... TLC................... ...................... ...................... ...................... Note 3, p. 94, Note
6, p. S60.
14. Carbophenothion............... GC.................... ...................... ...................... ...................... Note 4, p. 27; Note
6, p. S73.
15. Chlordane..................... GC.................... 608................... 6630 B & C............ D3086-90.............. Note 3, p. 7; Note
4, p. 27; Note 8.
GC/MS................. 625................... 6410 B................
16. Chloropropham................. TLC................... ...................... ...................... ...................... Note 3, p. 104; Note
6, p. S64.
17. 2,4-D......................... GC.................... ...................... 6640 B................ ...................... Note 3, p. 115; Note
4, p. 40.
18. 4,4'-DDD...................... GC.................... 608................... 6630 B & C............ D3086-90.............. Note 3, p. 7; Note
4, p. 27; Note 8.
GC/MS................. 625................... 6410 B................
19. 4,4'-DDE...................... GC.................... 608................... 6630 B & C............ D3086-90.............. Note 3, p. 7; Note
4, p. 27; Note 8.
GC/MS................. 625................... 6410 B................
20. 4,4'-DDT...................... GC.................... 608................... 6630 B & C............ D3086-90.............. Note 3, p. 7; Note
4, p. 27; Note 8.
GC/MS................. 625................... 6410 B................
21. Demeton-O..................... GC.................... ...................... ...................... ...................... Note 3, p. 25; Note
6, p. S51.
22. Demeton-S..................... GC.................... ...................... ...................... ...................... Note 3, p. 25; Note
6, p. S51.
23. Diazinon...................... GC.................... ...................... ...................... ...................... Note 3, p. 25; Note
4, p. 27; Note 6,
p. S51.
24. Dicamba....................... GC.................... ...................... ...................... ...................... Note 3, p. 115.
25. Dichlofenthion................ GC.................... ...................... ...................... ...................... Note 4, p. 27; Note
6, p. S73.
26. Dichloran..................... GC.................... ...................... 6630 B & C............ ...................... Note 3, p. 7.
[[Page 29]]
27. Dicofol....................... GC.................... ...................... ...................... D3086-90..............
28. Dieldrin...................... GC.................... 608................... 6630 B & C............ ...................... Note 3, p. 7; Note
4, p. 27; Note 8.
GC/MS................. 625................... 6410 B................
29. Dioxathion.................... GC.................... ...................... ...................... ...................... Note 4, p. 27; Note
6, p. S73.
30. Disulfoton.................... GC.................... ...................... ...................... ...................... Note 3, p. 25; Note
6 p. S51.
31. Diuron........................ TLC................... ...................... ...................... ...................... Note 3, p. 104; Note
6, p. S64.
32. Endosulfan I.................. GC.................... 608................... 6630 B & C............ D3086-90.............. Note 3, p. 7; Note
4, p. 27; Note 8.
GC/MS................. 625 \5\............... 6410 B................
33. Endosulfan II................. GC.................... 608................... 6630 B & C............ D3086-90.............. Note 3, p. 7; Note
8.
GC/MS................. 625 \5\............... 6410 B................
34. Endosulfan Sulfate............ GC.................... 608................... 6630 C................ ...................... Note 8.
GC/MS................. 625................... 6410 B................
35. Endrin........................ GC.................... 608................... 6630 B & C............ D3086-90.............. Note 3, p. 7; Note
...................... ...................... ...................... 4, p. 27; Note 8.
GC/MS................. 625 \5\............... 6410 B................
36. Endrin aldehyde............... GC.................... 608................... ...................... ...................... Note 8.
GC/MS................. 625...................
37. Ethion........................ GC.................... ...................... ...................... ...................... Note 4, p. 27; Note
6, p. S73.
38. Fenuron....................... TLC................... ...................... ...................... ...................... Note 3, p. 104; Note
6, p. S64.
39. Fenuron-TCA................... TLC................... ...................... ...................... ...................... Note 3, p. 104; Note
6, p. S64.
40. Heptachlor.................... GC.................... 608................... 6630 B & C............ 3086-90............... Note 3, p. 7; Note
4, p. 27; Note 8.
GC/MS................. 625................... 6410 B................
41. Heptachlor epoxide............ GC.................... 608................... 6630 B & C............ D3086-90.............. Note 3, p. 7; Note
...................... ...................... ...................... 4, p. 27; Note 6,
GC/MS................. 625................... 6410 B................ p. S73; Note 8.
42. Isodrin....................... GC.................... ...................... ...................... ...................... Note 4, p. 27; Note
6, p. S73.
43. Linuron....................... GC.................... ...................... ...................... ...................... Note 3, p. 104; Note
6, p. S64.
44. Malathion..................... GC.................... ...................... 6630 C................ ...................... Note 3, p. 25; Note
4, p. 27; Note 6,
p. S51
45. Methiocarb.................... TLC................... ...................... ...................... ...................... Note 3, p. 94; Note
6, p. S60.
46. Methoxychlor.................. GC.................... ...................... 6630 B & C............ D3086-90.............. Note 3, p. 7; Note
4, p. 27; Note 8.
47. Mexacarbate................... TLC................... ...................... ...................... ...................... Note 3, p. 94; Note
6, p. S60.
48. Mirex......................... GC.................... ...................... 6630 B & C............ ...................... Note 3, p. 7; Note
4, p. 27.
49. Monuron....................... TLC................... ...................... ...................... ...................... Note 3, p. 104; Note
6, p. S64.
50. Monuron....................... TLC................... ...................... ...................... ...................... Note 3, p. 104; Note
6, p. S64.
51. Nuburon....................... TLC................... ...................... ...................... ...................... Note 3, p. 104; Note
6, p. S64.
52. Parathion methyl.............. GC.................... ...................... 6630 C................ ...................... Note 3, p. 25; Note
4, p. 27.
53. Parathion ethyl............... GC.................... ...................... 6630 C................ ...................... Note 3, p. 25; Note
4, p. 27.
54. PCNB.......................... GC.................... ...................... 6630 B & C............ ...................... Note 3, p. 7.
55. Perthane...................... GC.................... ...................... ...................... D3086-90.............. Note 4, p. 27.
56. Prometron..................... GC.................... ...................... ...................... ...................... Note 3, p. 83; Note
6, p. S68; Note 9.
57. Prometryn..................... GC.................... ...................... ...................... ...................... Note 3, p. 83; Note
6, p. S68; Note 9.
58. Propazine..................... GC.................... ...................... ...................... ...................... Note 3, p. 83; Note
6, p. S68; Note 9.
59. Propham....................... TLC................... ...................... ...................... ...................... Note 3, p. 104; Note
6, p. S64.
60. Propoxur...................... TLC................... ...................... ...................... ...................... Note 3, p. 94; Note
6, p. S60.
61. Secbumeton.................... TLC................... ...................... ...................... ...................... Note 3, p. 83; Note
6, p. S68.
62. Siduron....................... TLC................... ...................... ...................... ...................... Note 3, p. 104; Note
6, p. S64.
63. Simazine...................... GC.................... ...................... ...................... ...................... Note 3, p. 83; Note
6, p. S68; Note 9.
64. Strobane...................... GC.................... ...................... 6630 B & C............ ...................... Note 3, p. 7.
65. Swep.......................... TLC................... ...................... ...................... ...................... Note 3, p. 104; Note
6, p. S64.
66. 2,4,5-T....................... GC.................... ...................... 6640 B................ ...................... Note 3, p. 115; Note
4, p. 40.
[[Page 30]]
67. 2,4,5-TP (Silvex)............. GC.................... ...................... 6640 B................ ...................... Note 3, p. 115; Note
4, p. 40.
68. Terbuthylazine................ GC.................... ...................... ...................... ...................... Note 3, p. 83; Note
6, p. S68.
69. Toxaphene..................... GC.................... 608................... 6630 B & C............ D3086--90............. Note 3, p. 7; Note
4, p. 27; Note 8.
GC/MS................. 625................... 6410B.................
70. Trifluralin................... GC.................... ...................... 6630 B................ ...................... Note 3, p. 7; Note
9.
--------------------------------------------------------------------------------------------------------------------------------------------------------
Table ID notes:
\1\ Pesticides are listed in this table by common name for the convenience of the reader. Additional pesticides may be found under Table 1C, where
entries are listed by chemical name.
\2\ The full text of Methods 608 and 625 are given at Appendix A. ``Test Procedures for Analysis of Organic Pollutants,'' of this Part 136. The
standardized test procedure to be used to determine the method detection limit (MDL) for these test procedures is given at Appendix B, ``Definition
and Procedure for the Determination of the Method Detection Limit,'' of this Part 136.
\3\ ``Methods for Benzidine, Chlorinated Organic Compounds, Pentachlorophenol and Pesticides in Water and Wastewater,'' U.S. Environmental Protection
Agency, September 1978. This EPA publication includes thin-layer chromatography (TLC) methods.
\4\ ``Methods for Analysis of Organic Substances in Water and Fluvial Sediments,'' Techniques of Water-Resources Investigations of the U.S. Geological
Survey, Book 5, Chapter A3 (1987).
\5\ The method may be extended to include [alpha]-BHC, [gamma]-BHC, endosulfan I, endosulfan II, and endrin. However, when they are known to exist,
Method 608 is the preferred method.
\6\ ``Selected Analytical Methods Approved and Cited by the United States Environmental Protection Agency.'' Supplement to the Fifteenth Edition of
Standard Methods for the Examination of Water and Wastewater (1981).
\7\ Each analyst must make an initial, one-time, demonstration of their ability to generate acceptable precision and accuracy with Methods 608 and 625
(See Appendix A of this Part 136) in accordance with procedures given in Section 8.2 of each of these methods. Additionally, each laboratory, on an on-
going basis, must spike and analyze 10% of all samples analyzed with Method 608 or 5% of all samples analyzed with Method 625 to monitor and evaluate
laboratory data quality in accordance with Sections 8.3 and 8.4 of these methods. When the recovery of any parameter falls outside the warning limits,
the analytical results for that parameter in the unspiked sample are suspect and cannot be reported to demonstrate regulatory compliance. These
quality control requirements also apply to the Standard Methods, ASTM Methods, and other Methods cited.
Note: These warning limits are promulgated as an ``Interim final action with a request for comments.''
\8\ ``Organochlorine Pesticides and PCBs in Wastewater Using Empore TM Disk'', 3M Corporation, Revised 10/28/94.
\9\ USGS Method 0-3106-93 from ``Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory--Determination of Triazine and
Other Nitrogen-containing Compounds by Gas Chromatography with Nitrogen Phosphorus Detectors'' U.S. Geological Survey Open File Report 94-37.
Table IE--List of Approved Radiologic Test Procedures
--------------------------------------------------------------------------------------------------------------------------------------------------------
Reference (method number or page)
---------------------------------------------------------------------------------------------------
Parameter and units Method Standard Methods 18th,
EPA\1\ 19th, 20th Ed. ASTM USGS \2\
--------------------------------------------------------------------------------------------------------------------------------------------------------
1. Alpha-Total, pCi per liter... Proportional or 900 7110 B D1943-90 pp. 75 and 78 \3\
scintillation
counter.
2. Alpha-Counting error, pCi per Proportional or Appendix B 7110 B D1943-90 p. 79
liter. scintillation
counter.
3. Beta-Total, pCi per liter.... Proportional 900.0 7110 B D1890-90 pp. 75 and 78 \3\
counter.
4. Beta-Counting error, pCi..... Proportional Appendix B 7110 B D1890-90 p. 79
counter.
5. (a) Radium Total pCi per Proportional 903.0 7500Ra B D2460-90 .......................
liter. counter.
(b) Ra, pCi per liter....... Scintillation 903.1 7500Ra C D3454-91 p. 81
counter.
--------------------------------------------------------------------------------------------------------------------------------------------------------
Table 1E notes:
\1\ ``Prescribed Procedures for Measurement of Radioactivity in Drinking Water,'' EPA-600/4-80-032 (1980), U.S. Environmental Protection Agency, August
1980.
\2\ Fishman, M.J. and Brown, Eugene, ``Selected Methods of the U.S. Geological Survey of Analysis of Wastewaters,'' U.S. Geological Survey, Open-File
Report 76-177 (1976).
\3\ The method found on p. 75 measures only the dissolved portion while the method on p. 78 measures only the suspended portion. Therefore, the two
results must be added to obtain the ``total''.
[[Page 31]]
Table IF--List of Approved Methods for Pharmaceutical Pollutants
----------------------------------------------------------------------------------------------------------------
Pharmaceuticals pollutants CAS registry No. Analytical method number
----------------------------------------------------------------------------------------------------------------
acetonitrile................... 75-05-8............................ 1666/1671/D3371/D3695.
n-amyl acetate................. 628-63-7........................... 1666/D3695.
n-amyl alcohol................. 71-41-0............................ 1666/D3695
benzene........................ 71-43-2............................ D4763/D3695/502.2/524.2.
n-butyl-acetate................ 123-86-4........................... 1666/D3695.
tert-butyl alcohol............. 75-65-0............................ 1666.
chlorobenzene.................. 108-90-7........................... 502.2/524.2.
chloroform..................... 67-66-3............................ 502.2/524.2/551.
o-dichlorobenzene.............. 95-50-1............................ 1625C/502.2/524.2.
1,2-dichloroethane............. 107-06-2........................... D3695/502.2/524.2.
diethylamine................... 109-89-7........................... 1666/1671.
dimethyl sulfoxide............. 67-68-5............................ 1666/1671.
ethanol........................ 64-17-5............................ 1666/1671/D3695.
ethyl acetate.................. 141-78-6........................... 1666/D3695.
n-heptane...................... 142-82-5........................... 1666/D3695.
n-hexane....................... 110-54-3........................... 1666/D3695.
isobutyraldehyde............... 78-84-2............................ 1666/1667.
isopropanol.................... 67-63-0............................ 1666/D3695.
isopropyl acetate.............. 108-21-4........................... 1666/D3695.
isopropyl ether................ 108-20-3........................... 1666/D3695.
methanol....................... 67-56-1............................ 1666/1671/D3695.
Methyl Cellosolve [Delta]...... 109-86-4........................... 1666/1671
methylene chloride............. 75-09-2............................ 502.2/524.2
methyl formate................. 107-31-3........................... 1666.
4-methyl-2-pentanone (MIBK).... 108-10-1........................... 1624C/1666/D3695/D4763/524.2.
phenol......................... 108-95-2........................... D4763.
n-propanol..................... 71-23-8............................ 1666/1671/D3695.
2-propanone (acetone).......... 67-64-1............................ D3695/D4763/524.2.
tetrahydrofuran................ 109-99-9........................... 1666/524.2.
toluene........................ 108-88-3........................... D3695/D4763/502.2/524.2.
triethlyamine.................. 121-44-8........................... 1666/1671.
xylenes........................ (Note 1)........................... 1624C/1666.
----------------------------------------------------------------------------------------------------------------
Table 1F note:
1. 1624C: m-xylene 108-38-3, o,p-xylene E-14095 (Not a CAS number; this is the number provided in the
Environmental Monitoring Methods Index (EMMI) database.); 1666: m,p-xylene 136777-61-2, o-xylene 95-47-6.
(b) The full texts of the methods from the following references
which are cited in Tables IA, IB, IC, ID, IE,and IF are incorporated by
reference into this regulation and may be obtained from the sources
identified. All costs cited are subject to change and must be verified
from the indicated sources. The full texts of all the test procedures
cited are available for inspection at the National Exposure Research
Laboratory, Office of Research and Development, U.S. Environmental
Protection Agency, 26 West Martin Luther King Dr., Cincinnati, OH 45268
and the National Archives and Records Administration (NARA). For
information on the availability of this material at NARA, call 202-741-
6030, or go to: http://www.archives.gov/federal--register/code--of--
federal--regulations/ibr--locations.html.
References, Sources, Costs, and Table Citations:
(1) The full texts of Methods 601-613, 624, 625, 1613, 1624, and
1625 are printed in appendix A of this part 136. The full text for
determining the method detection limit when using the test procedures is
given in appendix B of this part 136. The full text of Method 200.7 is
printed in appendix C of this part 136. Cited in: Table IB, Note 5;
Table IC, Note 2; and Table ID, Note 2.
(2) USEPA. 1978. Microbiological Methods for Monitoring the
Environment, Water, and Wastes. Environmental Monitoring and Support
Laboratory, U.S. Environmental Protection Agency, Cincinnati, Ohio. EPA/
600/8-78/017. Available from: National Technical Information Service,
5285 Port Royal Road, Springfield, Virginia 22161, Publ. No. PB-290329/
AS. Cost: $36.95. Table IA, Note 3.
(3) ``Methods for Chemical Analysis of Water and Wastes,'' U.S.
Environmental Protection Agency, EPA-600/4-
[[Page 32]]
79-020, March 1979, or ``Methods for Chemical Analysis of Water and
Wastes,'' U.S. Environmental Protection Agency, EPA-600/4-79-020,
Revised March 1983. Available from: ORD Publications, CERI, U.S.
Environmental Protection Agency, Cincinnati, Ohio 45268, Table IB, Note
1.
(4) ``Methods for Benzidine, Chlorinated Organic Compounds,
Pentachlorophenol and Pesticides in Water and Wastewater,'' U.S.
Environmental Protection Agency, 1978. Available from: ORD Publications,
CERI, U.S. Environmental Protection Agency, Cincinnati, Ohio 45268,
Table IC, Note 3; Table D, Note 3.
(5) ``Prescribed Procedures for Measurement of Radioactivity in
Drinking Water,'' U.S. Environmental Protection Agency, EPA-600/4-80-
032, 1980. Available from: ORD Publications, CERI, U.S. Environmental
Protection Agency, Cincinnati, Ohio 45268, Table IE, Note 1.
(6) American Public Health Association. 1992, 1995, and 1998.
Standard Methods for the Examination of Water and Wastewater. 18th,
19th, and 20th Edition (respectively). Available from: Amer. Publ. Hlth.
Assoc., 1015 15th Street, NW., Washington, DC 20005. Table IA, Note 4.
Tables IB, IC, ID, IE.
(7) Ibid, 15th Edition, 1980. Table IB, Note 30; Table ID.
(8) Ibid, 14th Edition, 1975. Table IB, Notes 17 and 27.
(9) ``Selected Analytical Methods Approved and Cited by the United
States Environmental Protection Agency,'' Supplement to the 15th Edition
of Standard Methods for the Examination of Water and Wastewater, 1981.
Available from: American Public Health Association, 1015 Fifteenth
Street NW., Washington, DC 20036. Cost available from publisher. Table
IB, Note 10; Table IC, Note 6; Table ID, Note 6.
(10) Annual Book of ASTM Standards, Water, and Environmental
Technology, Section 11, Volumes 11.01 and 11.02, 1994, 1996, 1999, and
Volume 11.02, 2000 in 40 CFR 136.3, Tables IA, IB, IC, ID, and IE.
(11) USGS. 1989. U.S. Geological Survey Techniques of Water-
Resources Investigations, Book 5, Laboratory Analysis, Chapter A4,
Methods for Collection and Analysis of Aquatic Biological and
Microbiological Samples, U.S. Geological Survey, U.S. Department of the
Interior, Reston, Virginia. Available from: USGS Books and Open-File
Reports Section, Federal Center, Box 25425, Denver, Colorado 80225.
Cost: $18.00. Table IA, Note 5.
(12) ``Methods for Determination of Inorganic Substances in Water
and Fluvial Sediments,'' by M.J. Fishman and Linda C. Friedman,
Techniques of Water-Resources Investigations of the U.S. Geological
Survey, Book 5 Chapter A1 (1989). Available from: U.S. Geological
Survey, Denver Federal Center, Box 25425, Denver, CO 80225. Cost:
$108.75 (subject to change). Table IB, Note 2.
(13) ``Methods for Determination of Inorganic Substances in Water
and Fluvial Sediments,'' N.W. Skougstad and others, editors. Techniques
of Water-Resources Investigations of the U.S. Geological Survey, Book 5,
Chapter A1 (1979). Available from: U.S. Geological Survey, Denver
Federal Center, Box 25425, Denver, CO 80225. Cost: $10.00 (subject to
change), Table IB, Note 8.
(14) ``Methods for the Determination of Organic Substances in Water
and Fluvial Sediments,'' Wershaw, R.L., et al, Techniques of Water-
Resources Investigations of the U.S. Geological Survey, Book 5, Chapter
A3 (1987). Available from: U.S. Geological Survey, Denver Federal
Center, Box 25425, Denver, CO 80225. Cost: $0.90 (subject to change).
Table IB, Note 24; Table ID, Note 4.
(15) ``Water Temperature--Influential Factors, Field Measurement and
Data Presentation,'' by H.H. Stevens, Jr., J. Ficke, and G.F. Smoot,
Techniques of Water-Resources Investigations of the U.S. Geological
Survey, Book 1, Chapter D1, 1975. Available from: U.S. Geological
Survey, Denver Federal Center, Box 25425, Denver, CO 80225. Cost: $1.60
(subject to change). Table IB, Note 32.
(16) ``Selected Methods of the U.S. Geological Survey of Analysis of
Wastewaters,'' by M.J. Fishman and Eugene Brown; U.S. Geological Survey
Open File Report 76-77 (1976). Available from: U.S. Geological Survey,
Branch of Distribution, 1200 South Eads Street, Arlington, VA 22202.
Cost: $13.50 (subject to change). Table IE, Note 2.
(17) ``Official Methods of Analysis of the Association of Official
Analytical
[[Page 33]]
Chemicals'', Methods manual, 15th Edition (1990). Price: $240.00.
Available from: The Association of Official Analytical Chemists, 2200
Wilson Boulevard, Suite 400, Arlington, VA 22201. Table IB, Note 3.
(18) ``American National Standard on Photographic Processing
Effluents,'' April 2, 1975. Available from: American National Standards
Institute, 1430 Broadway, New York, New York 10018. Table IB, Note 9.
(19) ``An Investigation of Improved Procedures for Measurement of
Mill Effluent and Receiving Water Color,'' NCASI Technical Bulletin No.
253, December 1971. Available from: National Council of the Paper
Industry for Air and Stream Improvements, Inc., 260 Madison Avenue, New
York, NY 10016. Cost available from publisher. Table IB, Note 18.
(20) Ammonia, Automated Electrode Method, Industrial Method Number
379-75WE, dated February 19, 1976. Technicon Auto Analyzer II. Method
and price available from Technicon Industrial Systems, Tarrytown, New
York 10591. Table IB, Note 7.
(21) Chemical Oxygen Demand, Method 8000, Hach Handbook of Water
Analysis, 1979. Method price available from Hach Chemical Company, P.O.
Box 389, Loveland, Colorado 80537. Table IB, Note 14.
(22) OIC Chemical Oxygen Demand Method, 1978. Method and price
available from Oceanography International Corporation, 512 West Loop,
P.O. Box 2980, College Station, Texas 77840. Table IB, Note 13.
(23) ORION Research Instruction Manual, Residual Chlorine Electrode
Model 97-70, 1977. Method and price available from ORION Research
Incorporation, 840 Memorial Drive, Cambridge, Massachusetts 02138. Table
IB, Note 16.
(24) Bicinchoninate Method for Copper. Method 8506, Hach Handbook of
Water Analysis, 1979, Method and price available from Hach Chemical
Company, P.O. Box 300, Loveland, Colorado 80537. Table IB, Note 19.
(25) Hydrogen Ion (pH) Automated Electrode Method, Industrial Method
Number 378-75WA. October 1976. Bran & Luebbe (Technicon) Auto Analyzer
II. Method and price available from Bran & Luebbe Analyzing
Technologies, Inc. Elmsford, N.Y. 10523. Table IB, Note 21.
(26) 1,10-Phenanthroline Method using FerroVer Iron Reagent for
Water, Hach Method 8008, 1980. Method and price available from Hach
Chemical Company, P.O. Box 389 Loveland, Colorado 80537. Table IB, Note
22.
(27) Periodate Oxidation Method for Manganese, Method 8034, Hach
Handbook for Water Analysis, 1979. Method and price available from Hach
Chemical Company, P.O. Box 389, Loveland, Colorado 80537. Table IB, Note
23.
(28) Nitrogen, Nitrite--Low Range, Diazotization Method for Water
and Wastewater, Hach Method 8507, 1979. Method and price available from
Hach Chemical Company, P.O. Box 389, Loveland, Colorado 80537. Table IB,
Note 25.
(29) Zincon Method for Zinc, Method 8009. Hach Handbook for Water
Analysis, 1979. Method and price available from Hach Chemical Company,
P.O. Box 389, Loveland, Colorado 80537. Table IB, Note 33.
(30) ``Direct Determination of Elemental Phosphorus by Gas-Liquid
Chromatography,'' by R.F. Addison and R.G. Ackman, Journal of
Chromatography, Volume 47, No. 3, pp. 421-426, 1970. Available in most
public libraries. Back volumes of the Journal of Chromatography are
available from Elsevier/North-Holland, Inc., Journal Information Centre,
52 Vanderbilt Avenue, New York, NY 10164. Cost available from publisher.
Table IB, Note 28.
(31) ``Direct Current Plasma (DCP) Optical Emission Spectrometric
Method for Trace Elemental Analysis of Water and Wastes'', Method AES
0029, 1986-Revised 1991, Fison Instruments, Inc., 32 Commerce Center,
Cherry Hill Drive, Danvers, MA 01923. Table B, Note 34.
(32) ``Closed Vessel Microwave Digestion of Wastewater Samples for
Determination of Metals, CEM Corporation, P.O. Box 200, Matthews, North
Carolina 28106-0200, April 16, 1992. Available from the CEM Corporation.
Table IB, Note 36.
(33) ``Organochlorine Pesticides and PCBs in Wastewater Using Empore
TM Disk'' Test Method 3M 0222, Revised 10/28/94. 3M
Corporation, 3M Center Building 220-9E-10, St. Paul, MN 55144-1000.
[[Page 34]]
Method available from 3M Corporation. Table IC, Note 8 and Table ID,
Note 8.
(34) USEPA. October 2002. Methods for Measuring the Acute Toxicity
of Effluents and Receiving Waters to Freshwater and Marine Organisms.
Fifth Edition. U.S. Environmental Protection Agency, Office of Water,
Washington, DC EPA 821-R-02-012. Available from: National Technical
Information Service, 5285 Port Royal Road, Springfield, Virginia 22161,
Pub. No. PB2002-108488. Table IA, Note 29.
(35) ``Nitrogen, Total Kjeldahl, Method PAI-DK01 (Block Digestion,
Steam Distillation, Titrimetric Detection)'', revised 12/22/94.
Available from Perstorp Analytical Corporation, 9445 SW Ridder Rd.,
Suite 310, P.O. Box 648, Wilsonville, OK 97070. Table IB, Note 39.
(36) ``Nitrogen, Total Kjeldahl, Method PAI-DK02 (Block Digestion,
Steam Distillation, Colorimetric Detection)'', revised 12/22/94.
Available from Perstorp Analytical Corporation, 9445 SW Ridder Rd.,
Suite 310, P.O. Box 648, Wilsonville, OK 97070. Table IB, Note 40.
(37) ``Nitrogen, Total Kjeldahl, Method PAI-DK03 (Block Digestion,
Automated FIA Gas Diffusion)'', revised 12/22/94. Available from
Perstorp Analytical Corporation, 9445 SW Ridder Rd., Suite 310, P.O. Box
648, Wilsonville, OK 97070. Table IB, Note 41.
(38) USEPA. October 2002. Short-Term Methods for Measuring the
Chronic Toxicity of Effluents and Receiving Waters to Freshwater
Organisms. Fourth Edition. U.S. Environmental Protection Agency, Office
of Water, Washington, DC EPA-821-R-02-013. Available from: National
Technical Information Service, 5285 Port Royal Road, Springfield,
Virginia 22161, Pub. No. PB2002-108489. Table IA, Note 30.
(39) USEPA. October 2002. Short-Term Methods for Measuring the
Chronic Toxicity of Effluents and Receiving Waters to Marine and
Estuarine Organisms. Third Edition. U.S. Environmental Protection
Agency, Office of Water, Washington, DC EPA-821-R-02-014. Available
from: National Technical Information Service, 5285 Port Royal Road,
Springfield, Virginia 22161, Pub. No. PB2002-108490. Table IA, Note 31.
(40) EPA Methods 1666, 1667, and 1671 listed in the table above are
published in the compendium titled Analytical Methods for the
Determination of Pollutants in Pharmaceutical Manufacturing Industry
Wastewaters (EPA 821-B-98-016). EPA Methods 502.2 and 524.2 have been
incorporated by reference into 40 CFR 141.24 and are in Methods for the
Determination of Organic Compounds in Drinking Water, EPA-600/4-88-039,
December 1988, Revised, July 1991, and Methods for the Determination of
Organic Compounds in Drinking Water-Supplement II, EPA-600/R-92-129,
August 1992, respectively. These EPA test method compendia are available
from the National Technical Information Service, NTIS PB91-231480 and
PB92-207703, U.S. Department of Commerce, 5285 Port Royal Road,
Springfield, Virginia 22161. The toll-free number is 800-553-6847. ASTM
test methods D3371, D3695, and D4763 are available from the American
Society for Testing and Materials, 100 Barr Harbor Drive, West
Conshohocken, PA 19428-2959.
(41) USEPA. 2002. Method 1631, Revision E, ``Mercury in Water by
Oxidation, Purge and Trap, and Cold Vapor Atomic Fluorescence
Spectrometry.'' September 2002. Office of Water, U.S. Environmental
Protection Agency (EPA-821-R-02-019). Available from: National Technical
Information Service, 5285 Port Royal Road, Springfield, Virginia 22161.
Publication No. PB2002-108220. Cost: $25.50 (subject to change).
(42) [Reserved]
(43) Method OIA-1677, Available Cyanide by Flow Injection, Ligand
Exchange, and Amperometry. August 1999. ALPKEM, OI Analytical, Box 648,
Wilsonville, Oregon 97070 (EPA-821-R-99-013). Available from: National
Technical Information Service, 5285 Port Royal Road, Springfield,
Virginia 22161. Publication No. PB99-132011. Cost: $22.50. Table IB,
Note 44.
(44) ``Methods of Analysis by the U.S. Geological Survey National
Water Quality Laboratory Determination of Ammonium Plus Organic Nitrogen
by a Kjeldahl Digestion Method and an Automated Photometric Finish that
Includes Digest Cleanup by Gas Diffusion'', Open File Report (OFR) 00-
170.
[[Page 35]]
Available from: U.S. Geological Survey, Denver Federal Center, Box
25425, Denver, CO 80225. Table IB, Note 45.
(45) ``Methods of Analysis by the U.S. Geological Survey National
Water Quality Laboratory--Determination of Chromium in Water by Graphite
Furnace Atomic Absorption Spectrophotometry'', Open File Report (OFR)
93-449. Available from: U.S. Geological Survey, Denver Federal Center,
Box 25425, Denver, CO 80225. Table IB, Note 46.
(46) ``Methods of Analysis by the U.S. Geological Survey National
Water Quality Laboratory--Determination of Molybdenum in Water by
Graphite Furnace Atomic Absorption Spectrophotometry'', Open File Report
(OFR) 97-198. Available from: U.S. Geological Survey, Denver Federal
Center, Box 25425, Denver, CO 80225. Table IB, Note 47.
(47) ``Methods of Analysis by the U.S. Geological Survey National
Water Quality Laboratory--Determination of Total Phosphorus by Kjeldahl
Digestion Method and an Automated Colorimetric Finish That Includes
Dialysis'' Open File Report (OFR) 92-146. Available from: U.S.
Geological Survey, Denver Federal Center, Box 25425, Denver, CO 80225.
Table IB, Note 48.
(48) ``Methods of Analysis by the U.S. Geological Survey National
Water Quality Laboratory--Determination of Arsenic and Selenium in Water
and Sediment by Graphite Furnace--Atomic Absorption Spectrometry'' Open
File Report (OFR) 98-639. Table IB, Note 49.
(49) ``Methods of Analysis by the U.S. Geological Survey National
Water Quality Laboratory--Determination of Elements in Whole-Water
Digests Using Inductively Coupled Plasma-Optical Emission Spectrometry
and Inductively Coupled Plasma-Mass Spectrometry'' , Open File Report
(OFR) 98-165. Available from: U.S. Geological Survey, Denver Federal
Center, Box 25425, Denver, CO 80225. Table IB, Note 50.
(50) ``Methods of Analysis by the U.S. Geological Survey National
Water Quality Laboratory--Determination of Triazine and Other Nitrogen-
containing Compounds by Gas Chromatography with Nitrogen Phosphorus
Detectors'' U.S.Geological Survey Open File Report 94-37. Available
from: U.S. Geological Survey, Denver Federal Center, Box 25425, Denver,
CO 80225. Table ID, Note 9.
(51) ``Methods of Analysis by the U.S. Geological Survey National
Water Quality Laboratory--Determination of Inorganic and Organic
Constituents in Water and Fluvial Sediments'', Open File Report (OFR)
93-125. Available from: U.S. Geological Survey, Denver Federal Center,
Box 25425, Denver, CO 80225. Table IB, Note 51; Table IC, Note 9.
(52) IDEXX Laboratories, Inc. 2002. Description of Colilert
[reg], Colilert-18 [reg]'', Quanti-Tray
[reg], Quanti-Tray [reg]/2000, Enterolert
[reg] methods are available from IDEXX Laboratories, Inc.,
One Idexx Drive, Westbrook, Maine 04092. Table IA, Notes 17 and 23.
(53) Hach Company, Inc. Revision 2, 1999. Description of m-
ColiBlue24 [reg] Method, Total Coliforms and E. coli, is
available from Hach Company, 100 Dayton Ave., Ames, IA 50010. Table IA,
Note 18.
(54) USEPA. 2002. Method 1103.1: Escherichia coli (E. coli) in Water
by Membrane Filtration Using membrane-Thermotolerant Escherichia coli
Agar (mTEC). U.S. Environmental Protection Agency, Office of Water,
Washington D.C. September 2002, EPA-821-R-02-020. Available at NTIS,
PB2003-100125. Table IA, Note 20.
(55) USEPA. 2002. Method 1106.1: Enterococci in Water by Membrane
Filtration Using membrane-Enterococcus-Esculin Iron Agar (mE-EIA). U.S.
Environmental Protection Agency, Office of Water, Washington D.C.
September 2002, EPA-821-R-02-021. Available at NTIS, PB2003-100126.
Table IA, Note 24.
(56) USEPA. 2002. Method 1603: Escherichia coli (E. coli) in Water
by Membrane Filtration Using Modified membrane-Thermotolerant
Escherichia coli Agar (Modified mTEC). U.S. Environmental Protection
Agency, Office of Water, Washington, DC September 2002, EPA-821-R-02-
023. Available at NTIS, PB2003-100128. Table IA, Note 21.
(57) Brenner et al. 1993. New Medium for the Simultaneous Detection
of Total Coliforms and Escherichia coli in Water. Appl. Environ.
Microbiol. 59:3534-
[[Page 36]]
3544. Available from the American Society for Microbiology, 1752 N
Street NW., Washington, DC 20036. Table IA, Note 22.
(58) USEPA. 2002. Method 1604: Total Coliforms and Escherichia coli
(E. coli) in Water by Membrane Filtration using a Simultaneous Detection
Technique (MI Medium). U.S. Environmental Protection Agency, Office of
Water, Washington D.C. September 2002, EPA 821-R-02-024. Available from
NTIS, PB2003-100129. Table IA, Note 22.
(59) USEPA. 2002. Method 1600: Enterococci in Water by Membrane
Filtration using membrane-Enterococcus Indoxyl-[beta]-D-Glucoside Agar
(mEI). U.S. Environmental Protection Agency, Office of Water, Washington
D.C. September 2002, EPA-821-R-02-022. Available from NTIS, PB2003-
100127. Table IA, Note 25.
(60) USEPA. 2001. Method 1622: Cryptosporidium in Water by
Filtration/IMS/FA. U.S. Environmental Protection Agency, Office of
Water, Washington, DC April 2001, EPA-821-R-01-026.
Available from NTIS, PB2002-108709. Table IA, Note 26.
(61) USEPA. 2001. Method 1623: Cryptosporidium and Giardia in Water
by Filtration/IMS/FA. U.S. Environmental Protection Agency, Office of
Water, Washington, DC April 2001, EPA-821-R-01-025. Available from NTIS,
PB2002-108710. Table IA, Note 27.
(62) AOAC. 1995. Official Methods of Analysis of AOAC International,
16th Edition, Volume I, Chapter 17. AOAC International. 481 North
Frederick Avenue, Suite 500, Gaithersburg, Maryland 20877-2417. Table
IA, Note 11.
(c) Under certain circumstances the Regional Administrator or the
Director in the Region or State where the discharge will occur may
determine for a particular discharge that additional parameters or
pollutants must be reported. Under such circumstances, additional test
procedures for analysis of pollutants may be specified by the Regional
Administrator, or the Director upon the recommendation of the Director
of the Environmental Monitoring Systems Laboratory--Cincinnati.
(d) Under certain circumstances, the Administrator may approve, upon
recommendation by the Director, Environmental Monitoring Systems
Laboratory--Cincinnati, additional alternate test procedures for
nationwide use.
(e) Sample preservation procedures, container materials, and maximum
allowable holding times for parameters cited in Tables IA, IB, IC, ID,
and IE are prescribed in Table II. Any person may apply for a variance
from the prescribed preservation techniques, container materials, and
maximum holding times applicable to samples taken from a specific
discharge. Applications for variances may be made by letters to the
Regional Administrator in the Region in which the discharge will occur.
Sufficient data should be provided to assure such variance does not
adversely affect the integrity of the sample. Such data will be
forwarded, by the Regional Administrator, to the Director of the
Environmental Monitoring Systems Laboratory--Cincinnati, Ohio for
technical review and recommendations for action on the variance
application. Upon receipt of the recommendations from the Director of
the Environmental Monitoring Systems Laboratory, the Regional
Administrator may grant a variance applicable to the specific charge to
the applicant. A decision to approve or deny a variance will be made
within 90 days of receipt of the application by the Regional
Administrator.
Table II--Required Containers, Preservation Techniques, and Holding Times
----------------------------------------------------------------------------------------------------------------
Parameter No./name Container \1\ Preservation 2, 3 Maximum holding time \4\
----------------------------------------------------------------------------------------------------------------
Table IA--Bacteria Tests:
1-5 Coliform, total, fecal, PP, G........... Cool, <10 [deg]C, 0.0008% 6 hours.
and E. coli. Na2S2O35.
6 Fecal streptococci.......... PP, G........... Cool, <10[deg] 0.0008% Na2S2O35. 6 hours.
7 Enterococci................. PP, G........... Cool, <10[deg] 0.0008% Na2S2O35. 6 hours.
Table IA--Protozoa Tests:
8 Cryptosporidium............. LDPE............ 0-8 [deg]C...................... 96 hours. \17\
9 Giardia..................... LDPE............ 0-8 [deg]C...................... 96 hours. \17\
Table IA--Aquatic Toxicity
Tests:
6-10 Toxicity, acute and P,G............. Cool, 4 [deg]C 16............... 36 hours.
chronic.
[[Page 37]]
Table IB--Inorganic Tests:
1. Acidity.................... P, G............ Cool, 4[deg]C................... 14 days.
2. Alkalinity................. P, G............ ......do........................ Do.
4. Ammonia.................... P, G............ Cool, 4[deg]C, H2SO4 to pH<2.... 28 days.
9. Biochemical oxygen demand.. P, G............ Cool, 4[deg]C................... 48 hours.
10. Boron..................... P, PFTE, or HNO3 TO pH<2.................... 6 months.
Quartz.
11. Bromide................... P, G............ None required................... 28 days.
14. Biochemical oxygen demand, P, G............ Cool, 4[deg]C................... 48 hours.
carbonaceous.
15. Chemical oxygen demand.... P, G............ Cool, 4[deg]C, H2SO4 to pH<2.... 28 days.
16. Chloride.................. P, G............ None required................... Do.
17. Chlorine, total residual.. P, G............ ......do........................ Analyze immediately.
21. Color..................... P, G............ Cool, 4[deg]C................... 48 hours.
23-24. Cyanide, total and P, G............ Cool, 4[deg]C, NaOH to pH12, 0.6g ascorbic acid 5.
25. Fluoride.................. P............... None required................... 28 days.
27. Hardness.................. P, G............ HNO3 to pH<2, H2SO4 to pH<2..... 6 months.
28. Hydrogen ion (pH)......... P, G............ None required................... Analyze immediately.
31, 43. Kjeldahl and organic P, G............ Cool, 4[deg]C, H2SO4 to pH<2.... 28 days.
nitrogen.
Metals:7
18. Chromium VI \7\........... P, G............ Cool, 4 [deg]C.................. 24 hours.
35. Mercury \17\.............. P, G............ HNO3 to pH<2.................... 28 days.
3, 5-8, 12,13, 19, 20, 22, 26, P, G............ do.............................. 6 months.
29, 30, 32-34, 36, 37, 45,
47, 51, 52, 58-60, 62, 63, 70-
72, 74, 75. Metals except
boron, chromium VI and
mercury \7\.
38. Nitrate................... P, G............ Cool, 4[deg]C................... 48 hours.
39. Nitrate-nitrite........... P, G............ Cool, 4[deg]C, H2SO4 to pH<2.... 28 days.
40. Nitrite................... P, G............ Cool, 4[deg]C................... 48 hours.
41. Oil and grease............ G............... Cool to 4[deg]C, HCl or H2SO4 to 28 days.
pH<2.
42. Organic Carbon............ P, G............ Cool to 4 [deg]C HC1 or H2SO4 or 28 days.
H3PO4, to pH<2.
44. Orthophosphate............ P, G............ Filter immediately, Cool, 48 hours.
4[deg]C.
46. Oxygen, Dissolved Probe... G Bottle and top None required................... Analyze immediately.
47. Winkler................... ......do........ Fix on site and store in dark... 8 hours.
48. Phenols................... G only.......... Cool, 4[deg]C, H2SO4 to pH<2.... 28 days.
49. Phosphorus (elemental).... G............... Cool, 4[deg]C................... 48 hours.
50. Phosphorus, total......... P, G............ Cool, 4[deg]C, H2SO4 to pH<2.... 28 days.
53. Residue, total............ P, G............ Cool, 4[deg]C................... 7 days.
54. Residue, Filterable....... P, G............ ......do........................ 7 days.
55. Residue, Nonfilterable P, G............ ......do........................ 7 days.
(TSS).
56. Residue, Settleable....... P, G............ ......do........................ 48 hours.
57. Residue, volatile......... P, G............ ......do........................ 7 days.
61. Silica.................... P, PFTE, or Cool, 4 [deg]C.................. 28 days.
Quartz.
64. Specific conductance...... P, G............ ......do........................ Do.
65. Sulfate................... P, G............ ......do........................ Do.
66. Sulfide................... P, G............ Cool, 4[deg]C add zinc acetate 7 days.
plus sodium hydroxide to pH9.
67. Sulfite................... P, G............ None required................... Analyze immediately.
68. Surfactants............... P ,G............ Cool, 4[deg]C................... 48 hours.
69. Temperature............... P, G............ None required................... Analyze.
73. Turbidity................. P, G............ Cool, 4[deg]C................... 48 hours.
Table IC--Organic Tests \8\
13, 18-20, 22, 24-28, 34-37, G, Teflon-lined Cool, 4 [deg]C, 0.008% Na2S2O3 14 days.
39-43, 45-47, 56, 76, 104, septum. \5\..
105, 108-111, 113. Purgeable
Halocarbons.
6, 57, 106. Purgeable aromatic ......do........ Cool, 4 [deg]C, 0.008% Do.
hydrocarbons. Na2S2O3,\5\ HCl to pH2\9\.
3, 4. Acrolein and ......do........ Cool, 4 [deg]C, 0.008% Do.
acrylonitrile. Na2S2O3,\5\ adjust pH to 4-510.
23, 30, 44, 49, 53, 77, 80, G, Teflon-lined Cool, 4 [deg]C, 0.008% Na2S2O3 7 days until extraction;
81, 98, 100, 112. Phenols 11. cap.. \5\. 40 days after extraction.
7, 38. Benzidines 11.......... ......do........ ......do........................ 7 days until extraction.13
14, 17, 48, 50-52. Phthalate ......do........ Cool, 4 [deg]C.................. 7 days until extraction;
esters 11. 40 days after extraction.
[[Page 38]]
82-84. Nitrosamines 11 14..... ......do........ Cool, 4 [deg]C, 0.008% Do.
Na2S2O3,\5\ store in dark.
88-94. PCBs 11................ .....do......... Cool, 4 [deg]C.................. Do.
54, 55, 75, 79. Nitroaromatics ......do........ Cool, 4 [deg]C, 0.008% Do.
and isophorone 11. Na2S2O3,\5\ store in dark.
1, 2, 5, 8-12, 32, 33, 58, 59, ......do........ ......do........................ Do.
74, 78, 99, 101. Polynuclear
aromatic hydrocarbons 11.
15, 16, 21, 31, 87. Haloethers ......do........ Cool, 4 [deg]C, 0.008% Na2S2O3 Do.
11. \5\.
29, 35-37, 63-65, 73, 107. ......do........ Cool, 4 [deg]C.................. Do.
Chlorinated hydrocarbons 11.
60-62, 66-72, 85, 86, 95-97,
102, 103. CDDs/CDFs 11.
aqueous: field and lab G............... Cool, 0-4 [deg]C, pH<9, 0.008% 1 year.
preservation.. Na2S2O3 \5\.
Solids, mixed phase, and ......do........ Cool, <4 [deg]C................. 7 days.
tissue: field preservation..
Solids, mixed phase, and ......do........ Freeze, <-10 [deg]C............. 1 year.
tissue: lab preservation.
Table ID--Pesticides Tests:
1-70. Pesticides \11\......... ......do........ Cool, 4[deg]C, pH 5-9 15........ Do.
Table IE--Radiological Tests:
1-5. Alpha, beta and radium... P, G............ HNO3 to pH<2.................... 6 months.
----------------------------------------------------------------------------------------------------------------
Table II Notes
\1\ Polyethylene (P) or glass (G). For microbiology, plastic sample containers must be made of sterilizable
materials (polypropylene or other autoclavable plastic).
2 Sample preservation should be performed immediately upon sample collection. For composite chemical samples
each aliquot should be preserved at the time of collection. When use of an automated sampler makes it
impossible to preserve each aliquot, then chemical samples may be preserved by maintaining at 4[deg]C until
compositing and sample splitting is completed.
3 When any sample is to be shipped by common carrier or sent through the United States Mails, it must comply
with the Department of Transportation Hazardous Materials Regulations (49 CFR part 172). The person offering
such material for transportation is responsible for ensuring such compliance. For the preservation
requirements of Table II, the Office of Hazardous Materials, Materials Transportation Bureau, Department of
Transportation has determined that the Hazardous Materials Regulations do not apply to the following
materials: Hydrochloric acid (HCl) in water solutions at concentrations of 0.04% by weight or less (pH about
1.96 or greater); Nitric acid (HNO3) in water solutions at concentrations of 0.15% by weight or less (pH about
1.62 or greater); Sulfuric acid (H2SO4) in water solutions at concentrations of 0.35% by weight or less (pH
about 1.15 or greater); and Sodium hydroxide (NaOH) in water solutions at concentrations of 0.080% by weight
or less (pH about 12.30 or less).
\4\ Samples should be analyzed as soon as possible after collection. The times listed are the maximum times that
samples may be held before analysis and still be considered valid. Samples may be held for longer periods only
if the permittee, or monitoring laboratory, has data on file to show that for the specific types of samples
under study, the analytes are stable for the longer time, and has received a variance from the Regional
Administrator under Sec. 136.3(e). Some samples may not be stable for the maximum time period given in the
table. A permittee, or monitoring laboratory, is obligated to hold the sample for a shorter time if knowledge
exists to show that this is necessary to maintain sample stability. See Sec. 136.3(e) for details. The term
``analyze immediately'' usually means within 15 minutes or less of sample collection.
5 Should only be used in the presence of residual chlorine.
6 Maximum holding time is 24 hours when sulfide is present. Optionally all samples may be tested with lead
acetate paper before pH adjustments in order to determine if sulfide is present. If sulfide is present, it can
be removed by the addition of cadmium nitrate powder until a negative spot test is obtained. The sample is
filtered and then NaOH is added to pH 12.
7 Samples should be filtered immediately on-site before adding preservative for dissolved metals.
8 Guidance applies to samples to be analyzed by GC, LC, or GC/MS for specific compounds.
9 Sample receiving no pH adjustment must be analyzed within seven days of sampling.
10 The pH adjustment is not required if acrolein will not be measured. Samples for acrolein receiving no pH
adjustment must be analyzed within 3 days of sampling.
11 When the extractable analytes of concern fall within a single chemical category, the specified preservative
and maximum holding times should be observed for optimum safeguard of sample integrity. When the analytes of
concern fall within two or more chemical categories, the sample may be preserved by cooling to 4[deg]C,
reducing residual chlorine with 0.008% sodium thiosulfate, storing in the dark, and adjusting the pH to 6-9;
samples preserved in this manner may be held for seven days before extraction and for forty days after
extraction. Exceptions to this optional preservation and holding time procedure are noted in footnote 5 (re
the requirement for thiosulfate reduction of residual chlorine), and footnotes 12, 13 (re the analysis of
benzidine).
12 If 1,2-diphenylhydrazine is likely to be present, adjust the pH of the sample to 4.00.2 to
prevent rearrangement to benzidine.
13 Extracts may be stored up to 7 days before analysis if storage is conducted under an inert (oxidant-free)
atmosphere.
14 For the analysis of diphenylnitrosamine, add 0.008% Na2S2O3 and adjust pH to 7-10 with NaOH within 24 hours
of sampling.
15 The pH adjustment may be performed upon receipt at the laboratory and may be omitted if the samples are
extracted within 72 hours of collection. For the analysis of aldrin, add 0.008% Na2S2O3.
\16\ Sufficient ice should be placed with the samples in the shipping container to ensure that ice is still
present when the samples arrive at the laboratory. However, even if ice is present when the samples arrive, it
is necessary to immediately measure the temperature of the samples and confirm that the 4C temperature maximum
has not been exceeded. In the isolated cases where it can be documented that this holding temperature can not
be met, the permittee can be given the option of on-site testing or can request a variance. The request for a
variance should include supportive data which show that the toxicity of the effluent samples is not reduced
because of the increased holding temperature.
\17\ Samples collected for the determination of trace level mercury (100 ng/L) using EPA Method 1631 must be
collected in tightly-capped fluoropolymer or glass bottles and preserved with BrCl or HCl solution within 48
hours of sample collection. The time to preservation may be extended to 28 days if a sample is oxidized in the
sample bottle. Samples collected for dissolved trace level mercury should be filtered in the laboratory.
However, if circumstances prevent overnight shipment, samples should be filtered in a designated clean area in
the field in accordance with procedures given in Method 1669. Samples that have been collected for
determination of total or dissolved trace level mercury must be analyzed within 90 days of sample collection.
[[Page 39]]
[38 FR 28758, Oct. 16, 1973, as amended at 41 FR 52781, Dec. 1, 1976; 49
FR 43251, 43258, 43259, Oct. 26, 1984; 50 FR 691, 692, 695, Jan. 4,
1985; 51 FR 23693, June 30, 1986; 52 FR 33543, Sept. 3, 1987; 55 FR
24534, June 15, 1990; 55 FR 33440, Aug. 15, 1990; 56 FR 50759, Oct. 8,
1991; 57 FR 41833, Sept. 11, 1992; 58 FR 4505, Jan. 31, 1994; 60 FR
17160, Apr. 4, 1995; 60 FR 39588, 39590, Aug. 2, 1995; 60 FR 44672, Aug.
28, 1995; 60 FR 53542, 53543, Oct. 16, 1995; 62 FR 48403, 48404, Sept.
15, 1997; 63 FR 50423, Sept. 21, 1998; 64 FR 4978, Feb. 2, 1999; 64 FR
10392, Mar. 4, 1999; 64 FR 26327, May 14, 1999; 64 FR 30433, 30434, June
8, 1999; 64 FR 73423, Dec. 30, 1999; 66 FR 32776, June 18, 2001; 67 FR
65226, Oct. 23, 2002; 67 FR 65886, Oct. 29, 2002; 67 FR 69971, Nov. 19,
2002; 68 FR 43278, July 21, 2003; 68 FR 54934, Sept. 19, 2003; 69 FR
18803, Apr. 9, 2004]
Sec. 136.4 Application for alternate test procedures.
(a) Any person may apply to the Regional Administrator in the Region
where the discharge occurs for approval of an alternative test
procedure.
(b) When the discharge for which an alternative test procedure is
proposed occurs within a State having a permit program approved pursuant
to section 402 of the Act, the applicant shall submit his application to
the Regional Administrator through the Director of the State agency
having responsibility for issuance of NPDES permits within such State.
(c) Unless and until printed application forms are made available,
an application for an alternate test procedure may be made by letter in
triplicate. Any application for an alternate test procedure under this
paragraph (c) shall:
(1) Provide the name and address of the responsible person or firm
making the discharge (if not the applicant) and the applicable ID number
of the existing or pending permit, issuing agency, and type of permit
for which the alternate test procedure is requested, and the discharge
serial number.
(2) Identify the pollutant or parameter for which approval of an
alternate testing procedure is being requested.
(3) Provide justification for using testing procedures other than
those specified in Table I.
(4) Provide a detailed description of the proposed alternate test
procedure, together with references to published studies of the
applicability of the alternate test procedure to the effluents in
question.
(d) An application for approval of an alternate test procedure for
nationwide use may be made by letter in triplicate to the Director,
Analytical Methods Staff, Office of Science and Technology (4303),
Office of Water, U.S. Environmental Protection Agency, 1200 Pennsylvania
Ave., NW., Washington, DC 20460. Any application for an alternate test
procedure under this paragraph (d) shall:
(1) Provide the name and address of the responsible person or firm
making the application.
(2) Identify the pollutant(s) or parameter(s) for which nationwide
approval of an alternate testing procedure is being requested.
(3) Provide a detailed description of the proposed alternate
procedure, together with references to published or other studies
confirming the general applicability of the alternate test procedure to
the pollutant(s) or para meter(s) in waste water discharges from
representative and specified industrial or other categories.
(4) Provide comparability data for the performance of the proposed
alternate test procedure compared to the performance of the approved
test procedures.
[38 FR 28760, Oct. 16, 1973, as amended at 41 FR 52785, Dec. 1, 1976; 62
FR 30763, June 5, 1997]
Sec. 136.5 Approval of alternate test procedures.
(a) The Regional Administrator of the region in which the discharge
will occur has final responsibility for approval of any alternate test
procedure proposed by the responsible person or firm making the
discharge.
(b) Within thirty days of receipt of an application, the Director
will forward such application proposed by the responsible person or firm
making the discharge, together with his recommendations, to the Regional
Administrator. Where the Director recommends rejection of the
application for scientific and technical reasons which he provides, the
Regional Administrator shall deny the application,
[[Page 40]]
and shall forward a copy of the rejected application and his decision to
the Director of the State Permit Program and to the Director of the
Analytical Methods Staff, Washington, DC.
(c) Before approving any application for an alternate test procedure
proposed by the responsible person or firm making the discharge, the
Regional Administrator shall forward a copy of the application to the
Director of the Analytical Methods Staff, Washington, DC.
(d) Within ninety days of receipt by the Regional Administrator of
an application for an alternate test procedure, proposed by the
responsible person or firm making the discharge, the Regional
Administrator shall notify the applicant and the appropriate State
agency of approval or rejection, or shall specify the additional
information which is required to determine whether to approve the
proposed test procedure. Prior to the expiration of such ninety day
period, a recommendation providing the scientific and other technical
basis for acceptance or rejection will be forwarded to the Regional
Administrator by the Director of the Analytical Methods Staff,
Washington, DC. A copy of all approval and rejection notifications will
be forwarded to the Director, Analytical Methods Staff, Washington, DC,
for the purposes of national coordination.
(e) Approval for nationwide use. (1) Within sixty days of the
receipt by the Director of the Analytical Methods Staff, Washington, DC,
of an application for an alternate test procedure for nationwide use,
the Director of the Analytical Methods Staff shall notify the applicant
in writing whether the application is complete. If the application is
incomplete, the applicant shall be informed of the information necessary
to make the application complete.
(2) Within ninety days of the receipt of a complete package, the
Analytical Methods Staff shall perform any analysis necessary to
determine whether the alternate method satisfies the applicable
requirements of this part, and the Director of the Analytical Methods
Staff shall recommend to the Administrator that he/she approve or reject
the application and shall also notify the applicant of such
recommendation.
(3) As expeditiously as practicable, an alternate method determined
by the Administrator to satisfy the applicable requirements of this part
shall be proposed by EPA for incorporation in subsection 136.3 of 40 CFR
part 136. EPA shall make available for review all the factual bases for
its proposal, including any performance data submitted by the applicant
and any available EPA analysis of those data.
(4) Following a period of public comment, EPA shall, as
expeditiously as practicable, publish in the Federal Register a final
decision to approve or reject the alternate method.
[38 FR 28760, Oct. 16, 1973, as amended at 41 FR 52785, Dec. 1, 1976; 55
FR 33440, Aug. 15, 1990; 62 FR 30763, June 5, 1997]
Appendix A to Part 136--Methods for Organic Chemical Analysis of
Municipal and Industrial Wastewater
Method 601--Purgeable Halocarbons
1. Scope and Application
1.1 This method covers the determination of 29 purgeable
halocarbons.
The following parameters may be determined by this method:
------------------------------------------------------------------------
STORET
Parameter No. CAS No.
------------------------------------------------------------------------
Bromodichloromethane........................... 32101 75-27-4
Bromoform...................................... 32104 75-25-2
Bromomethane................................... 34413 74-83-9
Carbon tetrachloride........................... 32102 56-23-5
Chlorobenzene.................................. 34301 108-90-7
Chloroethane................................... 34311 75-00-3
2-Chloroethylvinyl ether....................... 34576 100-75-8
Chloroform..................................... 32106 67-66-3
Chloromethane.................................. 34418 74-87-3
Dibromochloromethane........................... 32105 124-48-1
1,2-Dichlorobenzene............................ 34536 95-50-1
1,3-Dichlorobenzene............................ 34566 541-73-1
1,4-Dichlorobenzene............................ 34571 106-46-7
Dichlorodifluoromethane........................ 34668 75-71-8
1,1-Dichloroethane............................. 34496 75-34-3
1,2-Dichloroethane............................. 34531 107-06-2
1,1-Dichloroethane............................. 34501 75-35-4
trans-1,2-Dichloroethene....................... 34546 156-60-5
1,2-Dichloropropane............................ 34541 78-87-5
cis-1,3-Dichloropropene........................ 34704 10061-01-5
trans-1,3-Dichloropropene...................... 34699 10061-02-6
Methylene chloride............................. 34423 75-09-2
1,1,2,2-Tetrachloroethane...................... 34516 79-34-5
Tetrachloroethene.............................. 34475 127-18-4
1,1,1-Trichloroethane.......................... 34506 71-55-6
1,1,2-Trichloroethane.......................... 34511 79-00-5
Tetrachloroethene.............................. 39180 79-01-6
Trichlorofluoromethane......................... 34488 75-69-4
Vinyl chloride................................. 39715 75-01-4
------------------------------------------------------------------------
[[Page 41]]
1.2 This is a purge and trap gas chro ma tographic (GC) method
applicable to the determination of the compounds listed above in
municipal and industrial discharges as provided under 40 CFR 136.1. When
this method is used to analyze unfamiliar samples for any or all of the
compounds above, compound identifications should be supported by at
least one additional qualitative technique. This method describes
analytical conditions for a second gas chromatographic column that can
be used to confirm measurements made with the primary column. Method 624
provides gas chromatograph/mass spectrometer (GC/MS) conditions
appropriate for the qualitative and quantitative confirmation of results
for most of the parameters listed above.
1.3 The method detection limit (MDL, defined in Section 12.1)
1 for each parameter is listed in Table 1. The MDL for a
specific wastewater may differ from those listed, depending upon the
nature of interferences in the sample matrix.
1.4 Any modification of this method, beyond those expressly
permitted, shall be considered as a major modification subject to
application and approval of alternate test procedures under 40 CFR 136.4
and 136.5.
1.5 This method is restricted to use by or under the supervision of
analysts experienced in the operation of a purge and trap system and a
gas chromatograph and in the interpretation of gas chromatograms. Each
analyst must demonstrate the ability to generate acceptable results with
this method using the procedure described in Section 8.2.
2. Summary of Method
2.1 An inert gas is bubbled through a 5-mL water sample contained in
a specially-designed purging chamber at ambient temperature. The
halocarbons are efficiently transferred from the aqueous phase to the
vapor phase. The vapor is swept through a sorbent trap where the
halocarbons are trapped. After purging is completed, the trap is heated
and backflushed with the inert gas to desorb the halocarbons onto a gas
chromatographic column. The gas chromatograph is temperature programmed
to separate the halocarbons which are then detected with a halide-
specific detector.2, 3
2.2 The method provides an optional gas chromatographic column that
may be helpful in resolving the compounds of interest from interferences
that may occur.
3. Interferences
3.1 Impurities in the purge gas and organic compounds outgassing
from the plumbing ahead of the trap account for the majority of
contamination problems. The analytical system must be demonstrated to be
free from contamination under the conditions of the analysis by running
laboratory reagent blanks as described in Section 8.1.3. The use of non-
Teflon plastic tubing, non-Teflon thread sealants, or flow controllers
with rubber components in the purge and trap system should be avoided.
3.2 Samples can be contaminated by diffusion of volatile organics
(particularly fluorocarbons and methylene chloride) through the septum
seal ilto the sample during shipment and storage. A field reagent blank
prepared from reagent water and carried through the sampling and
handling protocol can serve as a check on such contamination.
3.3 Contamination by carry-over can occur whenever high level and
low level samples are sequentially analyzed. To reduce carry-over, the
purging device and sample syringe must be rinsed with reagent water
between sample analyses. Whenever an unusually concentrated sample is
encountered, it should be followed by an analysis of reagent water to
check for cross contamination. For samples containing large amounts of
water-soluble materials, suspended solids, high boiling compounds or
high organohalide levels, it may be necessary to wash out the purging
device with a detergent solution, rinse it with distilled water, and
then dry it in a 105[deg]C oven between analyses. The trap and other
parts of the system are also subject to contamination; therefore,
frequent bakeout and purging of the entire system may be required.
4. Safety
4.1 The toxicity or carcinogenicity of each reagent used in this
method has not been precisely defined; however, each chemical compound
should be treated as a potential health hazard. From this viewpoint,
exposure to these chemicals must be reduced to the lowest possible level
by whatever means available. The laboratory is responsible for
maintaining a current awareness file of OSHA regulations regarding the
safe handling of the chemicals specified in this method. A reference
file of material data handling sheets should also be made available to
all personnel involved in the chemical analysis. Additional references
to laboratory safety are available and have been identified
4-6 for the information of the analyst.
4.2 The following parameters covered by this method have been
tentatively classified as known or suspected, human or mammalian
carcinogens: carbon tetrachloride, chloroform, 1,4-dichlorobenzene, and
vinyl chloride. Primary standards of these toxic compounds should be
prepared in a hood. A NIOSH/MESA approved toxic gas respirator should be
worn when the analyst handles high concentrations of these toxic
compounds.
[[Page 42]]
5. Apparatus and Materials
5.1 Sampling equipment, for discrete sampling.
5.1.1 Vial--25-mL capacity or larger, equipped with a screw cap with
a hole in the center (Pierce 13075 or equivalent). Detergent
wash, rinse with tap and distilled water, and dry at 105 [deg]C before
use.
5.1.2 Septum--Teflon-faced silicone (Pierce 12722 or
equivalent). Detergent wash, rinse with tap and distilled water, and dry
at 105 [deg]C for 1 h before use.
5.2 Purge and trap system--The purge and trap system consists of
three separate pieces of equipment: a purging device, trap, and
desorber. Several complete systems are now commercially available.
5.2.1 The purging device must be designed to accept 5-mL samples
with a water column at least 3 cm deep. The gaseous head space between
the water column and the trap must have a total volume of less than 15
mL. The purge gas must pass through the water column as finely divided
bubbles with a diameter of less than 3 mm at the origin. The purge gas
must be introduced no more than 5 mm from the base of the water column.
The purging device illustrated in Figure 1 meets these design criteria.
5.2.2 The trap must be at least 25 cm long and have an inside
diameter of at least 0.105 in. The trap must be packed to contain the
following minimum lengths of adsorbents: 1.0 cm of methyl silicone
coated packing (Section 6.3.3), 7.7 cm of 2,6-diphenylene oxide polymer
(Section 6.3.2), 7.7 cm of silica gel (Section 6.3.4), 7.7 cm of coconut
charcoal (Section 6.3.1). If it is not necessary to analyze for
dichlorodifluoromethane, the charcoal can be eliminated, and the polymer
section lengthened to 15 cm. The minimum specifications for the trap are
illustrated in Figure 2.
5.2.3 The desorber must be capable of rapidly heating the trap to
180 [deg]C. The polymer section of the trap should not be heated higher
than 180 [deg]C and the remaining sections should not exceed 200 [deg]C.
The desorber illustrated in Figure 2 meets these design criteria.
5.2.4 The purge and trap system may be assembled as a separate unit
or be coupled to a gas chromatograph as illustrated in Figures 3 and 4.
5.3 Gas chromatograph--An analytical system complete with a
temperature programmable gas chromatograph suitable for on-column
injection and all required accessories including syringes, analytical
columns, gases, detector, and strip-chart recorder. A data system is
recommended for measuring peak areas.
5.3.1 Column 1--8 ft long x 0.1 in. ID stainless steel or glass,
packed with 1% SP-1000 on Carbopack B (60/80 mesh) or equivalent. This
column was used to develop the method performance statements in Section
12. Guidelines for the use of alternate column packings are provided in
Section 10.1.
5.3.2 Column 2--6 ft long x 0.1 in. ID stainless steel or glass,
packed with chemically bonded n-octane on Porasil-C (100/120 mesh) or
equivalent.
5.3.3 Detector--Electrolytic conductivity or microcoulometric
detector. These types of detectors have proven effective in the analysis
of wastewaters for the parameters listed in the scope (Section 1.1). The
electrolytic conductivity detector was used to develop the method
performance statements in Section 12. Guidelines for the use of
alternate detectors are provided in Section 10.1.
5.4 Syringes--5-mL glass hypodermic with Luerlok tip (two each), if
applicable to the purging device.
5.5 Micro syringes--25-[micro]L, 0.006 in. ID needle.
5.6 Syringe valve--2-way, with Luer ends (three each).
5.7 Syringe--5-mL, gas-tight with shut-off valve.
5.8 Bottle--15-mL, screw-cap, with Teflon cap liner.
5.9 Balance--Analytical, capable of accurately weighing 0.0001 g.
6. Reagents
6.1 Reagent water--Reagent water is defined as a water in which an
interferent is not observed at the MDL of the parameters of interest.
6.1.1 Reagent water can be generated by passing tap water through a
carbon filter bed containing about 1 lb of activated carbon (Filtrasorb-
300, Calgon Corp., or equivalent).
6.1.2 A water purification system (Millipore Super-Q or equivalent)
may be used to generate reagent water.
6.1.3 Reagent water may also be prepared by boiling water for 15
min. Subsequently, while maintaining the temperature at 90 [deg]C,
bubble a contaminant-free inert gas through the water for 1 h. While
still hot, transfer the water to a narrow mouth screw-cap bottle and
seal with a Teflon-lined septum and cap.
6.2 Sodium thiosulfate--(ACS) Granular.
6.3 Trap Materials:
6.3.1 Coconut charcoal--6/10 mesh sieved to 26 mesh, Barnabey
Cheney, CA-580-26 lot M-2649 or equivalent.
6.3.2 2,6-Diphenylene oxide polymer--Tenax, (60/80 mesh),
chromatographic grade or equivalent.
6.3.3 Methyl silicone packing--3% OV-1 on Chromosorb-W (60/80 mesh)
or equivalent.
6.3.4 Silica gel--35/60 mesh, Davison, grade-15 or equivalent.
6.4 Methanol--Pesticide quality or equivalent.
6.5 Stock standard solutions--Stock standard solutions may be
prepared from
[[Page 43]]
pure standard materials or purchased as certified solutions. Prepare
stock standard solutions in methanol using assayed liquids or gases as
appropriate. Because of the toxicity of some of the organohalides,
primary dilutions of these materials should be prepared in a hood. A
NIOSH/MESA approved toxic gas respirator should be used when the analyst
handles high concentrations of such materials.
6.5.1 Place about 9.8 mL of methanol into a 10-mL ground glass
stoppered volumetric flask. Allow the flask to stand, unstoppered, for
about 10 min or until all alcohol wetted surfaces have dried. Weigh the
flask to the learest 0.1 mg.
6.5.2 Add the assayed reference material:
6.5.2.1 Liquid--Using a 100 [micro]L syringe, immediately add two or
more drops of assayed reference material to the flask, then reweigh. Be
sure that the drops fall directly into the alcohol without contacting
the neck of the flask.
6.5.2.2 Gases--To prepare standards for any of the six halocarbons
that boil below 30 [deg] C (bromomethane, chloroethane, chloro methane,
dichlorodifluoromethane, trichlorofluoromethane, vinyl chloride), fill a
5-mL valved gas-tight syringe with the reference standard to the 5.0-mL
mark. Lower the needle to 5 mm above the methanol meniscus. Slowly
introduce the reference standard above the surface of the liquid (the
heavy gas will rapidly dissolve into the methanol).
6.5.3 Reweigh, dilute to volume, stopper, then mix by inverting the
flask several times. Calculate the concentration in [micro]g/[micro]L
from the net gain in weight. When compound purity is assayed to be 96%
or greater, the weight can be used without correction to calculate the
concentration of the stock standard. Commercially prepared stock
standards can be used at any concentration if they are certified by the
malufacturer or by an independent source.
6.5.4 Transfer the stock standard solution into a Teflon-sealed
screw-cap bottle. Store, with minimal headspace, at -10 to -20 [deg]C
and protect from light.
6.5.5 Prepare fresh standards weekly for the six gases and 2-
chloroethylvinyl ether. All other standards must be replaced after one
month, or sooner if comparison with check standards indicates a problem.
6.6 Secondary dilution standards--Using stock standard solutions,
prepare secondary dilution standards in methanol that contain the
compounds of interest, either singly or mixed together. The secondary
dilution standards should be prepared at concentrations such that the
aqueous calibration standards prepared in Section 7.3.1 or 7.4.1 will
bracket the working range of the analytical system. Secondary dilution
standards should be stored with minimal headspace and should be checked
frequently for signs of degradation or evaporation, especially just
prior to preparing calibration standards from them.
6.7 Quality control check sample concentrate--See Section 8.2.1.
7. Calibration
7.1 Assemble a purge and trap system that meets the specifications
in Section 5.2. Condition the trap overnight at 180 [deg]C by
backflushing with an inert gas flow of at least 20 mL/min. Condition the
trap for 10 min once daily prior to use.
7.2 Connect the purge and trap system to a gas chromatograph. The
gas chromatograph must be operated using temperature and flow rate
conditions equivalent to those given in Table 1. Calibrate the purge and
trap-gas chromatographic system using either the external standard
technique (Section 7.3) or the internal standard technique (Section
7.4).
7.3 External standard calibration procedure:
7.3.1 Prepare calibration standards at a miminum of three
concentration levels for each parameter by carefully adding 20.0
[micro]L of one or more secondary dilution standards to 100, 500, or
1000 [micro]L of reagent water. A 25-[micro]L syringe with a 0.006 in.
ID needle should be used for this operation. One of the external
standards should be at a concentration near, but above, the MDL (Table
1) and the other concentrations should correspond to the expected range
of concentrations found in real samples or should define the working
range of the detector. These aqueous standards can be stored up to 24 h,
if held in sealed vials with zero headspace as described in Section 9.2.
If not so stored, they must be discarded after 1 h.
7.3.2 Analyze each calibration standard according to Section 10, and
tabulate peak height or area responses versus the concentration in the
standard. The results can be used to prepare a calibration curve for
each compound. Alternatively, if the ratio of response to concentration
(calibration factor) is a constant over the working range (<10% relative
standard deviation, RSD), linearity through the origin can be assumed
and the average ratio or calibration factor can be used in place of a
calibration curve.
7.4 Internal standard calibration procedure--To use this approach,
the analyst must select one or more internal standards that are similar
in analytical behavior to the compounds of interest. The analyst must
further demonstrate that the measurement of the internal standard is not
affected by method or matrix interferences. Because of these
limitations, no internal standard can be suggested that is applicable to
all samples. The compounds recommended for use as surrogate spikes in
Section 8.7 have been used successfully as internal standards, because
of their generally unique retention times.
[[Page 44]]
7.4.1 Prepare calibration standards at a minimum of three
concentration levels for each parameter of interest as described in
Section 7.3.1.
7.4.2 Prepare a spiking solution containing each of the internal
standards using the procedures described in Sections 6.5 and 6.6. It is
recommended that the secondary dilution standard be prepared at a
concentration of 15 [micro]g/mL of each internal standard compound. The
addition of 10 [micro]L of this standard to 5.0 mL of sample or
calibration standard would be equivalent to 30 [micro]g/L.
7.4.3 Analyze each calibration standard according to Section 10,
adding 10 [micro]L of internal standard spiking solution directly to the
syringe (Section 10.4). Tabulate peak height or area responses against
concentration for each compound and internal standard, and calculate
response factors (RF) for each compound using Equation 1.
[GRAPHIC] [TIFF OMITTED] TC15NO91.094
Equation 1
where:
As=Response for the parameter to be measured.
Ais=Response for the internal standard.
Cis=Concentration of the internal standard.
Cs=Concentration of the parameter to be measured.
If the RF value over the working range is a constant (<10% RSD), the RF
can be assumed to be invariant and the average RF can be used for
calculations. Alternatively, the results can be used to plot a
calibration curve of response ratios, As/Ais, vs.
RF.
7.5 The working calibration curve, calibration factor, or RF must be
verified on each working day by the measurement of a QC check sample.
7.5.1 Prepare the QC check sample as described in Section 8.2.2.
7.5.2 Analyze the QC check sample according to Section 10.
7.5.3 For each parameter, compare the response (Q) with the
corresponding calibration acceptance criteria found in Table 2. If the
responses for all parameters of interest fall within the designated
ranges, analysis of actual samples can begin. If any individual Q falls
outside the range, proceed according to Section 7.5.4.
Note: The large number of parameters in Table 2 present a
substantial probability that one or more will not meet the calibration
acceptance criteria when all parameters are analyzed.
7.5.4 Repeat the test only for those parameters that failed to meet
the calibration acceptance criteria. If the response for a parameter
does not fall within the range in this second test, a new calibration
curve, calibration factor, or RF must be prepared for that parameter
according to Section 7.3 or 7.4.
8. Quality Control
8.1 Each laboratory that uses this method is required to operate a
formal quality control program. The minimum requirements of this program
consist of an initial demonstration of laboratory capability and an
ongoing analysis of spiked samples to evaluate and document data
quality. The laboratory must maintain records to document the quality of
data that is generated. Ongoing data quality checks are compared with
established performance criteria to determine if the results of analyses
meet the performance characteristics of the method. When results of
sample spikes indicate atypical method performance, a quality control
check standard must be analyzed to confirm that the measurements were
performed in an in-control mode of operation.
8.1.1 The analyst must make an initial, one-time, demonstration of
the ability to generate acceptable accuracy and precision with this
method. This ability is established as described in Section 8.2.
8.1.2 In recognition of advances that are occurring in
chromatography, the analyst is permitted certain options (detailed in
Section 10.1) to improve the separations or lower the cost of
measurements. Each time such a modification is made to the method, the
analyst is required to repeat the procedure in Section 8.2.
8.1.3 Each day, the analyst must analyze a reagent water blank to
demonstrate that interferences from the analytical system are under
control.
8.1.4 The laboratory must, on an ongoing basis, spike and analyze a
minimum of 10% of all samples to monitor and evaluate laboratory data
quality. This procedure is described in Section 8.3.
8.1.5 The laboratory must, on an ongoing basis, demonstrate through
the analyses of quality control check standards that the operation of
the measurement system is in control. This procedure is described in
Section 8.4. The frequency of the check standard analyses is equivalent
to 10% of all samples analyzed but may be reduced if spike recoveries
from samples (Section 8.3) meet all specified quality control criteria.
8.1.6 The laboratory must maintain performance records to document
the quality of data that is generated. This procedure is described in
Section 8.5.
8.2 To establish the ability to generate acceptable accuracy and
precision, the analyst must perform the following operations.
8.2.1 A quality control (QC) check sample concentrate is required
containing each parameter of interest at a concentration of 10 [micro]g/
mL in methanol. The QC check sample concentrate must be obtained from
the U.S.
[[Page 45]]
Environmental Protection Agency, Environmental Monitoring and Support
Laboratory in Cincinnati, Ohio, if available. If not available from that
source, the QC check sample concentrate must be obtained from another
external source. If not available from either source above, the QC check
sample concentrate must be prepared by the laboratory using stock
standards prepared independently from those used for calibration.
8.2.2 Prepare a QC check sample to contain 20 [micro]g/L of each
parameter by adding 200 [micro]L of QC check sample concentrate to 100
mL of reagent water.
8.2.3 Analyze four 5-mL aliquots of the well-mixed QC check sample
according to Section 10.
8.2.4 Calculate the average recovery (X) in [micro]g/L, and the
standard deviation of the recovery (s) in [micro]g/L, for each parameter
of interest using the four results.
8.2.5 For each parameter compare s and X with the corresponding
acceptance criteria for precision and accuracy, respectively, found in
Table 2. If s and X for all parameters of interest meet the acceptance
criteria, the system performance is acceptable and analysis of actual
samples can begin. If any individual s exceeds the precision limit or
any individual X falls outside the range for accuracy, then the system
performance is unacceptable for that parameter.
Note: The large number of parameters in Table 2 present a
substantial probability that one or more will fail at least one of the
acceptance criteria when all parameters are analyzed.
8.2.6 When one or more of the parameters tested fail at least one of
the acceptance criteria, the analyst must proceed according to Section
8.2.6.1 or 8.2.6.2.
8.2.6.1 Locate and correct the source of the problem and repeat the
test for all parameters of interest beginning with Section 8.2.3.
8.2.6.2 Beginning with Section 8.2.3, repeat the test only for those
parameters that failed to meet criteria. Repeated failure, however, will
confirm a general problem with the measurement system. If this occurs,
locate and correct the source of the problem and repeat the test for all
compounds of interest beginning with Section 8.2.3.
8.3 The laboratory must, on an ongoing basis, spike at least 10% of
the samples from each sample site being monitored to assess accuracy.
For laboratories analyzing one to ten samples per month, at least one
spiked sample per month is required.
8.3.1 The concentration of the spike in the sample should be
determined as follows:
8.3.1.1 If, as in compliance monitoring, the concentration of a
specific parameter in the sample is being checked against a regulatory
concentration limit, the spike should be at that limit or 1 to 5 times
higher than the background concentration determined in Section 8.3.2,
whichever concentration would be larger.
8.3.1.2 If the concentration of a specific parameter in the sample
is not being checked against a limit specific to that parameter, the
spike should be at 20 [micro]g/L or 1 to 5 times higher than the
background concentration determined in Section 8.3.2, whichever
concentration would be larger.
8.3.2 Analyze one 5-mL sample aliquot to determine the background
concentration (B) of each parameter. If necessary, prepare a new QC
check sample concentrate (Section 8.2.1) appropriate for the background
concentrations in the sample. Spike a second 5-mL sample aliquot with 10
[micro]L of the QC check sample concentrate and analyze it to determine
the concentration after spiking (A) of each parameter. Calculate each
percent recovery (P) as 100(A-B)%/T, where T is the known true value of
the spike.
8.3.3 Compare the percent recovery (P) for each parameter with the
corresponding QC acceptance criteria found in Table 2. These acceptance
criteria were calculated to include an allowance for error in
measurement of both the background and spike concentrations, assuming a
spike to background ratio of 5:1. This error will be accounted for to
the extent that the analyst's spike to background ratio approaches
5:1.7 If spiking was performed at a concentration lower than
20 [micro]g/L, the analyst must use either the QC acceptance criteria in
Table 2, or optional QC acceptance criteria calculated for the specific
spike concentration. To calculate optional acceptance criteria for the
recovery of a parameter: (1) Calculate accuracy (X') using the equation
in Table 3, substituting the spike concentration (T) for C; (2)
calculate overall precision (S') using the equation in Table 3,
substituting X' for X; (3) calculate the range for recovery at the spike
concentration as (100 X'/T)2.44(100 S'/
T)%.7
8.3.4 If any individual P falls outside the designated range for
recovery, that parameter has failed the acceptance criteria. A check
standard containing each parameter that failed the criteria must be
analyzed as described in Section 8.4.
8.4 If any parameter fails the acceptance criteria for recovery in
Section 8.3, a QC check standard containing each parameter that failed
must be prepared and analyzed.
Note: The frequency for the required analysis of a QC check standard
will depend upon the number of parameters being simultaneously tested,
the complexity of the sample matrix, and the performance of the
laboratory. If the entire list of parameters in Table 2 must be measured
in the sample in Section 8.3, the probability that the analysis of a QC
check standard will be required is high. In this case the QC check
standard should be routinely analyzed with the spiked sample.
8.4.1 Prepare the QC check standard by adding 10 [micro]L of QC
check sample concentrate
[[Page 46]]
(Section 8.2.1 or 8.3.2) to 5 mL of reagent water. The QC check standard
needs only to contain the parameters that failed criteria in the test in
Section 8.3.
8.4.2 Analyze the QC check standard to determine the concentration
measured (A) of each parameter. Calculate each percent recovery
(Ps) as 100 (A/T)%, where T is the true value of the standard
concentration.
8.4.3 Compare the percent recovery (Ps) for each
parameter with the corresponding QC acceptance criteria found in Table
2. Only parameters that failed the test in Section 8.3 need to be
compared with these criteria. If the recovery of any such parameter
falls outside the designated range, the laboratory performance for that
parameter is judged to be out of control, and the problem must be
immediately identified and corrected. The analytical result for that
parameter in the unspiked sample is suspect and may not be reported for
regulatory compliance purposes.
8.5 As part of the QC program for the laboratory, method accuracy
for wastewater samples must be assessed and records must be maintained.
After the analysis of five spiked wastewater samples as in Section 8.3,
calculate the average percent recovery (P) and the standard deviation of
the percent recovery (sp). Express the accuracy assessment as
a percent recovery interval from P-2sp to P+2sp.
If p=90% and sp=10%, for example, the accuracy interval is
expressed as 70-110%. Update the accuracy assessment for each parameter
on a regular basis (e.g. after each five to ten new accuracy
measurements).
8.6 It is recommended that the laboratory adopt additional quality
assurance practices for use with this method. The specific practices
that are most productive depend upon the needs of the laboratory and the
nature of the samples. Field duplicates may be analyzed to assess the
precision of the environmental measurements. When doubt exists over the
identification of a peak on the chromatogram, confirmatory techniques
such as gas chromatography with a dissimilar column, specific element
detector, or mass spectrometer must be used. Whenever possible, the
laboratory should analyze standard reference materials and participate
in relevant performance evaluation studies.
8.7 The analyst should monitor both the performance of the
analytical system and the effectiveness of the method in deal ing with
each sample matrix by spiking each sample, standard, and reagent water
blank with surrogate halocarbons. A combination of bromochloromethane,
2-bromo-1-chloropropane, and 1,4-dichlorobu tane is recommended to
encompass the range of the temperature program used in this method. From
stock standard solutions prepared as in Section 6.5, add a volume to
give 750 [micro]g of each surrogate to 45 mL of reagent water contained
in a 50-mL volumetric flask, mix and dilute to volume for a
concentration of 15 ng/[micro]L. Add 10 [micro]L of this surrogate
spiking solution directly into the 5-mL syringe with every sample and
reference standard analyzed. Prepare a fresh surrogate spiking solution
on a weekly basis. If the internal standard calibration procedure is
being used, the surrogate compounds may be added directly to the
internal standard spiking solution (Section 7.4.2).
9. Sample Collection, Preservation, and Handling
9.1 All samples must be iced or refrigerated from the time of
collection until analysis. If the sample contains free or combined
chlorine, add sodium thiosulfate preservative (10 mg/40 mL is sufficient
for up to 5 ppm Cl2) to the empty sample bottle just prior to
shipping to the sampling site. EPA Methods 330.4 and 330.5 may be used
for measurement of residual chlorine.8 Field test kits are
available for this purpose.
9.2 Grab samples must be collected in glass containers having a
total volume of at least 25 mL. Fill the sample bottle just to
overflowing in such a manner that no air bubbles pass through the sample
as the bottle is being filled. Seal the bottle so that no air bubbles
are entrapped in it. If preservative has been added, shake vigorously
for 1 min. Maintain the hermetic seal on the sample bottle until time of
analysis.
9.3 All samples must be analyzed within 14 days of
collection.3
10. Procedure
10.1 Table 1 summarizes the recommended operating conditions for the
gas chromatograph. Included in this table are estimated retention times
and MDL that can be achieved under these conditions. An example of the
separations achieved by Column 1 is shown in Figure 5. Other packed
columns, chromatographic conditions, or detectors may be used if the
requirements of Section 8.2 are met.
10.2 Calibrate the system daily as described in Section 7.
10.3 Adjust the purge gas (nitrogen or helium) flow rate to 40 mL/
min. Attach the trap inlet to the purging device, and set the purge and
trap system to purge (Figure 3). Open the syringe valve located on the
purging device sample introduction needle.
10.4 Allow the sample to come to ambient temperature prior to
introducing it to the syringe. Remove the plunger from a 5-mL syringe
and attach a closed syringe valve. Open the sample bottle (or standard)
and carefully pour the sample into the syringe barrel to just short of
overflowing. Replace the syringe plunger and compress the sample. Open
the syringe valve and vent any residual air while adjusting the sample
volume to 5.0 mL. Since this process of taking an aliquot destroys the
validity of the sample for future
[[Page 47]]
analysis, the analyst should fill a second syringe at this time to
protect against possible loss of data. Add 10.0 [micro]L of the
surrogate spiking solution (Section 8.7) and 10.0 [micro]L of the
internal standard spiking solution (Section 7.4.2), if applicable,
through the valve bore, then close the valve.
10.5 Attach the syringe-syringe valve assembly to the syringe valve
on the purging device. Open the syringe valves and inject the sample
into the purging chamber.
10.6 Close both valves and purge the sample for 11.00.1 min at ambient temperature.
10.7 After the 11-min purge time, attach the trap to the
chromatograph, adjust the purge and trap system to the desorb mode
(Figure 4), and begin to temperature program the gas chromatograph.
Introduce the trapped materials to the GC column by rapidly heating the
trap to 180 [deg]C while backflushing the trap with an inert gas between
20 and 60 mL/min for 4 min. If rapid heating of the trap cannot be
achieved, the GC column must be used as a secondary trap by cooling it
to 30 [deg]C (subambient temperature, if poor peak geometry or random
retention time problems persist) instead of the initial program
temperature of 45 [deg]C
10.8 While the trap is being desorbed into the gas chromatograph,
empty the purging chamber using the sample introduction syringe. Wash
the chamber with two 5-mL flushes of reagent water.
10.9 After desorbing the sample for 4 min, recondition the trap by
returning the purge and trap system to the purge mode. Wait 15 s then
close the syringe valve on the purging device to begin gas flow through
the trap. The trap temperature should be maintained at 180 [deg]C After
approximately 7 min, turn off the trap heater and open the syringe valve
to stop the gas flow through the trap. When the trap is cool, the next
sample can be analyzed.
10.10 Identify the parameters in the sample by comparing the
retention times of the peaks in the sample chromatogram with those of
the peaks in standard chromatograms. The width of the retention time
window used to make identifications should be based upon measurements of
actual retention time variations of standards over the course of a day.
Three times the standard deviation of a retention time for a compound
can be used to calculate a suggested window size; however, the
experience of the analyst should weigh heavily in the interpretation of
chromatograms.
10.11 If the response for a peak exceeds the working range of the
system, prepare a dilution of the sample with reagent water from the
aliquot in the second syringe and reanalyze.
11. Calculations
11.1 Determine the concentration of individual compounds in the
sample.
11.1.1 If the external standard calibration procedure is used,
calculate the concentration of the parameter being measured from the
peak response using the calibration curve or calibration factor
determined in Section 7.3.2.
11.1.2 If the internal standard calibration procedure is used,
calculate the concentration in the sample using the response factor (RF)
determined in Section 7.4.3 and Equation 2.
Equation 2
[GRAPHIC] [TIFF OMITTED] TC15NO91.095
where:
As=Response for the parameter to be measured.
Ais=Response for the internal standard.
Cis=Concentration of the internal standard.
11.2 Report results in [micro]g/L without correction for recovery
data. All QC data obtained should be reported with the sample results.
12. Method Performance
12.1 The method detection limit (MDL) is defined as the minimum
concentration of a substance that can be measured and re ported with 99%
confidence that the value is above zero. \1\ The MDL concentration
listed in Table 1 were obtained using reagent water.11.
Similar results were achieved using representative wastewaters. The MDL
actu ally achieved in a given analysis will vary depending on instrument
sensitivity and matrix effects.
12.2 This method is recommended for use in the concentration range
from the MDL to 1000xMDL. Direct aqueous injection techniques should be
used to measure concentration levels above 1000xMDL.
12.3 This method was tested by 20 laboratories using reagent water,
drinking water, surface water, and three industrial wastewaters spiked
at six concentrations over the range 8.0 to 500 [micro]g/L.9
Single operator precision, overall precision, and method accuracy were
found to be directly related to the concentration of the parameter and
essentially independent of the sample matrix. Linear equations to
describe these relationships are presented in Table 3.
References
1. 40 CFR part 136, appendix B.
2. Bellar, T.A., and Lichtenberg, J.J. ``Determining Volatile
Organics at Microgram-per-Litre-Levels by Gas Chromatography,'' Journal
of the American Water Works Association, 66, 739 (1974).
3. Bellar, T.A., and Lichtenberg, J.J. ``Semi-Automated Headspace
Analysis of Drinking Waters and Industrial Waters for
[[Page 48]]
Purgeable Volatile Organic Compounds,'' Proceedings from Symposium on
Measurement of Organic Pollutants in Water and Wastewater, American
Society for Testing and Materials, STP 686, C.E. Van Hall, editor, 1978.
4. ``Carcinogens--Working With Carcinogens,'' Department of Health,
Education, and Welfare, Public Health Service, Center for Disease
Control, National Institute for Occupational Safety and Health,
Publication No. 77-206, August 1977.
5. ``OSHA Safety and Health Standards, General Industry'' (29 CFR
part 1910), Occupational Safety and Health Administration, OSHA 2206
(Revised, January 1976).
6. ``Safety in Academic Chemistry Laboratories,'' American Chemical
Society Publication, Committee on Chemical Safety, 3rd Edition, 1979.
7. Provost, L.P., and Elder, R.S. ``Interpretation of Percent
Recovery Data,'' American Laboratory, 15, 58-63 (1983). (The value 2.44
used in the equation in Section 8.3.3 is two times the value 1.22
derived in this report.)
8. ``Methods 330.4 (Titrimetric, DPD-FAS) and 330.5
(Spectrophotometric, DPD) for Chlorine, Total Residual,'' Methods for
Chemical Analysis of Water and Wastes, EPA 600/4-79-020, U.S.
Environmental Protection Agency, Environmental Monitoring and Support
Laboratory, Cincinnati, Ohio 45268, March 1979.
9. ``EPA Method Study 24, Method 601--Purgeable Halocarbons by the
Purge and Trap Method,'' EPA 600/4-84-064, National Technical
Information Service, PB84-212448, Springfield, Virginia 22161, July
1984.
10. ``Method Validation Data for EPA Method 601,'' Memorandum from
B. Potter, U.S. Environmental Protection Agency, Environmental
Monitoring and Support Laboratory, Cincinnati, Ohio 45268, November 10,
1983.
11. Bellar, T. A., Unpublished data, U.S. Environmental Protection
Agency, Environmental Monitoring and Support Laboratory, Cincinnati,
Ohio 45268, 1981.
Table 1--Chromatographic Conditions and Method Detection Limits
----------------------------------------------------------------------------------------------------------------
Retention time (min) Method detection
Parameter ------------------------------------ limit ([micro]g/
Column 1 Column 2 L)
----------------------------------------------------------------------------------------------------------------
Chloromethane............................................. 1.50 5.28 0.08
Bromomethane.............................................. 2.17 7.05 1.18
Dichlorodifluoromethane................................... 2.62 nd 1.81
Vinyl chloride............................................ 2.67 5.28 0.18
Chloroethane.............................................. 3.33 8.68 0.52
Methylene chloride........................................ 5.25 10.1 0.25
Trichlorofluoromethane.................................... 7.18 nd nd
1,1-Dichloroethene........................................ 7.93 7.72 0.13
1,1-Dichloroethane........................................ 9.30 12.6 0.07
trans-1,2-Dichloroethene.................................. 10.1 9.38 0.10
Chloroform................................................ 10.7 12.1 0.05
1,2-Dichloroethane........................................ 11.4 15.4 0.03
1,1,1-Trichloroethane..................................... 12.6 13.1 0.03
Carbon tetrachloride...................................... 13.0 14.4 0.12
Bromodichloromethane...................................... 13.7 14.6 0.10
1,2-Dichloropropane....................................... 14.9 16.6 0.04
cis-1,3-Dichloropropene................................... 15.2 16.6 0.34
Trichloroethene........................................... 15.8 13.1 0.12
Dibromochloromethane...................................... 16.5 16.6 0.09
1,1,2-Trichloroethane..................................... 16.5 18.1 0.02
trans-1,3-Dichloropropene................................. 16.5 18.0 0.20
2-Chloroethylvinyl ether.................................. 18.0 nd 0.13
Bromoform................................................. 19.2 19.2 0.20
1,1,2,2-Tetrachloroethane................................. 21.6 nd 0.03
Tetrachloroethene......................................... 21.7 15.0 0.03
Chlorobenzene............................................. 24.2 18.8 0.25
1,3-Dichlorobenzene....................................... 34.0 22.4 0.32
1,2-Dichlorobenzene....................................... 34.9 23.5 0.15
1,4-Dichlorobenzene....................................... 35.4 22.3 0.24
----------------------------------------------------------------------------------------------------------------
Column 1 conditions: Carbopack B (60/80 mesh) coated with 1% SP-1000 packed in an 8 ft x 0.1 in. ID stainless
steel or glass column with helium carrier gas at 40 mL/min flow rate. Column temperature held at 45 [deg]C for
3 min then programmed at 8 [deg]C/min to 220 [deg]C and held for 15 min.
Column 2 conditions: Porisil-C (100/120 mesh) coated with n-octane packed in a 6 ft x 0.1 in. ID stainless steel
or glass column with helium carrier gas at 40 mL/min flow rate. Column temperature held at 50 [deg]C for 3 min
then programmed at 6 [deg]C/min to 170 [deg]C and held for 4 min.
nd=not determined.
[[Page 49]]
Table 2--Calibration and QC Acceptance Criteria--Method 601 a
----------------------------------------------------------------------------------------------------------------
Limit for
Range for Q s Range for X Range P,
Parameter ([micro]g/L) ([micro]g/ ([micro]g/L) Ps (%)
L)
----------------------------------------------------------------------------------------------------------------
Bromodichloromethane.................................... 15.2-24.8 4.3 10.7-32.0 42-172
Bromoform............................................... 14.7-25.3 4.7 5.0-29.3 13-159
Bromomethane............................................ 11.7-28.3 7.6 3.4-24.5 D-144
Carbon tetrachloride.................................... 13.7-26.3 5.6 11.8-25.3 43-143
Chlorobenzene........................................... 14.4-25.6 5.0 10.2-27.4 38-150
Chloroethane............................................ 15.4-24.6 4.4 11.3-25.2 46-137
2-Chloroethylvinyl ether................................ 12.0-28.0 8.3 4.5-35.5 14-186
Chloroform.............................................. 15.0-25.0 4.5 12.4-24.0 49-133
Chloromethane........................................... 11.9-28.1 7.4 D-34.9 D-193
Dibromochloromethane.................................... 13.1-26.9 6.3 7.9-35.1 24-191
1,2-Dichlorobenzene..................................... 14.0-26.0 5.5 1.7-38.9 D-208
1,3-Dichlorobenzene..................................... 9.9-30.1 9.1 6.2-32.6 7-187
1,4-Dichlorobenzene..................................... 13.9-26.1 5.5 11.5-25.5 42-143
1,1-Dichloroethane...................................... 16.8-23.2 3.2 11.2-24.6 47-132
1,2-Dichloroethane...................................... 14.3-25.7 5.2 13.0-26.5 51-147
1,1-Dichloroethene...................................... 12.6-27.4 6.6 10.2-27.3 28-167
trans-1,2-Dichloroethene................................ 12.8-27.2 6.4 11.4-27.1 38-155
1,2-Dichloropropane..................................... 14.8-25.2 5.2 10.1-29.9 44-156
cis-1,3-Dichloropropene................................. 12.8-27.2 7.3 6.2-33.8 22-178
trans-1,3-Dichloropropene............................... 12.8-27.2 7.3 6.2-33.8 22-178
Methylene chloride...................................... 15.5-24.5 4.0 7.0-27.6 25-162
1,1,2,2-Tetrachloroethane............................... 9.8-30.2 9.2 6.6-31.8 8-184
Tetrachloroethene....................................... 14.0-26.0 5.4 8.1-29.6 26-162
1,1,1-Trichloroethane................................... 14.2-25.8 4.9 10.8-24.8 41-138
1,1,2-Trichloroethane................................... 15.7-24.3 3.9 9.6-25.4 39-136
Trichloroethene......................................... 15.4-24.6 4.2 9.2-26.6 35-146
Trichlorofluoromethane.................................. 13.3-26.7 6.0 7.4-28.1 21-156
Vinyl chloride.......................................... 13.7-26.3 5.7 8.2-29.9 28-163
----------------------------------------------------------------------------------------------------------------
a Criteria were calculated assuming a QC check sample concentration of 20 [micro]g/L.
Q=Concentration measured in QC check sample, in [micro]g/L (Section 7.5.3).
s=Standard deviation of four recovery measurements, in [micro]g/L (Section 8.2.4).
X=Average recovery for four recovery measurements, in [micro]g/L (Section 8.2.4).
P, Ps=Percent recovery measured (Section 8.3.2, Section 8.4.2).
D=Detected; result must be greater than zero.
Note: These criteria are based directly upon the method performance data in Table 3. Where necessary, the limits
for recovery have been broadened to assure applicability of the limits to concentrations below those used to
develop Table 3.
Table 3--Method Accuracy and Precision as Functions of Concentration--Method 601
----------------------------------------------------------------------------------------------------------------
Single analyst
Parameter Accuracy, as recovery, precision, sr' Overall precision, S'
X' ([micro]g/L) ([micro]g/L) ([micro]g/L)
----------------------------------------------------------------------------------------------------------------
Bromodichloromethane................ 1.12C-1.02 0.11X+0.04 0.20X+1.00
Bromoform........................... 0.96C-2.05 0.12X+0.58 0.21X+2.41
Bromomethane........................ 0.76C-1.27 0.28X+0.27 0.36X+0.94
Carbon tetrachloride................ 0.98C-1.04 0.15X+0.38 0.20X+0.39
Chlorobenzene....................... 1.00C-1.23 0.15X-0.02 0.18X+1.21
Choroethane......................... 0.99C-1.53 0.14X-0.13 0.17X+0.63
2-Chloroethylvinyl ether a.......... 1.00C 0.20X 0.35X
Chloroform.......................... 0.93C-0.39 0.13X+0.15 0.19X-0.02
Chloromethane....................... 0.77C+0.18 0.28X-0.31 0.52X+1.31
Dibromochloromethane................ 0.94C+2.72 0.11X+1.10 0.24X+1.68
1,2-Dichlorobenzene................. 0.93C+1.70 0.20X+0.97 0.13X+6.13
1,3-Dichlorobenzene................. 0.95C+0.43 0.14X+2.33 0.26X+2.34
1,4-Dichlorobenzene................. 0.93C-0.09 0.15X+0.29 0.20X+0.41
1,1-Dichloroethane.................. 0.95C-1.08 0.09X+0.17 0.14X+0.94
1,2-Dichloroethane.................. 1.04C-1.06 0.11X+0.70 0.15X+0.94
1,1-Dichloroethene.................. 0.98C-0.87 0.21X-0.23 0.29X-0.40
trans-1,2-Dichloroethene............ 0.97C-0.16 0.11X+1.46 0.17X+1.46
1,2-Dichloropropane a............... 1.00C 0.13X 0.23X
cis-1,3-Dichloropropene a........... 1.00C 0.18X 0.32X
trans-1,3-Dichloropropene a......... 1.00C 0.18X 0.32X
Methylene chloride.................. 0.91C-0.93 0.11X+0.33 0.21X+1.43
1,1,2,2-Tetrachloroethene........... 0.95C+0.19 0.14X+2.41 0.23X+2.79
Tetrachloroethene................... 0.94C+0.06 0.14X+0.38 0.18X+2.21
1,1,1-Trichloroethane............... 0.90C-0.16 0.15X+0.04 0.20X+0.37
1,1,2-Trichloroethane............... 0.86C+0.30 0.13X-0.14 0.19X+0.67
Trichloroethene..................... 0.87C+0.48 0.13X-0.03 0.23X+0.30
Trichlorofluoromethane.............. 0.89C-0.07 0.15X+0.67 0.26X+0.91
Vinyl chloride...................... 0.97C-0.36 0.13X+0.65 0.27X+0.40
----------------------------------------------------------------------------------------------------------------
X'=Expected recovery for one or more measurements of a sample containing a concentration of C, in [micro]g/L.
[[Page 50]]
sn'=Expected single analyst standard deviation of measurements at an average concentration found of X, in
[micro]g/L.
S\1\=Expected interlaboratory standard deviation of measurements at an average concentration found of X, in
[micro]g/L.
C=True value for the concentration, in [micro]g/L.
X=Average recovery found for measurements of samples containing a concentration of C, in [micro]g/L.
a Estimates based upon the performance in a single laboratory.\10\
[GRAPHIC] [TIFF OMITTED] TC02JY92.000
[[Page 51]]
[GRAPHIC] [TIFF OMITTED] TC02JY92.001
[[Page 52]]
[GRAPHIC] [TIFF OMITTED] TC02JY92.002
[[Page 53]]
[GRAPHIC] [TIFF OMITTED] TC02JY92.003
[[Page 54]]
Method 602--Purgeable Aromatics
1. Scope and Application
1.1 This method covers the determination of various purgeable
aromatics. The following parameters may be determined by this method:
------------------------------------------------------------------------
STORET
Parameter No. CAS No.
------------------------------------------------------------------------
Benzene.......................................... 34030 71-43-2
Chlorobenzene.................................... 34301 108-90-7
1,2-Dichlorobenzene.............................. 34536 95-50-1
1,3-Dichlorobenzene.............................. 34566 541-73-1
1,4-Dichlorobenzene.............................. 34571 106-46-7
Ethylbenzene..................................... 34371 100-41-4
Toluene.......................................... 34010 108-88-3
------------------------------------------------------------------------
1.2 This is a purge and trap gas chromatographic (GC) method
applicable to the determination of the compounds listed above in
municipal and industrial discharges as provided under 40 CFR 136.1. When
this method is used to analyze unfamiliar samples for any or all of the
compounds above, compound identifications should be supported by at
least one additional qualitative technique. This method describes
analytical conditions for a second gas chromatographic column that can
be used to confirm measurements made with the primary column. Method 624
provides gas chromatograph/mass spectrometer (GC/MS) conditions
appropriate for the qualitative and quantitative confirmation of results
for all of the parameters listed above.
1.3 The method detection limit (MDL, defined in Section 12.1)
1 for each parameter is listed in Table 1. The MDL for a
specific wastewater may differ from those listed, depending upon the
nature of interferences in the sample matrix.
1.4 Any modification of this method, beyond those expressly
permitted, shall be considered as a major modification subject to
application and approval of alternate test procedures under 40 CFR 136.4
and 136.5.
1.5 This method is restricted to use by or under the supervision of
analysts experienced in the operation of a purge and trap system and a
gas chromatograph and in the interpretation of gas chromatograms. Each
analyst must demonstrate the ability to generate acceptable results with
this method using the procedure described in Section 8.2.
2. Summary of Method
2.1 An inert gas is bubbled through a 5-mL water sample contained in
a specially-designed purging chamber at ambient temperature. The
aromatics are efficiently transferred from the aqueous phase to the
vapor phase. The vapor is swept through a sorbent trap where the
aromatics are trapped. After purging is completed, the trap is heated
and backflushed with the inert gas to desorb the aromatics onto a gas
chromatographic column. The gas chromatograph is temperature programmed
to separate the aromatics which are then detected with a photoionization
detector.2, 3
2.2 The method provides an optional gas chromatographic column that
may be helpful in resolving the compounds of interest from interferences
that may occur.
3. Interferences
3.1 Impurities in the purge gas and organic compounds outgassing
from the plumbing ahead of the trap account for the majority of
contamination problems. The analytical system must be demonstrated to be
free from contamination under the conditions of the analysis by running
laboratory reagent blanks as described in Section 8.1.3. The use of non-
Teflon plastic tubing, non-Teflon thread sealants, or flow controllers
with rubber components in the purge and trap system should be avoided.
3.2 Samples can be contaminated by diffusion of volatile organics
through the septum seal into the sample during shipment and storage. A
field reagent blank prepared from reagent water and carried through the
sampling and handling protocol can serve as a check on such
contamination.
3.3 Contamination by carry-over can occur whenever high level and
low level samples are sequentially analyzed. To reduce carry-over, the
purging device and sample syringe must be rinsed with reagent water
between sample analyses. Whenever an unusually concentrated sample is
encountered, it should be followed by an analysis of reagent water to
check for cross contamination. For samples containing large amounts of
water-soluble materials, suspended solids, high boiling compounds or
high aromatic levels, it may be necessary to wash the purging device
with a detergent solution, rinse it with distilled water, and then dry
it in an oven at 105 [deg]C between analyses. The trap and other parts
of the system are also subject to contamination; therefore, frequent
bakeout and purging of the entire system may be required.
4. Safety
4.1 The toxicity or carcinogenicity of each reagent used in this
method has not been precisely defined; however, each chemical compound
should be treated as a potential health hazard. From this viewpoint,
exposure to these chemicals must be reduced to the lowest possible level
by whatever means available. The laboratory is responsible for
maintaining a current awareness file of OSHA regulations regarding the
safe handling of the chemicals specified in this method. A reference
file of material data handling sheets should also be made available to
all personnel involved in the chemical analysis. Additional references
to laboratory safety
[[Page 55]]
are available and have been identified 4-6 for the
information of the analyst.
4.2 The following parameters covered by this method have been
tentatively classified as known or suspected, human or mam malian
carcinogens: benzene and 1,4- dichlorobenzene. Primary standards of
these toxic compounds should be prepared in a hood. A NIOSH/MESA
approved toxic gas respirator should be worn when the analyst handles
high con centrations of these toxic compounds.
5. Apparatus and Materials
5.1 Sampling equipment, for discrete sampling.
5.1.1 Vial]25-mL capacity or larger, equipped with a screw cap with
a hole in the center (Pierce 13075 or equivalent). Detergent
wash, rinse with tap and distilled water, and dry at 105 [deg]C before
use.
5.1.2 Septum--Teflon-faced silicone (Pierce 12722 or
equivalent). Deter gent wash, rinse with tap and distilled water, and
dry at 105 [deg]C for 1 h before use.
5.2 Purge and trap system--The purge and trap system consists of
three separate pieces of equipment: A purging device, trap, and
desorber. Several complete systems are now commercially available.
5.2.1 The purging device must be designed to accept 5-mL samples
with a water column at least 3 cm deep. The gaseous head space between
the water column and the trap must have a total volume of less than 15
mL. The purge gas must pass through the water column as finely divided
bubbles with a diameter of less than 3 mm at the origin. The purge gas
must be introduced no more than 5 mm from the base of the water column.
The purging device illustrated in Figure 1 meets these design criteria.
5.2.2 The trap must be at least 25 cm long and have an inside
diameter of at least 0.105 in.
5.2.2.1 The trap is packed with 1 cm of methyl silicone coated
packing (Section 6.4.2) and 23 cm of 2,6-diphenylene oxide polymer
(Section 6.4.1) as shown in Figure 2. This trap was used to develop the
method performance statements in Section 12.
5.2.2.2 Alternatively, either of the two traps described in Method
601 may be used, although water vapor will preclude the measurement of
low concentrations of benzene.
5.2.3 The desorber must be capable of rapidly heating the trap to
180 [deg]C. The polymer section of the trap should not be heated higher
than 180 [deg]C and the remaining sections should not exceed 200 [deg]C.
The desorber illustrated in Figure 2 meets these design criteria.
5.2.4 The purge and trap system may be assembled as a separate unit
or be coupled to a gas chromatograph as illustrated in Figures 3, 4, and
5.
5.3 Gas chromatograph--An analytical system complete with a
temperature programmable gas chromatograph suitable for on-column
injection and all required accessories including syringes, analytical
columns, gases, detector, and strip-chart recorder. A data system is
recommended for measuring peak areas.
5.3.1 Column 1--6 ft long x 0.082 in. ID stainless steel or glass,
packed with 5% SP-1200 and 1.75% Bentone-34 on Supelcoport (100/120
mesh) or equivalent. This column was used to develop the method
performance statements in Section 12. Guidelines for the use of
alternate column packings are provided in Section 10.1.
5.3.2 Column 2--8 ft long x 0.1 in ID stainless steel or glass,
packed with 5% 1,2,3-Tris(2-cyanoethoxy)propane on Chromosorb W-AW (60/
80 mesh) or equivalent.
5.3.3 Detector--Photoionization detector (h-Nu Systems, Inc. Model
PI-51-02 or equivalent). This type of detector has been proven effective
in the analysis of wastewaters for the parameters listed in the scope
(Section 1.1), and was used to develop the method performance statements
in Section 12. Guidelines for the use of alternate detectors are
provided in Section 10.1.
5.4 Syringes--5-mL glass hypodermic with Luerlok tip (two each), if
applicable to the purging device.
5.5 Micro syringes--25-[micro]L, 0.006 in. ID needle.
5.6 Syringe valve--2-way, with Luer ends (three each).
5.7 Bottle--15-mL, screw-cap, with Teflon cap liner.
5.8 Balance--Analytical, capable of accurately weighing 0.0001 g.
6. Reagents
6.1 Reagent water--Reagent water is defined as a water in which an
interferent is not observed at the MDL of the parameters of interest.
6.1.1 Reagent water can be generated by passing tap water through a
carbon filter bed containing about 1 lb of activated carbon (Filtrasorb-
300, Calgon Corp., or equivalent).
6.1.2 A water purification system (Millipore Super-Q or equivalent)
may be used to generate reagent water.
6.1.3 Reagent water may also be prepared by boiling water for 15
min. Subsequently, while maintaining the temperature at 90 [deg]C,
bubble a contaminant-free inert gas through the water for 1 h. While
still hot, transfer the water to a narrow mouth screw-cap bottle and
seal with a Teflon-lined septum and cap.
6.2 Sodium thiosulfate--(ACS) Granular.
6.3 Hydrochloric acid (1+1)--Add 50 mL of concentrated HCl (ACS) to
50 mL of reagent water.
6.4 Trap Materials:
[[Page 56]]
6.4.1 2,6-Diphenylene oxide polymer--Tenax, (60/80 mesh),
chromatographic grade or equiv alent.
6.4.2 Methyl silicone packing--3% OV-1 on Chromosorb-W (60/80 mesh)
or equivalent.
6.5 Methanol--Pesticide quality or equivalent.
6.6 Stock standard solutions--Stock stand ard solutions may be
prepared from pure standard materials or purchased as certified
solutions. Prepare stock standard solutions in methanol using assayed
liquids. Because of the toxicity of benzene and 1,4-dichloro benzene,
primary dilutions of these mate rials should be prepared in a hood. A
NIOSH/MESA approved toxic gas respirator should be used when the analyst
handles high concentrations of such materials.
6.6.1 Place about 9.8 mL of methanol into a 10-mL ground glass
stoppered volumetric flask. Allow the flask to stand, unstoppered, for
about 10 min or until all alcohol wetted surfaces have dried. Weigh the
flask to the nearest 0.1 mg.
6.6.2 Using a 100-[micro]L syringe, immediately add two or more
drops of assayed reference material to the flask, then reweigh. Be sure
that the drops fall directly into the alcohol without contacting the
neck of the flask.
6.6.3 Reweigh, dilute to volume, stopper, then mix by inverting the
flask several times. Calculate the concentration in [micro]g/[micro]L
from the net gain in weight. When compound purity is assayed to be 96%
or greater, the weight can be used without correction to calculate the
concentration of the stock standard. Commercially prepared stock
standards can be used at any concentration if they are certified by the
manufacturer or by an independent source.
6.6.4 Transfer the stock standard solution into a Teflon-sealed
screw-cap bottle. Store at 4 [deg]C and protect from light.
6.6.5 All standards must be replaced after one month, or sooner if
comparison with check standards indicates a problem.
6.7 Secondary dilution standards--Using stock standard solutions,
prepare secondary dilution standards in methanol that contain the
compounds of interest, either singly or mixed together. The secondary
dilution standards should be prepared at concentrations such that the
aqueous calibration standards prepared in Section 7.3.1 or 7.4.1 will
bracket the working range of the analytical system. Secondary solution
standards must be stored with zero headspace and should be checked
frequently for signs of degradation or evaporation, especially just
prior to preparing calibration standards from them.
6.8 Quality control check sample concentrate--See Section 8.2.1.
7. Calibration
7.1 Assemble a purge and trap system that meets the specifications
in Section 5.2. Condition the trap overnight at 180 [deg]C by
backflushing with an inert gas flow of at least 20 mL/min. Condition the
trap for 10 min once daily prior to use.
7.2 Connect the purge and trap system to a gas chromatograph. The
gas chromatograph must be operated using temperature and flow rate
conditions equivalent to those given in Table 1. Calibrate the purge and
trap-gas chromatographic system using either the external standard
technique (Section 7.3) or the internal standard technique (Section
7.4).
7.3 External standard calibration procedure:
7.3.1 Prepare calibration standards at a minimum of three
concentration levels for each parameter by carefully adding 20.0
[micro]L of one or more secondary dilution standards to 100, 500, or
1000 mL of reagent water. A 25-[micro]L syringe with a 0.006 in. ID
needle should be used for this operation. One of the external standards
should be at a concentration near, but above, the MDL (Table 1) and the
other concentrations should correspond to the expected range of
concentrations found in real samples or should define the working range
of the detector. These aqueous standards must be prepared fresh daily.
7.3.2 Analyze each calibration standard according to Section 10, and
tabulate peak height or area responses versus the concentration in the
standard. The results can be used to prepare a calibration curve for
each compound. Alternatively, if the ratio of response to concentration
(calibration factor) is a constant over the working range (<10% relative
standard deviation, RSD), linearity through the origin can be assumed
and the average ratio or calibration factor can be used in place of a
calibration curve.
7.4 Internal standard calibration procedure--To use this approach,
the analyst must select one or more internal standards that are similar
in analytical behavior to the compounds of interest. The analyst must
further demonstrate that the measurement of the internal standard is not
affected by method or matrix interferences. Because of these
limitations, no internal standard can be suggested that is applicable to
all samples. The compound, [alpha],[alpha],[alpha],-trifluorotoluene,
recommended as a surrogate spiking compound in Section 8.7 has been used
successfully as an internal standard.
7.4.1 Prepare calibration standards at a minimum of three
concentration levels for each parameter of interest as described in
Section 7.3.1.
7.4.2 Prepare a spiking solution containing each of the internal
standards using the procedures described in Sections 6.6 and 6.7. It is
recommended that the secondary dilution standard be prepared at a
concentration of 15 [micro]g/mL of each internal standard compound. The
addition of 10 [micro]l of this
[[Page 57]]
standard to 5.0 mL of sample or calibration standard would be equivalent
to 30 [micro]g/L.
7.4.3 Analyze each calibration standard according to Section 10,
adding 10 [micro]L of internal standard spiking solution directly to the
syringe (Section 10.4). Tabulate peak height or area responses against
concentration for each compound and internal standard, and calculate
response factors (RF) for each compound using Equation 1.
RF= (As)(Cis) (Ais)(Cs)
----------------------------------------------------------------------------------------------------------------
Equation 1
where:
As=Response for the parameter to be measured.
Ais=Response for the internal standard.
Cis=Concentration of the internal standard
Cs=Concentration of the parameter to be measured.
If the RF value over the working range is a constant (<10% RSD), the RF
can be assumed to be invariant and the average RF can be used for
calculations. Alternatively, the results can be used to plot a
calibration curve of response ratios, As/Ais, vs.
RF.
7.5 The working calibration curve, calibration factor, or RF must be
verified on each working day by the measurement of a QC check sample.
7.5.1 Prepare the QC check sample as described in Section 8.2.2.
7.5.2 Analyze the QC check sample according to Section 10.
7.5.3 For each parameter, compare the response (Q) with the
corresponding calibration acceptance criteria found in Table 2. If the
responses for all parameters of interest fall within the designated
ranges, analysis of actual samples can begin. If any individual Q falls
outside the range, a new calibration curve, calibration factor, or RF
must be prepared for that parameter according to Section 7.3 or 7.4.
8. Quality Control
8.1 Each laboratory that uses this method is required to operate a
formal quality control program. The mimimum requirements of this program
consist of an initial demonstration of laboratory capability and an
ongoing analysis of spiked samples to evaluate and document data
quality. The laboratory must maintain records to document the quality of
data that is generated. Ongoing data quality checks are compared with
established performance criteria to determine if the results of analyses
meet the performance characteristics of the method. When results of
sample spikes indicate atypical method performance, a quality control
check standard must be analyzed to confirm that the measurements were
performed in an in-control mode of operation.
8.1.1 The analyst must make an initial, one-time, demonstration of
the ability to generate acceptable accuracy and precision with this
method. This ability is established as described in Section 8.2.
8.1.2 In recognition of advances that are occurring in
chromatography, the analyst is permitted certain options (detailed in
Section 10.1) to improve the separations or lower the cost of
measurements. Each time such a modification is made to the method, the
analyst is required to repeat the procedure in Section 8.2.
8.1.3 Each day, the analyst must analyze a reagent water blank to
demonstrate that interferences from the analytical system are under
control.
8.1.4 The laboratory must, on an ongoing basis, spike and analyze a
minimum of 10% of all samples to monitor and evaluate laboratory data
quality. This procedure is described in Section 8.3.
8.1.5 The laboratory must, on an ongoing basis, demonstrate through
the analyses of quality control check standards that the operation of
the measurement system is in control. This procedure is described in
Section 8.4. The frequency of the check standard analyses is equivalent
to 10% of all samples analyzed but may be reduced if spike recoveries
from samples (Section 8.3) meet all specified quality control criteria.
8.1.6 The laboratory must maintain performance records to document
the quality of data that is generated. This procedure is described in
Section 8.5.
8.2 To establish the ability to generate acceptable accuracy and
precision, the analyst must perform the following operations.
8.2.1 A quality control (QC) check sample concentrate is required
containing each parameter of interest at a concentration of 10 [micro]g/
mL in methanol. The QC check sample concentrate must be obtained from
the U.S. Environmental Protection Agency, Environmental Monitoring and
Support Laboratory in Cincinnati, Ohio, if available. If not available
from that source, the QC check sample concentrate must be obtained from
another external source. If not available from either source above, the
QC check sample concentrate must be prepared by the laboratory using
stock standards prepared independently from those used for calibration.
8.2.2 Prepare a QC check sample to contain 20 [micro]g/L of each
parameter by adding 200 [micro]L of QC check sample concentrate to 100
mL of reagant water.
8.2.3 Analyze four 5-mL aliquots of the well-mixed QC check sample
according to Section 10.
8.2.4 Calculate the average recovery (X) in [micro]g/L, and the
standard deviation of the recovery (s) in [micro]g/L, for each parameter
of interest using the four results.
8.2.5 For each parameter compare s and X with the corresponding
acceptance criteria
[[Page 58]]
for precision and accuracy, respectively, found in Table 2. If s and X
for all parameters of interest meet the acceptance criteria, the system
performance is acceptable and analysis of actual samples can begin. If
any individual s exceeds the precision limit or any individual X falls
outside the range for accuracy, the system performance is unacceptable
for that parameter.
Note: The large number of parameters in Table 2 present a
substantial probability that one or more will fail at least one of the
acceptance criteria when all parameters are analyzed.
8.2.6 When one or more of the parameters tested fail at least one of
the acceptance criteria, the analyst must proceed according to Section
8.2.6.1 or 8.2.6.2.
8.2.6.1 Locate and correct the source of the problem and repeat the
test for all parameters of interest beginning with Section 8.2.3.
8.2.6.2 Beginning with Section 8.2.3, repeat the test only for those
parameters that failed to meet criteria. Repeated failure, however, will
confirm a general problem with the measurement system. If this occurs,
locate and correct the source of the problem and repeat the test for all
compounds of interest beginning with Section 8.2.3.
8.3 The laboratory must, on an ongoing basis, spike at least 10% of
the samples from each sample site being monitored to assess accuracy.
For laboratories analyzing one to ten samples per month, at least one
spiked sample per month is required.
8.3.1 The concentration of the spike in the sample should be
determined as follows:
8.3.1.1 If, as in compliance monitoring, the concentration of a
specific parameter in the sample is being checked against a regulatory
concentration limit, the spike should be at that limit or 1 to 5 times
higher than the background concentration determined in Section 8.3.2,
whichever concentration would be larger.
8.3.1.2 If the concentration of a specific parameter in the sample
is not being checked against a limit specific to that parameter, the
spike should be at 20 [micro]g/L or 1 to 5 times higher than the
background concentration determined in Section 8.3.2, whichever
concentration would be larger.
8.3.2 Analyze one 5-mL sample aliquot to determine the background
concentration (B) of each parameter. If necessary, prepare a new QC
check sample concentrate (Section 8.2.1) appropriate for the background
concentrations in the sample. Spike a second 5-mL sample aliquot with 10
[micro]L of the QC check sample concentrate and analyze it to determine
the concentration after spiking (A) of each parameter. Calculate each
percent recovery (P) as 100(A-B)%/T, where T is the known true value of
the spike.
8.3.3 Compare the percent recovery (P) for each parameter with the
corresponding QC acceptance criteria found in Table 2. These acceptance
criteria were calculated to include an allowance for error in
measurement of both the background and spike concentrations, assuming a
spike to background ratio of 5:1. This error will be accounted for to
the extent that the analyst's spike to background ratio approaches
5:1.\7\ If spiking was performed at a concentration lower than 20
[micro]g/L, the analyst must use either the QC acceptance criteria in
Table 2, or optional QC acceptance criteria calculated for the specific
spike concentration. To calculate optional acceptance criteria for the
recovery of a parameter: (1) Calculate accuracy (X') using the equation
in Table 3, substituting the spike concentration (T) for C; (2)
calculate overall precision (S') using the equation in Table 3,
substituting X' for X; (3) calculate the range for recovery at the spike
concentration as (100 X'/T) 2.44(100 S'/T)%.\7\
8.3.4 If any individual P falls outside the designated range for
recovery, that parameter has failed the acceptance criteria. A check
standard containing each parameter that failed the criteria must be
analyzed as described in Section 8.4.
8.4 If any parameter fails the acceptance criteria for recovery in
Section 8.3, a QC check standard containing each parameter that failed
must be prepared and analyzed.
Note: The frequency for the required analysis of a QC check standard
will depend upon the number of parameters being simultaneously tested,
the complexity of the sample matrix, and the performance of the
laboratory.
8.4.1 Prepare the QC check standard by adding 10 [micro]L of QC
check sample concentrate (Section 8.2.1 or 8.3.2) to 5 mL of reagent
water. The QC check standard needs only to contain the parameters that
failed criteria in the test in Section 8.3.
8.4.2 Analyze the QC check standard to determine the concentration
measured (A) of each parameter. Calculate each percent recovery
(Ps) as 100 (A/T)%, where T is the true value of the standard
concentration.
8.4.3 Compare the percent recovery (Ps) for each
parameter with the corresponding QC acceptance criteria found in Table
2. Only parameters that failed the test in Section 8.3 need to be
compared with these criteria. If the recovery of any such parameter
falls outside the designated range, the laboratory performance for that
parameter is judged to be out of control, and the problem must be
immediately identified and corrected. The analytical result for that
parameter in the unspiked sample is suspect and may not be reported for
regulatory compliance purposes.
8.5 As part of the QC program for the laboratory, method accuracy
for wastewater samples must be assessed and records must be maintained.
After the analysis of five spiked wastewater samples as in Section 8.3,
calculate the average percent recovery (P)
[[Page 59]]
and the standard deviation of the percent recovery (sp).
Express the accuracy assessment as a percent recovery interval from P-
2sp to P+2sp. If P=90% and sp=10%, for
example, the accuracy interval is expressed as 70-110%. Update the
accuracy assessment for each parameter on a regular basis (e.g. after
each five to ten new accuracy measurements).
8.6 It is recommended that the laboratory adopt additional quality
assurance practices for use with this method. The specific practices
that are most productive depend upon the needs of the laboratory and the
nature of the samples. Field duplicates may be analyzed to assess the
precision of the environmental measurements. When doubt exists over the
identification of a peak on the chromatogram, confirmatory techniques
such as gas chromatography with a dissimilar column, specific element
detector, or mass spectrometer must be used. Whenever possible, the
laboratory should analyze standard reference materials and participate
in relevant performance evaluation studies.
8.7 The analyst should monitor both the performance of the
analytical system and the effectiveness of the method in dealing with
each sample matrix by spiking each sample, standard, and reagent water
blank with surrogate compounds (e.g. [alpha], [alpha], [alpha],-
trifluorotoluene) that encompass the range of the temperature program
used in this method. From stock standard solutions prepared as in
Section 6.6, add a volume to give 750 [micro]g of each surrogate to 45
mL of reagent water contained in a 50-mL volumetric flask, mix and
dilute to volume for a concentration of 15 mg/[micro]L. Add 10 [micro]L
of this surrogate spiking solution directly into the 5-mL syringe with
every sample and reference standard analyzed. Prepare a fresh surrogate
spiking solution on a weekly basis. If the internal standard calibration
procedure is being used, the surrogate compounds may be added directly
to the internal standard spiking solution (Section 7.4.2).
9. Sample Collection, Preservation, and Handling
9.1 The samples must be iced or refrigerated from the time of
collection until analysis. If the sample contains free or combined
chlorine, add sodium thiosulfate preservative (10 mg/40 mL is sufficient
for up to 5 ppm Cl2) to the empty sample bottle just prior to
shipping to the sampling site. EPA Method 330.4 or 330.5 may be used for
measurement of residual chlorine.8 Field test kits are
available for this purpose.
9.2 Collect about 500 mL of sample in a clean container. Adjust the
pH of the sample to about 2 by adding 1+1 HCl while stirring. Fill the
sample bottle in such a manner that no air bubbles pass through the
sample as the bottle is being filled. Seal the bottle so that no air
bubbles are entrapped in it. Maintain the hermetic seal on the sample
bottle until time of analysis.
9.3 All samples must be analyzed within 14 days of
collection.3
10. Procedure
10.1 Table 1 summarizes the recommended operating conditions for the
gas chrom atograph. Included in this table are estimated retention times
and MDL that can be achieved under these conditions. An ex ample of the
separations achieved by Column 1 is shown in Figure 6. Other packed
columns, chromatographic conditions, or detectors may be used if the
requirements of Section 8.2 are met.
10.2 Calibrate the system daily as described in Section 7.
10.3 Adjust the purge gas (nitrogen or helium) flow rate to 40 mL/
min. Attach the trap inlet to the purging device, and set the purge and
trap system to purge (Figure 3). Open the syringe valve located on the
purging device sample introduction needle.
10.4 Allow the sample to come to ambient temperature prior to
introducing it to the syringe. Remove the plunger from a 5-mL syringe
and attach a closed syringe valve. Open the sample bottle (or standard)
and carefully pour the sample into the syringe barrel to just short of
overflowing. Replace the syringe plunger and compress the sample. Open
the syringe valve and vent any residual air while adjusting the sample
volume to 5.0 mL. Since this process of taking an aliquot destroys the
validity of the sample for future analysis, the analyst should fill a
second syringe at this time to protect against possible loss of data.
Add 10.0 [micro]L of the surrogate spiking solution (Section 8.7) and
10.0 [micro]L of the internal standard spiking solution (Section 7.4.2),
if applicable, through the valve bore, then close the valve.
10.5 Attach the syringe-syringe valve assembly to the syringe valve
on the purging device. Open the syringe valves and inject the sample
into the purging chamber.
10.6 Close both valves and purge the sample for 12.00.1 min at ambient temperature.
10.7 After the 12-min purge time, disconnect the purging device from
the trap. Dry the trap by maintaining a flow of 40 mL/min of dry purge
gas through it for 6 min (Figure 4). If the purging device has no
provision for bypassing the purger for this step, a dry purger should be
inserted into the device to minimize moisture in the gas. Attach the
trap to the chromatograph, adjust the purge and trap system to the
desorb mode (Figure 5), and begin to temperature program the gas
chromatograph. Introduce the trapped materials to the GC column by
rapidly heating the trap to 180 [deg]C while backflushing the trap with
an inert gas between 20 and 60 mL/min for 4 min. If rapid heating of the
trap cannot be achieved, the GC column must be used as
[[Page 60]]
a secondary trap by cooling it to 30 [deg]C (subambient temperature, if
poor peak geometry and random retention time problems persist) instead
of the initial program temperature of 50 [deg]C.
10.8 While the trap is being desorbed into the gas chromatograph
column, empty the purging chamber using the sample introduction syringe.
Wash the chamber with two 5-mL flushes of reagent water.
10.9 After desorbing the sample for 4 min, recondition the trap by
returning the purge and trap system to the purge mode. Wait 15 s, then
close the syringe valve on the purging device to begin gas flow through
the trap. The trap temperature should be maintained at 180 [deg]C. After
approximately 7 min, turn off the trap heater and open the syringe valve
to stop the gas flow through the trap. When the trap is cool, the next
sample can be analyzed.
10.10 Identify the parameters in the sample by comparing the
retention times of the peaks in the sample chromatogram with those of
the peaks in standard chromatograms. The width of the retention time
window used to make identifications should be based upon measurements of
actual retention time variations of standards over the course of a day.
Three times the standard deviation of a retention time for a compound
can be used to calculate a suggested window size; however, the
experience of the analyst should weigh heavily in the interpretation of
chromatograms.
10.11 If the response for a peak exceeds the working range of the
system, prepare a dilution of the sample with reagent water from the
aliquot in the second syringe and reanalyze.
11. Calculations
11.1 Determine the concentration of individual compounds in the
sample.
11.1.1 If the external standard calibration procedure is used,
calculate the concentration of the parameter being measured from the
peak response using the calibration curve or calibration factor
determined in Section 7.3.2.
11.1.2 If the internal standard calibration procedure is used,
calculate the concentration in the sample using the response factor (RF)
determined in Section 7.4.3 and Equation 2.
[GRAPHIC] [TIFF OMITTED] TC15NO91.096
Equation 2
where:
As = Response for the parameter to be measured.
Ais = Response for the internal standard.
Cis = Concentration of the internal standard.
11.2 Report results in [micro]g/L without correction for recovery
data. All QC data obtained should be reported with the sample results.
12. Method Performance
12.1 The method detection limit (MDL) is defined as the minimum
concentration of a substance that can be measured and reported with 99%
confidence that the value is above zero.1 The MDL
concentrations listed in Table 1 were obtained using reagent
water.9 Similar results were achieved using representative
wastewaters. The MDL actually achieved in a given analysis will vary
depending on instrument sensitivity and matrix effects.
12.2 This method has been demonstrated to be applicable for the
concentration range from the MDL to 100 x MDL.9 Direct
aqueous injection techniques should be used to measure concentration
levels above 1000 x MDL.
12.3 This method was tested by 20 laboratories using reagent water,
drinking water, surface water, and three industrial wastewaters spiked
at six concentrations over the range 2.1 to 550 [micro]g/L.9
Single operator precision, overall precision, and method accuracy were
found to be directly related to the concentration of the parameter and
essentially independent of the sample matrix. Linear equations to
describe these relationships are presented in Table 3.
References
1. 40 CFR part 136, appendix B.
2. Lichtenberg, J.J. ``Determining Volatile Organics at Microgram-
per-Litre-Levels by Gas Chromatography,'' Journal American Water Works
Association, 66, 739 (1974).
3. Bellar, T.A., and Lichtenberg, J.J. ``Semi-Automated Headspace
Analysis of Drinking Waters and Industrial Waters for Purgeable Volatile
Organic Compounds,'' Proceedings of Symposium on Measurement of Organic
Pollutants in Water and Wastewater. American Society for Testing and
Materials, STP 686, C.E. Van Hall, editor, 1978.
4. ``Carcinogens--Working with Carcinogens,'' Department of Health,
Education, and Welfare, Public Health Service, Center for Disease
Control, National Institute for Occupational Safety and Health.
Publication No. 77-206, August 1977.
5. ``OSHA Safety and Health Standards, General Industry,'' (29 CFR
part 1910), Occupational Safety and Health Administration, OSHA 2206
(Revised, January 1976).
6. ``Safety in Academic Chemistry Laboratories,'' American Chemical
Society Publication, Committee on Safety, 3rd Edition, 1979.
7. Provost, L.P., and Elder, R.S. ``Interpretation of Percent
Recovery Data,'' American Laboratory, 15, 58-63 (1983). (The value 2.44
used in the equation in Section 8.3.3. is two times the value 1.22
derived in this report.)
[[Page 61]]
8.``Methods 330.4 (Titrimetric, DPD-FAS) and 330.5
(Spectrophotometric, DPD) for Chlorine, Total Residual,'' Methods for
Chemical Analysis of Water and Wastes, EPA-600/4-79-020, U.S.
Environmental Protection Agency, Office of Research and Development,
Environmental Monitoring and Support Laboratory, Cincinnati, Ohio 45268.
March 1979.
9. ``EPA Method Study 25, Method 602, Purgeable Aromatics,'' EPA
600/4-84-042, National Technical Information Service, PB84-196682,
Springfield, Virginia 22161, May 1984.
Table 1--Chromatographic Conditions and Method Detection Limits
------------------------------------------------------------------------
Retention time (min) Method
---------------------- detection
Parameter limit
Column 1 Column 2 ([micro]g/
L)
------------------------------------------------------------------------
Benzene............................... 3.33 2.75 0.2
Toluene............................... 5.75 4.25 0.2
Ethylbenzene.......................... 8.25 6.25 0.2
Chlorobenzene......................... 9.17 8.02 0.2
1,4-Dichlorobenzene................... 16.8 16.2 0.3
1,3-Dichlorobenzene................... 18.2 15.0 0.4
1,2-Dichlorobenzene................... 25.9 19.4 0.4
------------------------------------------------------------------------
Column 1 conditions: Supelcoport (100/120 mesh) coated with 5% SP-1200/
1.75% Bentone-34 packed in a 6 ft x 0.085 in. ID stainless steel
column with helium carrier gas at 36 mL/min flow rate. Column
temperature held at 50 [deg]C for 2 min then programmed at 6 [deg]C/
min to 90 [deg]C for a final hold.
Column 2 conditions: Chromosorb W-AW (60/80 mesh) coated with 5% 1,2,3-
Tris(2-cyanoethyoxy)propane packed in a 6 ft x 0.085 in. ID stainless
steel column with helium carrier gas at 30 mL/min flow rate. Column
temperature held at 40 [deg]C for 2 min then programmed at 2 [deg]C/
min to 100 [deg]C for a final hold.
Table 2--Calibration and QC Acceptance Criteria--Method 602 a
----------------------------------------------------------------------------------------------------------------
Limit for Range for X
Range for Q s ([micro]g/ Range for
Parameter ([micro]g/ ([micro]g/ L) P, Ps(%)
L) L)
----------------------------------------------------------------------------------------------------------------
Benzene........................................................ 15.4-24.6 4.1 10.0-27.9 39-150
Chlorobenzene.................................................. 16.1-23.9 3.5 12.7-25.4 55-135
1,2-Dichlorobenzene............................................ 13.6-26.4 5.8 10.6-27.6 37-154
1,3-Dichlorobenzene............................................ 14.5-25.5 5.0 12.8-25.5 50-141
1,4-Dichlorobenzene............................................ 13.9-26.1 5.5 11.6-25.5 42-143
Ethylbenzene................................................... 12.6-27.4 6.7 10.0-28.2 32-160
Toluene........................................................ 15.5-24.5 4.0 11.2-27.7 46-148
----------------------------------------------------------------------------------------------------------------
Q=Concentration measured in QC check sample, in [micro]g/L (Section 7.5.3).
s=Standard deviation of four recovery measurements, in [micro]g/L (Section 8.2.4).
X=Average recovery for four recovery measurements, in [micro]g/L (Section 8.2.4).
Ps, P=Percent recovery measured (Section 8.3.2, Section 8.4.2).
a Criteria were calculated assuming a QC check sample concentration of 20 [micro]g/L.
Note: These criteria are based directly upon the method performance data in Table 3. Where necessary, the limits
for recovery have been broadened to assure applicability of the limits to concentrations below those used to
develop Table 3.
Table 3--Method Accuracy and Precision as Functions of Concentration--Method 602
----------------------------------------------------------------------------------------------------------------
Accuracy, as Single analyst Overall
Parameter recovery, X' precision, s' precision, S'
([micro]g/L) ([micro]g/L) ([micro]g/L)
----------------------------------------------------------------------------------------------------------------
Benzene......................................................... 0.92C+0.57 0.09X+0.59 0.21X+0.56
Chlorobenzene................................................... 0.95C+0.02 0.09X+0.23 0.17X+0.10
1,2-Dichlorobenzene............................................. 0.93C+0.52 0.17X-0.04 0.22X+0.53
1,3-Dichlorobenzene............................................. 0.96C-0.05 0.15X-0.10 0.19X+0.09
1,4-Dichlorobenzene............................................. 0.93C-0.09 0.15X+0.28 0.20X+0.41
Ethylbenzene.................................................... 0.94C+0.31 0.17X+0.46 0.26X+0.23
Toluene......................................................... 0.94C+0.65 0.09X+0.48 0.18X+0.71
----------------------------------------------------------------------------------------------------------------
X'=Expected recovery for one or more measurements of a sample containing a concentration of C, in [micro]g/L.
S'=Expected single analyst standard deviation of measurements at an average concentration found of X, in X
[micro]g/L.
S'=Expected interlaboratory standard deviation of measurements at an average concentration found of X, in
[micro]g/L.
C=True value for the Concentration, in [micro]g/L.
X=Average recovery found for measurements of samples containing a concentration of C, in [micro]g/L.
[[Page 62]]
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[GRAPHIC] [TIFF OMITTED] TC02JY92.005
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[[Page 66]]
Method 603--Acrolein and Acrylonitrile
1. Scope and Application
1.1 This method covers the determination of acrolein and
acrylonitrile. The following parameters may be determined by this
method:
------------------------------------------------------------------------
STORET
Parameter No. CAS No.
------------------------------------------------------------------------
Acrolein......................................... 34210 107-02-8
Acrylonitrile.................................... 34215 107-13-1
------------------------------------------------------------------------
1.2 This is a purge and trap gas chromatographic (GC) method
applicable to the determination of the compounds listed above in
municipal and industrial discharges as provided under 40 CFR 136.1. When
this method is used to analyze unfamiliar samples for either or both of
the compounds above, compound identifications should be supported by at
least one additional qualitative technique. This method describes
analytical conditions for a second gas chromatographic column that can
be used to confirm measurements made with the primary column. Method 624
provides gas chromatograph/mass spectrometer (GC/MS) conditions
appropriate for the qualitative and quantitative confirmation of results
for the parameters listed above, if used with the purge and trap
conditions described in this method.
1.3 The method detection limit (MDL, defined in Section 12.1)
1 for each parameter is listed in Table 1. The MDL for a
specific wastewater may differ from those listed, depending upon the
nature of interferences in the sample matrix.
1.4 Any modification of this method, beyond those expressly
permitted, shall be considered as a major modification subject to
application and approval of alternate test procedures under 40 CFR 136.4
and 136.5.
1.5 This method is restricted to use by or under the supervision of
analysts experienced in the operation of a purge and trap system and a
gas chromatograph and in the interpretation of gas chromatograms. Each
analyst must demonstrate the ability to generate acceptable results with
this method using the procedure described in Section 8.2.
2. Summary of Method
2.1 An inert gas is bubbled through a 5-mL water sample contained in
a heated purging chamber. Acrolein and acrylonitrile are transferred
from the aqueous phase to the vapor phase. The vapor is swept through a
sorbent trap where the analytes are trapped. After the purge is
completed, the trap is heated and backflushed with the inert gas to
desorb the compound onto a gas chromatographic column. The gas
chromatograph is temperature programmed to separate the analytes which
are then detected with a flame ionization detector.2, 3
2.2 The method provides an optional gas chromatographic column that
may be helpful in resolving the compounds of interest from the
interferences that may occur.
3. Interferences
3.1 Impurities in the purge gas and organic compound outgassing from
the plumbing of the trap account for the majority of contamination
problems. The analytical system must be demonstrated to be free from
contamination under the conditions of the analysis by running laboratory
reagent blanks as described in Section 8.1.3. The use of non-Teflon
plastic tubing, non-Teflon thread sealants, or flow controllers with
rubber components in the purge and trap system should be avoided.
3.2 Samples can be contaminated by diffusion of volatile organics
through the septum seal into the sample during shipment and storage. A
field reagent blank prepared from reagent water and carried through the
sampling and handling protocol can serve as a check on such
contamination.
3.3 Contamination by carry-over can occur whenever high level and
low level samples are sequentially analyzed. To reduce carry-over, the
purging device and sample syringe must be rinsed between samples with
reagent water. Whenever an unusually concentrated sample is encountered,
it should be followed by an analysis of reagent water to check for cross
contamination. For samples containing large amounts of water-soluble
materials, suspended solids, high boiling compounds or high analyte
levels, it may be necessary to wash the purging device with a detergent
solution, rinse it with distilled water, and then dry it in an oven at
105 [deg]C between analyses. The trap and other parts of the system are
also subject to contamination, therefore, frequent bakeout and purging
of the entire system may be required.
4. Safety
4.1 The toxicity or carcinogenicity of each reagent used in this
method has not been precisely defined; however, each chemical compound
should be treated as a potential health hazard. From this view point,
exposure to these chemicals must be reduced to the lowest possible level
by whatever means available. The laboratory is responsible for
maintaining a current awareness file of OSHA regulations regarding the
safe handling of the chemicals specified in this method. A reference
file of material data handling sheets should also be made available to
all personnel involved in the chemical analysis. Additional references
to laboratory safety are available and have been identified
4, 6 for the information of the analyst.
[[Page 67]]
5. Apparatus and Materials
5.1 Sampling equipment, for discrete sampling.
5.1.1 Vial--25-mL capacity or larger, equipped with a screw cap with
a hole in the center (Pierce 13075 or equivalent). Detergent
wash, rinse with tap and distilled water, and dry at 105 [deg]C before
use.
5.1.2 Septum--Teflon-faced silicone (Pierce 12722 or
equivalent). Detergent wash, rinse with tap and distilled water and dry
at 105 [deg]C for 1 h before use.
5.2 Purge and trap system--The purge and trap system consists of
three separate pieces of equipment: a purging device, trap, and
desorber. Several complete systems are now commercially available.
5.2.1 The purging device must be designed to accept 5-mL, samples
with a water column at least 3 cm deep. The gaseous head space between
the water column and the trap must have a total volume of less than 15
mL. The purge gas must pass through the water column as finely divided
bubbles with a diameter of less than 3 mm at the origin. The purge gas
must be introduced no more than 5 mm from the base of the water column.
The purging device must be capable of being heated to 85 [deg]C within
3.0 min after transfer of the sample to the purging device and being
held at 85 2 [deg]C during the purge cycle. The
entire water column in the purging device must be heated. Design of this
modification to the standard purging device is optional, however, use of
a water bath is suggested.
5.2.1.1 Heating mantle--To be used to heat water bath.
5.2.1.2 Temperature controller--Equipped with thermocouple/sensor to
accurately control water bath temperature to 2
[deg]C. The purging device illustrated in Figure 1 meets these design
criteria.
5.2.2 The trap must be at least 25 cm long and have an inside
diameter of at least 0.105 in. The trap must be packed to contain 1.0 cm
of methyl silicone coated packing (Section 6.5.2) and 23 cm of 2,6-
diphenylene oxide polymer (Section 6.5.1). The minimum specifications
for the trap are illustrated in Figure 2.
5.2.3 The desorber must be capable of rapidly heating the trap to
180 [deg]C, The desorber illustrated in Figure 2 meets these design
criteria.
5.2.4 The purge and trap system may be assembled as a separate unit
as illustrated in Figure 3 or be coupled to a gas chromatograph.
5.3 pH paper--Narrow pH range, about 3.5 to 5.5 (Fisher Scientific
Short Range Alkacid No. 2, 14-837-2 or equivalent).
5.4 Gas chromatograph--An analytical system complete with a
temperature programmable gas chromatograph suitable for on-column
injection and all required accessories including syringes, analytical
columns, gases, detector, and strip-chart recorder. A data system is
recommended for measuring peak areas.
5.4.1 Column 1--10 ft long x 2 mm ID glass or stainless steel,
packed with Porapak-QS (80/100 mesh) or equivalent. This column was used
to develop the method performance statements in Section 12. Guidelines
for the use of alternate column packings are provided in Section 10.1.
5.4.2 Column 2--6 ft long x 0.1 in. ID glass or stainless steel,
packed with Chromosorb 101 (60/80 mesh) or equivalent.
5.4.3 Detector--Flame ionization detector. This type of detector has
proven effective in the analysis of wastewaters for the parameters
listed in the scope (Section 1.1), and was used to develop the method
performance statements in Section 12. Guidelines for the use of
alternate detectors are provided in Section 10.1.
5.5 Syringes--5-mL, glass hypodermic with Luerlok tip (two each).
5.6 Micro syringes--25-[micro]L, 0.006 in. ID needle.
5.7 Syringe valve--2-way, with Luer ends (three each).
5.8 Bottle--15-mL, screw-cap, with Teflon cap liner.
5.9 Balance--Analytical, capable of accurately weighing 0.0001 g.
6. Reagents
6.1 Reagent water--Reagent water is defined as a water in which an
interferent is not observed at the MDL of the parameters of interest.
6.1.1 Reagent water can be generated by passing tap water through a
carbon filter bed containing about 1 lb of activated carbon (Filtrasorb-
300, Calgon Corp., or equivalent).
6.1.2 A water purification system (Millipore Super-Q or equivalent)
may be used to generate reagent water.
6.1.3 Regent water may also be prepared by boiling water for 15 min.
Subsequently, while maintaining the temperature at 90 [deg]C, bubble a
contaminant-free inert gas through the water for 1 h. While still hot,
transfer the water to a narrow mouth screw-cap bottle and seal with a
Teflon-lined septum and cap.
6.2 Sodium thiosulfate--(ACS) Granular.
6.3 Sodium hydroxide solution (10 N)--Dissolve 40 g of NaOH (ACS) in
reagent water and dilute to 100 mL.
6.4 Hydrochloric acid (1+1)--Slowly, add 50 mL of concentrated HCl
(ACS) to 50 mL of reagent water.
6.5 Trap Materials:
6.5.1 2,6-Diphenylene oxide polymer--Tenax (60/80 mesh),
chromatographic grade or equivalent.
6.5.2 Methyl silicone packing--3% OV-1 on Chromosorb-W (60/80 mesh)
or equivalent.
[[Page 68]]
6.6 Stock standard solutions--Stock standard solutions may be
prepared from pure standard materials or purchased as certified
solutions. Prepare stock standard solutions in reagent water using
assayed liquids. Since acrolein and acrylonitrile are lachrymators,
primary dilutions of these compounds should be prepared in a hood. A
NIOSH/MESA approved toxic gas respirator should be used when the analyst
handles high concentrations of such materials.
6.6.1 Place about 9.8 mL of reagent water into a 10-mL ground glass
stoppered volumetric flask. For acrolein standards the reagent water
must be adjusted to pH 4 to 5. Weight the flask to the nearest 0.1 mg.
6.6.2 Using a 100-[micro]L syringe, immediately add two or more
drops of assayed reference material to the flask, then reweigh. Be sure
that the drops fall directly into the water without contacting the neck
of the flask.
6.6.3 Reweigh, dilute to volume, stopper, then mix by inverting the
flask several times. Calculate the concentration in [micro]g/[micro]L
from the net gain in weight. When compound purity is assayed to be 96%
or greater, the weight can be used without correction to calculate the
concentration of the stock staldard. Optionally, stock standard
solutions may be prepared using the pure standard material by
volumetrically measuring the appropriate amounts and determining the
weight of the material using the density of the material. Commercially
prepared stock standards may be used at any concentration if they are
certified by the manufactaurer or by an independent source.
6.6.4 Transfer the stock standard solution into a Teflon-sealed
screw-cap bottle. Store at 4 [deg]C and protect from light.
6.6.5 Prepare fresh standards daily.
6.7 Secondary dilution standards--Using stock standard solutions,
prepare secondary dilution standards in reagent water that contain the
compounds of interest, either singly or mixed together. The secondary
dilution standards should be prepared at concentrations such that the
aqueous calibration standards prepared in Section 7.3.1 or 7.4.1 will
bracket the working range of the analytical system. Secondary dilution
standards should be prepared daily and stored at 4 [deg]C.
6.8 Quality control check sample concentrate--See Section 8.2.1.
7. Calibration
7.1 Assemble a purge and trap system that meets the specifications
in Section 5.2. Condition the trap overnight at 180 [deg]C by
backflushing with an inert gas flow of at least 20 mL/min. Condition the
trap for 10 min once daily prior to use.
7.2 Connect the purge and trap system to a gas chromatograph. The
gas chromatograph must be operated using temperature and flow rate
conditions equivalent to those given in Table 1. Calibrate the purge and
trap-gas chromatographic system using either the external standard
technique (Section 7.3) or the internal standard technique (Section
7.4).
7.3 External standard calibration procedure:
7.3.1 Prepare calibration standards at a minimum of three
concentration levels for each parameter by carefully adding 20.0
[micro]L of one or more secondary dilution standards to 100, 500, or
1000 mL of reagent water. A 25-[micro]L syringe with a 0.006 in. ID
needle should be used for this operation. One of the external standards
should be at a concentration near, but above, the MDL and the other
concentrations should correspond to the expected range of concentrations
found in real samples or should define the working range of the
detector. These standards must be prepared fresh daily.
7.3.2 Analyze each calibration standard according to Section 10, and
tabulate peak height or area responses versus the concentration of the
standard. The results can be used to prepare a calibration curve for
each compound. Alternatively, if the ratio of response to concentration
(calibration factor) is a constant over the working range (< 10%
relative standard deviation, RSD), linearity through the origin can be
assumed and the average ratio or calibration factor can be used in place
of a calibration curve.
7.4 Internal standard calibration procedure--To use this approach,
the analyst must select one or more internal standards that are similar
in analytical behavior to the compounds of interest. The analyst must
further demonstrate that the measurement of the internal standard is not
affected by method or matrix interferences. Because of these
limitations, no internal standard can be suggested that is applicable to
all samples.
7.4.1 Prepare calibration standards at a minimum of three
concentration levels for each parameter of interest as described in
Section 7.3.1.
7.4.2 Prepare a spiking solution containing each of the internal
standards using the procedures described in Sections 6.6 and 6.7. It is
recommended that the secondary dilution standard be prepared at a
concentration of 15 [micro]g/mL of each internal standard compound. The
addition of 10 [micro]L of this standard to 5.0 mL of sample or
calibration standard would be equivalent to 30 [micro]g/L.
7.4.3 Analyze each calibration standard according to Section 10,
adding 10 [micro]L of internal standard spiking solution directly to the
syringe (Section 10.4). Tabulate peak height or area responses against
concentration for each compound and internal standard, and calculate
response factors (RF) for each compound using Equation 1.
[[Page 69]]
RF= (As)(Cis) (Ais)(Cs)
----------------------------------------------------------------------------------------------------------------
Equation 1
where:
As=Response for the parameter to be measured.
Ais=Response for the internal standard.
Cis=Concentration of the internal standard.
Cs=Concentration of the parameter to be measured.
If the RF value over the working range is a constant (<10% RSD), the RF
can be assumed to be invariant and the average RF can be used for
calculations. Alternatively, the results can be used to plot a
calibration curve of response ratios, As/Ais, vs.
RF.
7.5 The working calibration curve, calibration factor, or RF must be
verified on each working day by the measurement of a QC check sample.
7.5.1 Prepare the QC check sample as described in Section 8.2.2.
7.5.2 Analyze the QC check sample according to Section 10.
7.5.3 For each parameter, compare the response (Q) with the
corresponding calibration acceptance criteria found in Table 2. If the
responses for all parameters of interest fall within the designated
ranges, analysis of actual samples can begin. If any individual Q falls
outside the range, a new calibration curve, calibration factor, or RF
must be prepared for that parameter according to Section 7.3 or 7.4.
8. Quality Control
8.1 Each laboratory that uses this method is required to operate a
formal quality control program. The minimum requirements of this program
consist of an initial demonstration of laboratory capability and an
ongoing analysis of spiked samples to evaluate and document data
quality. The laboratory must maintain records to document the quality of
data that is generated. Ongoing data quality checks are compared with
established performance criteria to determine if the results of analyses
meet the performance characteristics of the method. When results of
sample spikes indicate atypical method performance, a quality control
check standard must be analyzed to confirm that the measurements were
performed in an in-control mode of operation.
8.1.1 The analyst must make an initial, one-time, demonstration of
the ability to generate acceptable accuracy and precision with this
method. This ability is established as described in Section 8.2.
8.1.2 In recognition of advances that are occurring in
chromatography, the analyst is permitted certain options (detailed in
Section 10.1) to improve the separations or lower the cost of
measurements. Each time such a modification is made to the method, the
analyst is required to repeat the procedure in Section 8.2.
8.1.3 Each day, the analyst must analyze a reagent water blank to
demonstrate that interferences from the analytical system are under
control.
8.1.4 The laboratory must, on an ongoing basis, spike and analyze a
minimum of 10% of all samples to monitor and evaluate laboratory data
quality. This procedure is described in Section 8.3.
8.1.5 The laboratory must, on an ongoing basis, demonstrate through
the analyses of quality control check standards that the operation of
the measurement system is in control. This procedure is described in
Section 8.4. The frequency of the check standard analyses is equivalent
to 10% of all samples analyzed but may be reduced if spike recoveries
from samples (Section 8.3) meet all specified quality control criteria.
8.1.6 The laboratory must maintain performance records to document
the quality of data that is generated. This procedure is described in
Section 8.5.
8.2 To establish the ability to generate acceptable accuracy and
precision, the analyst must perform the following operations.
8.2.1 A quality control (QC) check sample concentrate is required
containing each parameter of interest at a concentration of 25 [micro]g/
mL in reagent water. The QC check sample concentrate must be obtained
from the U.S. Environmental Protection Agency, Environmental Monitoring
and Support Laboratory in Cincinnati, Ohio, if available. If not
available from that source, the QC check sample concentrate must be
obtained from another external source. If not available from either
source above, the QC check sample concentrate must be prepared by the
laboratory using stock standards prepared independently from those used
for calibration.
8.2.2 Prepare a QC check sample to contain 50 [micro]g/L of each
parameter by adding 200 [micro]L of QC check sample concentrate to 100
mL of reagent water.
8.2.3 Analyze four 5-mL aliquots of the well-mixed QC check sample
according to Section 10.
8.2.4 Calculate the average recovery (X) in [micro]g/L, and the
standard deviation of the recovery (s) in [micro]g/L, for each parameter
using the four results.
8.2.5 For each parameter compare s and X with the corresponding
acceptance criteria for precision and accuracy, respectively, found in
Table 3. If s and X for all parameters of interest meet the acceptance
criteria, the system performance is acceptable and analysis of actual
samples can begin. If either s exceeds the precision limit or X falls
outside the range for accuracy, the system performance is unacceptable
for that parameter. Locate and correct the source of the
[[Page 70]]
problem and repeat the test for each compound of interest.
8.3 The laboratory must, on an ongoing basis, spike at least 10% of
the samples from each sample site being monitored to assess accuracy.
For laboratories analyzing one to ten samples per month, at least one
spiked sample per month is required.
8.3.1 The concentration of the spike in the sample should be
determined as follows:
8.3.1.1 If, as in compliance monitoring, the concentration of a
specific parameter in the sample is being checked against a regulatory
concentration limit, the spike should be at that limit or 1 to 5 times
higher than the background concentration determined in Section 8.3.2,
whichever concentration would be larger.
8.3.1.2 If the concentration of a specific parameter in the sample
is not being checked against a limit specific to that parameter, the
spike should be at 50 [micro]g/L or 1 to 5 times higher than the
background concentration determined in Section 8.3.2, whichever
concentration would be larger.
8.3.2 Analyze one 5-mL sample aliquot to determine the background
concentration (B) of each parameter. If necessary, prepare a new QC
check sample concentrate (Section 8.2.1) appropriate for the background
concentrations in the sample. Spike a second 5-mL sample aliquot with 10
[micro]L of the QC check sample concentrate and analyze it to determine
the concentration after spiking (A) of each parameter. Calculate each
percent recovery (P) as 100(A-B)%/T, where T is the known true value of
the spike.
8.3.3 Compare the percent recovery (P) for each parameter with the
corresponding QC acceptance criteria found in Table 3. These acceptance
criteria were calculated to include an allowance for error in
measurement of both the background and spike concentrations, assuming a
spike to background ratio of 5:1. This error will be accounted for to
the extent that the analyst's spike to background ratio approaches
5:1.7
8.3.4 If any individual P falls outside the designated range for
recovery, that parameter has failed the acceptance criteria. A check
standard containing each parameter that failed the criteria must be
analyzed as described in Section 8.4.
8.4 If any parameter fails the acceptance criteria for recovery in
Section 8.3, a QC check standard containing each parameter that failed
must be prepared and analyzed.
Note: The frequency for the required analysis of a QC check standard
will depend upon the number of parameters being simultaneously tested,
the complexity of the sample matrix, and the performance of the
laboratory.
8.4.1 Prepare the QC check standard by adding 10 [micro]L of QC
check sample concentrate (Section 8.2.1 or 8.3.2) to 5 mL of reagent
water. The QC check standard needs only to contain the parameters that
failed criteria in the test in Section 8.3.
8.4.2 Analyze the QC check standard to determine the concentration
measured (A) of each parameter. Calculate each percent recovery
(Ps) as 100 (A/T)%, where T is the true value of the standard
concentration.
8.4.3 Compare the percent recovery (Ps) for each
parameter with the corresponding QC acceptance criteria found in Table
3. Only parameters that failed the test in Section 8.3 need to be
compared with these criteria. If the recovery of any such parameter
falls outside the designated range, the laboratory performance for that
parameter is judged to be out of control, and the problem must be
immediately identified and corrected. The analytical result for that
parameter in the unspiked sample is suspect and may not be reported for
regulatory compliance purposes.
8.5 As part of the QC program for the laboratory, method accuracy
for wastewater samples must be assessed and records must be maintained.
After the analysis of five spiked wastewater samples as in Section 8.3,
calculate the average percent recovery (P) and the standard deviation of
the percent recovery (sp). Express the accuracy assessment as
a percent recovery interval from P-2sp to P+2sp.
If P=90% and sp=10%, for example, the accuracy interval is
expressed as 70-110%. Update the accuracy assessment for each parameter
on a regular basis (e.g. after each five to ten new accuracy
measurements).
8.6 It is recommended that the laboratory adopt additional quality
assurance practices for use with this method. The specific practices
that are most productive depend upon the needs of the laboratory and the
nature of the samples. Field duplicates may be analyzed to assess the
precision of the environmental measurements. When doubt exists over the
identification of a peak on the chromatogram, confirmatory techniques
such as gas chromatography with a dissimilar column or mass spectrometer
must be used. Whenever possible, the laboratory should analyze standard
reference materials and participate in relevant performance evaluation
studies.
9. Sample Collection, Preservation, and Handling
9.1 All samples must be iced or refrigerated from the time of
collection until analysis. If the sample contains free or combined
chlorine, add sodium thiosulfate preservative (10 mg/40 mL is sufficient
for up to 5 ppm Cl2) to the empty sample bottle just prior to
shipping to the sampling site. EPA Methods 330.4 and 330.5 may be used
for measurement of residual chlorine.8 Field test kits are
available for this purpose.
9.2 If acrolein is to be analyzed, collect about 500 mL of sample in
a clean glass container. Adjust the pH of the sample to 4 to 5 using
acid or base, measuring with narrow
[[Page 71]]
range pH paper. Samples for acrolein analysis receiving no pH adjustment
must be analyzed within 3 days of sampling.
9.3 Grab samples must be collected in glass containers having a
total volume of at least 25 mL. Fill the sample bottle just to
overflowing in such a manner that no air bubbles pass through the sample
as the bottle is being filled. Seal the bottle so that no air bubbles
are entrapped in it. If preservative has been added, shake vigorously
for 1 min. Maintain the hermetic seal on the sample bottle until time of
analysis.
9.4 All samples must be analyzed within 14 days of
collection.3
10. Procedure
10.1 Table 1 summarizes the recommended operating conditions for the
gas chromatograph. Included in this table are estimated retention times
and MDL that can be achieved under these conditions. An example of the
separations achieved by Column 1 is shown in Figure 5. Other packed
columns, chromatographic conditions, or detectors may be used if the
requirements of Section 8.2 are met.
10.2 Calibrate the system daily as described in Section 7.
10.3 Adjust the purge gas (nitrogen or helium) flow rate to 20 mL-
min. Attach the trap inlet to the purging device, and set the purge and
trap system to purge (Figure 3). Open the syringe valve located on the
purging device sample introduction needle.
10.4 Remove the plunger from a 5-mL syringe and attach a closed
syringe valve. Open the sample bottle (or standard) and carefully pour
the sample into the syringe barrel to just short of overflowing. Replace
the syringe plunger and compress the sample. Open the syringe valve and
vent any residual air while adjusting the sample volume to 5.0 mL. Since
this process of taking an aliquot destroys the validity of the sample
for future analysis, the analyst should fill a second syringe at this
time to protect against possible loss of data. Add 10.0 [micro]L of the
internal standard spiking solution (Section 7.4.2), if applicable,
through the valve bore then close the valve.
10.5 Attach the syringe-syringe valve assembly to the syringe valve
on the purging device. Open the syringe valves and inject the sample
into the purging chamber.
10.6 Close both valves and purge the sample for 15.0 0.1 min while heating at 85 2
[deg]C.
10.7 After the 15-min purge time, attach the trap to the
chromatograph, adjust the purge and trap system to the desorb mode
(Figure 4), and begin to temperature program the gas chromatograph.
Introduce the trapped materials to the GC column by rapidly heating the
trap to 180 [deg]C while backflushing the trap with an inert gas between
20 and 60 mL/min for 1.5 min.
10.8 While the trap is being desorbed into the gas chromatograph,
empty the purging chamber using the sample introduction syringe. Wash
the chamber with two 5-mL flushes of reagent water.
10.9 After desorbing the sample for 1.5 min, recondition the trap by
returning the purge and trap system to the purge mode. Wait 15 s then
close the syringe valve on the purging device to begin gas flow through
the trap. The trap temperature should be maintained at 210 [deg]C. After
approximately 7 min, turn off the trap heater and open the syringe valve
to stop the gas flow through the trap. When the trap is cool, the next
sample can be analyzed.
10.10 Identify the parameters in the sample by comparing the
retention times of the peaks in the sample chromatogram with those of
the peaks in standard chromatograms. The width of the retention time
window used to make identifications should be based upon measurements of
actual retention time variations of standards over the course of a day.
Three times the standard deviation of a retention time for a compound
can be used to calculate a suggested window size; however, the
experience of the analyst should weigh heavily in the interpretation of
chromatograms.
11. Calculations
11.1 Determine the concentration of individual compounds in the
sample.
11.1.1 If the external standard calibration procedure is used,
calculate the concentration of the parameter being measured from the
peak response using the calibration curve or calibration factor
determined in Section 7.3.2.
11.1.2 If the internal standard calibration procedure is used,
calculate the concentration in the sample using the response factor (RF)
determined in Section 7.4.3 and Equation 2.
[GRAPHIC] [TIFF OMITTED] TC15NO91.097
Equation 2
where:
As=Response for the parameter to be measured.
Ais=Response for the internal standard.
Cis=Concentration of the internal standard.
11.2 Report results in [micro]g/L without correction for recovery
data. All QC data obtained should be reported with the sample results.
12. Method Performance
12.1 The method detection limit (MDL) is defined as the minimum
concentration of a substance that can be measured and reported with 99%
confidence that the value is above
[[Page 72]]
zero.1 The MDL concentrations listed in Table 1 were obtained
using reagent water.9 The MDL actually achieved in a given
analysis will vary depending on instrument sensitivity and matrix
effects.
12.2 This method is recommended for the concentration range from the
MDL to 1,000xMDL. Direct aqueous injection techniques should be used to
measure concentration levels above 1,000xMDL.
12.3 In a single laboratory (Battelle-Columbus), the average
recoveries and standard deviations presented in Table 2 were
obtained.9 Seven replicate samples were analyzed at each
spike level.
References
1. 40 CFR part 136, appendix B.
2. Bellar, T.A., and Lichtenberg, J.J. ``Determining Volatile
Organics at Microgram-per-Litre-Levels by Gas Chromatography,'' Journal
American Water Works Association, 66, 739 (1974).
3. ``Evaluate Test Procedures for Acrolein and Acrylonitrile,''
Special letter report for EPA Project 4719-A, U.S. Environmental
Protection Agency, Environmental Monitoring and Support Laboratory,
Cincinnati, Ohio 45268, 27 June 1979.
4. ``Carcinogens--Working With Carcinogens,'' Department of Health,
Education, and Welfare, Public Health Service, Center for Disease
Control, National Institute for Occupational Safety and Health,
Publication No. 77-206, August 1977.
5. ``OSHA Safety and Health Standards, General Industry,'' (29 CFR
part 1910), Occupational Safety and Health Administration, OSHA 2206
(Revised, January 1976).
6. ``Safety in Academic Chemistry Laboratories,'' American Chemical
Society Publication, Committee on Chemical Safety, 3rd Edition, 1979.
7. Provost, L.P., and Elder, R.S. ``Interpretation of Percent
Recovery Data,'' American Laboratory, 15, 58-63 (1983).
8. ``Methods 330.4 (Titrimetric, DPD-FAS) and 330.5
(Spectrophotometric, DPD) for Chlorine, Total Residual,'' Methods for
Chemical Analysis of Water and Wastes, EPA-600/4-79-020, U.S.
Environmental Protection Agency, Environmental Monitoring and Support
Laboratory, Cincinnati, Ohio 45268, March 1979.
9. ``Evaluation of Method 603 (Modified),'' EPA-600/4-84-ABC,
National Technical Information Service, PB84-, Springfield, Virginia
22161, Nov. 1984.
Table 1--Chromatographic Conditions and Method Detection Limits
------------------------------------------------------------------------
Retention time (min) Method
------------------------ detection
Parameter limit
Column 1 Column 2 ([micro]g/
L)
------------------------------------------------------------------------
Acrolein............................ 10.6 8.2 0.7
Acrylonitrile....................... 12.7 9.8 0.5
------------------------------------------------------------------------
Column 1 conditions: Porapak-QS (80/100 mesh) packed in a 10 ft x 2 mm
ID glass or stainless steel column with helium carrier gas at 30 mL/
min flow rate. Column temperature held isothermal at 110 [deg]C for
1.5 min (during desorption), then heated as rapidly as possible to 150
[deg]C and held for 20 min; column bakeout at 190 [deg]C for 10
min.\9\
Column 2 conditions: Chromosorb 101 (60/80 mesh) packed in a 6 ft. x 0.1
in. ID glass or stainless steel column with helium carrier gas at 40
mL/min flow rate. Column temperature held isothermal at 80 [deg]C for
4 min, then programmed at 50 [deg]C/min to 120 [deg]C and held for 12
min.
Table 2--Single Laboratory Accuracy and Precision--Method 603
----------------------------------------------------------------------------------------------------------------
Spike Average Standard
Sample conc. recovery deviation Average
Parameter matrix ([micro]g/ ([micro]g/ ([micro]g/ percent
L) L) L) recovery
----------------------------------------------------------------------------------------------------------------
Acrolein............................................... RW 5.0 5.2 0.2 104
RW 50.0 51.4 0.7 103
POTW 5.0 4.0 0.2 80
POTW 50.0 44.4 0.8 89
IW 5.0 0.1 0.1 2
IW 100.0 9.3 1.1 9
Acrylonitrile.......................................... RW 5.0 4.2 0.2 84
RW 50.0 51.4 1.5 103
POTW 20.0 20.1 0.8 100
POTW 100.0 101.3 1.5 101
IW 10.0 9.1 0.8 91
IW 100.0 104.0 3.2 104
----------------------------------------------------------------------------------------------------------------
ARW=Reagent water.
APOTW=Prechlorination secondary effluent from a municipal sewage treatment plant.
AIW=Industrial wastewater containing an unidentified acrolein reactant.
Table 3--Calibration and QC Acceptance Criteria--Method 603 \a\
----------------------------------------------------------------------------------------------------------------
Limit for
Range for Q S Range for X Range for
Parameter ([micro]g/ ([micro]g/ ([micro]g/ P, Ps (%)
L) L) L)
----------------------------------------------------------------------------------------------------------------
Acrolein..................................................... 45.9-54.1 4.6 42.9-60.1 88-118
[[Page 73]]
Acrylonitrile................................................ 41.2-58.8 9.9 33.1-69.9 71-135
----------------------------------------------------------------------------------------------------------------
a=Criteria were calculated assuming a QC check sample concentration of 50 [micro]g/L.9
Q=Concentration measured in QC check sample, in [micro]g/L (Section 7.5.3).
s=Standard deviation of four recovery measurements, in [micro]g/L (Section 8.2.4).
X=Average recovery for four recovery measurements, in [micro]g/L (Section 8.2.4).
P, Ps=Percent recovery measured (Section 8.3.2, Section 8.4.2).
[GRAPHIC] [TIFF OMITTED] TC02JY92.008
[[Page 74]]
[GRAPHIC] [TIFF OMITTED] TC02JY92.009
[[Page 75]]
[GRAPHIC] [TIFF OMITTED] TC02JY92.010
[[Page 76]]
[GRAPHIC] [TIFF OMITTED] TC02JY92.011
Method 604--Phenols
1. Scope and Application
1.1 This method covers the determination of phenol and certain
substituted phenols. The following parameters may be determined by this
method:
------------------------------------------------------------------------
STORET
Parameter No. CAS No.
------------------------------------------------------------------------
4-Chloro-3-methylphenol.......................... 34452 59-50-7
2--Chlorophenol.................................. 34586 95-57-8
2,4-Dichlorophenol............................... 34601 120-83-2
2,4-Dimethylphenol............................... 34606 105-67-9
2,4-Dinitrophenol................................ 34616 51-28-5
2-Methyl-4,6-dinitrophenol....................... 34657 534-52-1
2-Nitrophenol.................................... 34591 88-75-5
4-Nitrophenol.................................... 34646 100-02-7
Pentachlorophenol................................ 39032 87-86-5
Phenol........................................... 34694 108-95-2
2,4,6-Trichlorophenol............................ 34621 88-06-2
------------------------------------------------------------------------
1.2 This is a flame ionization detector gas chromatographic (FIDGC)
method applicable to the determination of the compounds listed above in
municipal and industrial discharges as provided under 40 CFR 136.1. When
this method is used to analyze unfamiliar samples for any or all of the
compounds above, compound identifications should be supported by at
least one additional qualitative technique. This method describes
analytical conditions for derivatization, cleanup, and electron capture
detector gas chromatography (ECDGC) that can be used to confirm
measurements made by FIDGC. Method 625 provides gas chromatograph/mass
spectrometer (GC/MS) conditions appropriate for the qualitative and
quantitative confirmation of results for all of the parameters listed
above, using the extract produced by this method.
1.3 The method detection limit (MDL, defined in Section 14.1) \1\
for each parameter is listed in Table 1. The MDL for a specific
wastewater may differ from those listed, depending upon the nature of
interferences in the sample matrix. The MDL listed in Table 1 for each
parameter was achieved with a flame ionization detector (FID). The MDLs
that were achieved when the derivatization cleanup and electron capture
detector (ECD) were employed are presented in Table 2.
[[Page 77]]
1.4 Any modification of this method, beyond those expressly
permitted, shall be considered as a major modification subject to
application and approval of alternate test procedures under 40 CFR 136.4
and 136.5.
1.5 This method is restricted to use by or under the supervision of
analysts experienced in the use of a gas chromatograph and in the
interpretation of gas chromatograms. Each analyst must demonstrate the
ability to generate acceptable results with this method using the
procedure described in Section 8.2.
2. Summary of Method
2.1 A measured volume of sample, approximately 1-L, is acidified and
extracted with methylene chloride using a separatory funnel. The
methylene chloride extract is dried and exchanged to 2-propanol during
concentration to a volume of 10 mL or less. The extract is separated by
gas chromatography and the phenols are then measured with an FID.\2\
2.2 A preliminary sample wash under basic conditions can be employed
for samples having high general organic and organic base interferences.
2.3 The method also provides for a derivatization and column
chromatography cleanup procedure to aid in the elimination of
interferences.2, 3 The derivatives are analyzed by ECDGC.
3. Interferences
3.1 Method interferences may be caused by contaminants in solvents,
reagents, glassware, and other sample processing hardware that lead to
discrete artifacts and/or elevated baselines in gas chromatograms. All
of these materials must be routinely demonstrated to be free from
interferences under the conditions of the analysis by running laboratory
reagent blanks as described in Section 8.1.3.
3.1.1 Glassware must be scrupulously cleaned.\4\ Clean all glassware
as soon as possible after use by rinsing with the last solvent used in
it. Solvent rinsing should be followed by detergent washing with hot
water, and rinses with tap water and distilled water. The glassware
should then be drained dry, and heated in a muffle furnace at 400 [deg]C
for 15 to 30 min. Some thermally stable materials, such as PCBs, may not
be eliminated by this treatment. Solvent rinses with acetone and
pesticide quality hexane may be substituted for the muffle furnace
heating. Thorough rinsing with such solvents usually eliminates PCB
interference. Volumetric ware should not be heated in a muffle furnace.
After drying and cooling, glassware should be sealed and stored in a
clean environment to prevent any accumulation of dust or other
contaminants. Store inverted or capped with aluminum foil.
3.1.2 The use of high purity reagents and solvents helps to minimize
interference problems. Purification of solvents by distillation in all-
glass systems may be required.
3.2 Matrix interferences may be caused by contaminants that are
coextracted from the sample. The extent of matrix interferences will
vary considerably from source to source, depending upon the nature and
diversity of the industrial complex or municipality being sampled. The
derivatization cleanup procedure in Section 12 can be used to overcome
many of these interferences, but unique samples may require additional
cleanup approaches to achieve the MDL listed in Tables 1 and 2.
3.3 The basic sample wash (Section 10.2) may cause significantly
reduced recovery of phenol and 2,4-dimethylphenol. The analyst must
recognize that results obtained under these conditions are minimum
concentrations.
4. Safety
4.1 The toxicity or carcinogenicity of each reagent used in this
mothod has not been precisely defined; however, each chemical compound
should be treated as a potential health hazard. From this viewpoint,
exposure to these chemicals must be reduced to the lowest possible level
by whatever means available. The laboratory is responsible for
maintaining a current awareness file of OSHA regulations regarding the
safe handling of the chemicals specified in this method. A reference
file of material data handling sheets should also be made available to
all personnel involved in the chemical analysis. Additional references
to laboratory safety are available and have been identified
5-7 for the information of analyst.
4.2 Special care should be taken in handling pentafluorobenzyl
bromide, which is a lachrymator, and 18-crown-6-ether, which is highly
toxic.
5. Apparatus and Materials
5.1 Sampling equipment, for discrete or composite sampling.
5.1.1 Grab sample bottle--1-L or 1-qt, amber glass, fitted with a
screw cap lined with Teflon. Foil may be substituted for Teflon if the
sample is not corrosive. If amber bottles are not available, protect
samples from light. The bottle and cap liner must be washed, rinsed with
acetone or methylene chloride, and dried before use to minimize
contamination.
5.1.2 Automatic sampler (optional)--The sampler must incorporate
glass sample containers for the collection of a minimum of 250 mL of
sample. Sample containers must be kept refrigerated at 4 [deg]C and
protected from light during compositing. If the sampler uses a
peristaltic pump, a minimum length of compressible silicone rubber
tubing may be
[[Page 78]]
used. Before use, however, the compressible tubing should be thoroughly
rinsed with methanol, followed by repeated rinsings with distilled water
to minimize the potential for contamination of the sample. An
integrating flow meter is required to collect flow proportional
composites.
5.2 Glassware (All specifications are suggested. Catalog numbers are
included for illustration only.):
5.2.1 Separatory funnel--2-L, with Teflon stopcock.
5.2.2 Drying column--Chromatographic column, 400 mm long x 19 mm ID,
with coarse frit filter disc.
5.2.3 Chromatographic column--100 mm long x 10 mm ID, with Teflon
stopcock.
5.2.4 Concentrator tube, Kuderna-Danish--10-mL, graduated (Kontes K-
570050-1025 or equivalent). Calibration must be checked at the volumes
employed in the test. Ground glass stopper is used to prevent
evaporation of extracts.
5.2.5 Evaporative flask, Kuderna-Danish--500-mL (Kontes K-570001-
0500 or equivalent). Attach to concentrator tube with springs.
5.2.6 Snyder column, Kuderna-Danish--Three-ball macro (Kontes K-
503000-0121 or equivalent).
5.2.7 Snyder column, Kuderna-Danish--Two-ball micro (Kontes K-
569001-0219 or equivalent).
5.2.8 Vials--10 to 15-mL, amber glass, with Teflon-lined screw cap.
5.2.9 Reaction flask--15 to 25-mL round bottom flask, with standard
tapered joint, fitted with a water-cooled condenser and U-shaped drying
tube containing granular calcium chloride.
5.3 Boiling chips--Approximately 10/40 mesh. Heat to 400 [deg]C for
30 min or Soxhlet extract with methylene chloride.
5.4 Water bath--Heated, with concentric ring cover, capable of
temperature control (2[deg]C). The bath should be
used in a hood.
5.5 Balance--Analytical, capable of accurately weighting 0.0001 g.
5.6 Gas chromatograph--An analytical system complete with a
temperature programmable gas chromatograph suitable for on-column
injection and all required accessories including syringes, analytical
columns, gases, detector, and strip-chart recorder. A data system is
recommended for measuring peak areas.
5.6.1 Column for underivatized phenols--1.8 m long x 2 mm ID glass,
packed with 1% SP-1240DA on Supelcoport (80/100 mesh) or equivalent.
This column was used to develop the method performance statements in
Section 14. Guidelines for the use of alternate column packings are
provided in Section 11.1.
5.6.2 Column for derivatized phenols--1.8 m long x 2 mm ID glass,
packed with 5% OV-17 on Chromosorb W-AW-DMCS (80/100 mesh) or
equivalent. This column has proven effective in the analysis of
wastewaters for derivatization products of the parameters listed in the
scope (Section 1.1), and was used to develop the method performance
statements in Section 14. Guidelines for the use of alternate column
packings are provided in Section 11.1.
5.6.3 Detectors--Flame ionization and electron capture detectors.
The FID is used when determining the parent phenols. The ECD is used
when determining the derivatized phenols. Guidelines for the use of
alternatve detectors are provided in Section 11.1.
6. Reagents
6.1 Reagent water--Reagent water is defined as a water in which an
interferent is not observed at the MDL of the parameters of interest.
6.2 Sodium hydroxide solution (10 N)--Dissolve 40 g of NaOH (ACS) in
reagent water and dilute to 100 mL.
6.3 Sodium hydroxide solution (1 N)--Dissolve 4 g of NaOH (ACS) in
reagent water and dilute to 100 mL.
6.4 Sodium sulfate--(ACS) Granular, anhydrous. Purify by heating at
400[deg]C for 4 h in a shallow tray.
6.5 Sodium thiosulfate--(ACS) Granular.
6.6 Sulfuric acid (1+1)--Slowly, add 50 mL of
H2SO4 (ACS, sp. gr. 1.84) to 50 mL of reagent
water.
6.7 Sulfuric acid (1 N)--Slowly, add 58 mL of
H2SO4 (ACS, sp. gr. 1.84) to reagent water and
dilute to 1 L.
6.8 Potassium carbonate--(ACS) Powdered.
6.9 Pentafluorobenzyl bromide ([alpha]-Bromopentafluorotoluene)--97%
minimum purity.
Note: This chemical is a lachrymator. (See Section 4.2.)
6.10 18-crown-6-ether (1,4,7,10,13,16-Hexaoxacyclooctadecane)--98%
minimum purity.
Note: This chemical is highly toxic.
6.11 Derivatization reagent--Add 1 mL of pentafluorobenzyl bromide
and 1 g of 18-crown-6-ether to a 50-mL volumetric flask and dilute to
volume with 2-propanol. Prepare fresh weekly. This operation should be
carried out in a hood. Store at 4 [deg]C and protect from light.
6.12 Acetone, hexane, methanol, methylene chloride, 2-propanol,
toluene--Pesticide quality or equivalent.
6.13 Silica gel--100/200 mesh, Davison, grade-923 or equivalent.
Activate at 130 [deg]C overnight and store in a desiccator.
6.14 Stock standard solutions (1.00 [micro]g/[micro]L)--Stock
standard solutions may be prepared from pure standard materials or
purchased as certified solutions.
6.14.1 Prepare stock standard solutions by accurately weighing about
0.0100 g of pure material. Dissolve the material in 2-propanol
[[Page 79]]
and dilute to volume in a 10-mL volumetric flask. Larger volumes can be
used at the convenience of the analyst. When compound purity is assayed
to be 96% or greater, the weight can be used without correction to
calculate the concentration of the stock standard. Commercially prepared
stock standards can be used at any concentration if they are certified
by the manufacturer or by an independent source.
6.14.2 Transfer the stock standard solutions into Teflon-sealed
screw-cap bottles. Store at 4 [deg]C and protect from light. Stock
standard solutions should be checked frequently for signs of degradation
or evaporation, especially just prior to preparing calibration standards
from them.
6.14.3 Stock standard solutions must be replaced after six months,
or sooner if comparison with check standards indicates a problem.
6.15 Quality control check sample concentrate--See Section 8.2.1.
7. Calibration
7.1 To calibrate the FIDGC for the anaylsis of underivatized
phenols, establish gas chromatographic operating conditions equivalent
to those given in Table 1. The gas chromatographic system can be
calibrated using the external standard technique (Section 7.2) or the
internal standard technique (Section 7.3).
7.2 External standard calibration procedure for FIDGC:
7.2.1 Prepare calibration standards at a minimum of three
concentration levels for each parameter of interest by adding volumes of
one or more stock standards to a volumetric flask and diluting to volume
with 2-propanol. One of the external standards should be at a
concentration near, but above, the MDL (Table 1) and the other
concentrations should correspond to the expected range of concentrations
found in real samples or should define the working range of the
detector.
7.2.2 Using injections of 2 to 5 [micro]l, analyze each calibration
standard according to Section 11 and tabulate peak height or area
responses against the mass injected. The results can be used to prepare
a calibration curve for each compound. Alternatively, if the ratio of
response to amount injected (calibration factor) is a constant over the
working range (<10% relative standard deviation, RSD), linearity through
the origin can be assumed and the average ratio or calibration factor
can be used in place of a calibration curve.
7.3 Internal standard calibration procedure for FIDGC--To use this
approach, the analyst must select one or more internal standards that
are similar in analytical behavior to the compounds of interest. The
analyst must further demonstrate that the measurement of the internal
standard is not affected by method or matrix interferences. Because of
these limitations, no internal standard can be suggested that is
applicable to all samples.
7.3.1 Prepare calibration standards at a minimum of three
concentration levels for each parameter of interest by adding volumes of
one or more stock standards to a volumetric flask. To each calibration
standard, add a known constant amount of one or more internal standards,
and dilute to volume with 2-propanol. One of the standards should be at
a concentration near, but above, the MDL and the other concentrations
should correspond to the expected range of concentrations found in real
samples or should define the working range of the detector.
7.3.2 Using injections of 2 to 5 [micro]L, analyze each calibration
standard according to Section 11 and tabulate peak height or area
responses against concentration for each compound and internal standard.
Calculate response factors (RF) for each compound using Equation 1.
RF= (As)(Cis) (Ais)(Cs)
----------------------------------------------------------------------------------------------------------------
Equation 1
where:
As=Response for the parameter to be measured.
Ais=Response for the internal standard.
Cis=Concentration of the internal standard ([micro]g/L).
Cs=Concentration of the parameter to be measured ([micro]g/
L).
If the RF value over the working range is a constant (<10% RSD), the
RF can be assumed to be invariant and the average RF can be used for
calculations. Alternatively, the results can be used to plot a
calibration curve of response ratios, As/Ais, vs.
RF.
7.4 The working calibration curve, calibration factor, or RF must be
verified on each working day by the measurement of one or more
calibration standards. If the response for any parameter varies from the
predicted response by more than 15%, a new
calibration curve must be prepared for that compound.
7.5 To calibrate the ECDGC for the analysis of phenol derivatives,
establish gas chromatographic operating conditions equivalent to those
given in Table 2.
7.5.1 Prepare calibration standards at a minimum of three
concentration levels for each parameter of interest by adding volumes of
one or more stock standards to a volumetric flask and diluting to volume
with 2-propanol. One of the external standards should be at a
concentration near, but above, the MDL (Table 2) and the other
concentrations should correspond to the expected
[[Page 80]]
range of concentrations found in real samples or should define the
working range of the detector.
7.5.2 Each time samples are to be derivatized, simultaneously treat
a 1-mL aliquot of each calibration standard as described in Section 12.
7.5.3 After derivatization, analyze 2 to 5 [micro]L of each column
eluate collected according to the method beginning in Section 12.8 and
tabulate peak height or area responses against the calculated equivalent
mass of underivatized phenol injected. The results can be used to
prepare a calibration curve for each compound.
7.6 Before using any cleanup procedure, the analyst must process a
series of calibration standards through the procedure to validate
elution patterns and the absence of interferences from the reagents.
8. Quality Control
8.1 Each laboratory that uses this method is required to operate a
formal quality control program. The minimum requirements of this program
consist of an initial demonstration of laboratory capability and an
ongoing analysis of spiked samples to evaluate and document data
quality. The laboratory must maintain records to document the quality of
data that is generated. Ongoing data quality checks are compared with
established performance criteria to determine if the results of analyses
meet the performance characteristics of the method. When results of
sample spikes indicate atypical method performance, a quality control
check standard must be analyzed to confirm that the measurements were
performed in an in-control mode of operation.
8.1.1 The analyst must make an initial, one-time, demonstration of
the ability to generate acceptable accuracy and precision with this
method. This ability is established as described in Section 8.2.
8.1.2 In recognition of advances that are occurring in
chromatography, the analyst is permitted certain options (detailed in
Sections 10.6 and 11.1) to improve the separations or lower the cost of
measurements. Each time such a modification is made to the method, the
analyst is required to repeat the procedure in Section 8.2.
8.1.3 Before processing any samples the analyst must analyze a
reagent water blank to demonstrate that interferences from the
analytical system and glassware are under control. Each time a set of
samples is extracted or reagents are changed a reagent water blank must
be processed as a safeguard against laboratory contamination.
8.1.4 The laboratory must, on an ongoing basis, spike and analyze a
minimum of 10% of all samples to monitor and evaluate laboratory data
quality. This procedure is described in Section 8.3.
8.1.5 The laboratory must, on an ongoing basis, demonstrate through
the analyses of quality control check standards that the operation of
the measurement system is in control. This procedure is described in
Section 8.4. The frequency of the check standard analyses is equivalent
to 10% of all samples analyzed but may be reduced if spike recoveries
from samples (Section 8.3) meet all specified quality control criteria.
8.1.6 The laboratory must maintain performance records to document
the quality of data that is generated. This procedure is described in
Section 8.5.
8.2 To establish the ability to generate acceptable accuracy and
precision, the analyst must perform the following operations.
8.2.1 A quality control (QC) check sample concentrate is required
containing each parameter of interest at a concentration of 100
[micro]g/mL in 2-propanol. The QC check sample concentrate must be
obtained from the U.S. Environmental Protection Agency, Environmental
Monitoring and Support Laboratory in Cincinnati, Ohio, if available. If
not available from that source, the QC check sample concentrate must be
obtained from another external source. If not available from either
source above, the QC check sample concentrate must be prepared by the
laboratory using stock standards prepared independently from those used
for calibration.
8.2.2 Using a pipet, prepare QC check samples at a concentration of
100 [micro]g/L by adding 1.00 mL of QC check sample concentrate to each
of four 1-L aliquots of reagent water.
8.2.3 Analyze the well-mixed QC check samples according to the
method beginning in Section 10.
8.2.4 Calculate the average recovery (X) in [micro]g/L, and the
standard deviation of the recovery (s) in [micro]g/L, for each parameter
using the four results.
8.2.5 For each parameter compare s and X with the corresponding
acceptance criteria for precision and accuracy, respectively, found in
Table 3. If s and X for all parameters of interest meet the acceptance
criteria, the system performance is acceptable and analysis of actual
samples can begin. If any individual s exceeds the precision limit or
any individual X falls outside the range for accuracy, the system
performance is unacceptable for that parameter.
Note: The large number of parameters in Talbe 3 present a
substantial probability that one or more will fail at least one of the
acceptance criteria when all parameters are analyzed.
8.2.6 When one or more of the parameters tested fail at least one of
the acceptance criteria, the analyst must proceed according to Section
8.2.6.1 or 8.2.6.2.
8.2.6.1 Locate and correct the source of the problem and repeat the
test for all parameters of interest beginning with Section 8.2.2.
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8.2.6.2 Beginning with Section 8.2.2, repeat the test only for those
parameters that failed to meet criteria. Repeated failure, however, will
confirm a general problem with the measurement system. If this occurs,
locate and correct the source of the problem and repeat the test for all
compounds of interest beginning with Section 8.2.2.
8.3 The laboratory must, on an ongoing basis, spike at least 10% of
the samples from each sample site being monitored to assess accuracy.
For laboratories analyzing one to ten samples per month, at least one
spiked sample per month is required.
8.3.1 The concentration of the spike in the sample should be
determined as follows:
8.3.1.1 If, as in compliance monitoring, the concentration of a
specific parameter in the sample is being checked against a regulatory
concentration limit, the spike should be at that limit or 1 to 5 times
higher than the background concentration determined in Section 8.3.2,
whichever concentration would be larger.
8.3.1.2 If the concentration of a specific parameter in the sample
is not being checked against a limit specific to that parameter, the
spike should be at 100 [micro]g/L or 1 to 5 times higher than the
background concentration determined in Section 8.3.2, whichever
concentration would be larger.
8.3.1.3 If it is impractical to determine background levels before
spiking (e.g., maximum holding times will be exceeded), the spike
concentration should be (1) the regulatory concentration limit, if any,
or, if none, (2) the larger of either 5 times higher than the expected
background concentration or 100 [micro]g/L.
8.3.2 Analyze one sample aliquot to determine the background
concentration (B) of each parameter. If necessary, prepare a new QC
check sample concentrate (Section 8.2.1) appropriate for the background
concentrations in the sample. Spike a second sample aliquot with 1.0 mL
of the QC check sample concentrate and analyze it to determine the
concentration after spiking (A) of each parameter. Calculate each
percent recovery (P) as 100(A-B)%/T, where T is the known true value of
the spike.
8.3.3 Compare the percent recovery (P) for each parameter with the
corresponding QC acceptance criteria found in Table 3. These acceptance
criteria were calculated to include an allowance for error in
measurement of both the background and spike concentrations, assuming a
spike to background ratio of 5:1. This error will be accounted for to
the extent that the analyst's spike to background ratio approaches
5:1.8 If spiking was performed at a concentration lower than
100 [micro]g/L, the analyst must use either the QC acceptance criteria
in Table 3, or optional QC acceptance criteria calculated for the
specific spike concentration. To calculate optional acceptance criteria
for the recovery of a parameter: (1) Calculate accuracy (X') using the
equation in Table 4, substituting the spike concentration (T) for C; (2)
calculate overall precision (S') using the equation in Table 4,
substituting X' for X; (3) calculate the range for recovery at the spike
concentration as (100 X'/T)2.44(100 S'/
T)%.8
8.3.4 If any individual P falls outside the designated range for
recovery, that parameter has failed the acceptance criteria. A check
standard containing each parameter that failed the criteria must be
analyzed as described in Section 8.4.
8.4 If any parameter fails the acceptance criteria for recovery in
Section 8.3, a QC check standard containing each parameter that failed
must be prepared and analyzed.
Note: The frequency for the required analysis of a QC check standard
will depend upon the number of parameters being simultaneously tested,
the complexity of the sample matrix, and the performance of the
laboratory.
8.4.1 Prepare the QC check standard by adding 1.0 mL of QC check
sample concentrate (Section 8.2.1 or 8.3.2) to 1 L of reagent water. The
QC check standard needs only to contain the parameters that failed
criteria in the test in Section 8.3.
8.4.2 Analyze the QC check standard to determine the concentration
measured (A) of each parameter. Calculate each percent recovery
(Ps) as 100 (A/T)%, where T is the true value of the standard
concentration.
8.4.3 Compare the percent recovery (Ps) for each
parameter with the corresponding QC acceptance criteria found in Table
3. Only parameters that failed the test in Section 8.3 need to be
compared with these criteria. If the recovery of any such parameter
falls outside the designated range, the laboratory performance for that
parameter is judged to be out of control, and the problem must be
immediately identified and corrected. The analytical result for that
parameter in the unspiked sample is suspect and may not be reported for
regulatory compliance purposes.
8.5 As part of the QC program for the laboratory, method accuracy
for wastewater samples must be assessed and records must be maintained.
After the analysis of five spiked wastewater samples as in Section 8.3,
calculate the average percent recovery (P) and the standard deviation of
the percent recovery (sp). Express the accuracy assessment as
a percent recovery interval from P-2sp to P+2sp.
If P=90% and sp=10%, for example, the accuracy interval is
expressed as 70-110%. Update the accuracy assessment for each parameter
on a regular basis (e.g. after each five to ten new accuracy
measurements).
8.6. It is recommended that the laboratory adopt additional quality
assurance practices for use with this method. The specific practices
that are most productive depend upon the needs of the laboratory and
[[Page 82]]
the nature of the samples. Field duplicates may be analyzed to assess
the precision of the environmental measurements. When doubt exists over
the identification of a peak on the chromatogram, confirmatory
techniques such as gas chromatography with a dissimilar column, specific
element detector, or mass spectrometer must be used. Whenever possible,
the laboratory should analyze standard reference materials and
participate in relevant performance evaluation studies.
9. Sample Collection, Preservation, and Handling
9.1 Grab samples must be collected in glass containers. Conventional
sampling practices 9 should be followed, except that the
bottle must not be prerinsed with sample before collection. Composite
samples should be collected in refrigerated glass containers in
accordance with the requirements of the program. Automatic sampling
equipment must be as free as possible of Tygon tubing and other
potential sources of contamination.
9.2 All samples must be iced or refrigerated at 4 [deg]C from the
time of collection until extraction. Fill the sample bottles and, if
residual chlorine is present, add 80 mg of sodium thiosulfate per liter
of sample and mix well. EPA Methods 330.4 and 330.5 may be used for
measurement of residual chlorine.10 Field test kits are
available for this purpose.
9.3 All samples must be extracted within 7 days of collection and
completely analyzed within 40 days of extraction.2
10. Sample Extraction
10.1 Mark the water meniscus on the side of sample bottle for later
determination of sample volume. Pour the entire sample into a 2-L
separatory funnel.
10.2 For samples high in organic content, the analyst may solvent
wash the sample at basic pH as prescribed in Sections 10.2.1 and 10.2.2
to remove potential method interferences. Prolonged or exhaustive
contact with solvent during the wash may result in low recovery of some
of the phenols, notably phenol and 2,4-dimethylphenol. For relatively
clean samples, the wash should be omitted and the extraction, beginning
with Section 10.3, should be followed.
10.2.1 Adjust the pH of the sample to 12.0 or greater with sodium
hydroxide solution.
10.2.2 Add 60 mL of methylene chloride to the sample by shaking the
funnel for 1 min with periodic venting to release excess pressure.
Discard the solvent layer. The wash can be repeated up to two additional
times if significant color is being removed.
10.3 Adjust the sample to a pH of 1 to 2 with sulfuric acid.
10.4 Add 60 mL of methylene chloride to the sample bottle, seal, and
shake 30 s to rinse the inner surface. Transfer the solvent to the
separatory funnel and extract the sample by shaking the funnel for 2
min. with periodic venting to release excess pressure. Allow the organic
layer to separate from the water phase for a minimum of 10 min. If the
emulsion interface between layers is more than one-third the volume of
the solvent layer, the analyst must employ mechanical techniques to
complete the phase separation. The optimum technique depends upon the
sample, but may include stirring, filtration of the emulsion through
glass wool, centrifugation, or other physical methods. Collect the
methylene chloride extract in a 250-mL Erlenmeyer flask.
10.5 Add a second 60-mL volume of methylene chloride to the sample
bottle and repeat the extraction procedure a second time, combining the
extracts in the Erlenmeyer flask. Perform a third extraction in the same
manner.
10.6 Assemble a Kuderna-Danish (K-D) concentrator by attaching a 10-
mL concentrator tube to a 500-mL evaporative flask. Other concentration
devices or techniques may be used in place of the K-D concentrator if
the requirements of Section 8.2 are met.
10.7 Pour the combined extract through a solvent-rinsed drying
column containing about 10 cm of anhydrous sodium sulfate, and collect
the extract in the K-D concentrator. Rinse the Erlenmeyer flask and
column with 20 to 30 mL of methylene chloride to complete the
quantitative transfer.
10.8 Add one or two clean boiling chips to the evaporative flask and
attach a three-ball Snyder column. Prewet the Snyder column by adding
about 1 mL of methylene chloride to the top. Place the K-D apparatus on
a hot water bath (60 to 65 [deg]C) so that the concentrator tube is
partially immersed in the hot water, and the entire lower rounded
surface of the flask is bathed with hot vapor. Adjust the vertical
position of the apparatus and the water temperature as required to
complete the concentration in 15 to 20 min. At the proper rate of
distillation the balls of the column will actively chatter but the
chambers will not flood with condensed solvent. When the apparent volume
of liquid reaches 1 mL, remove the K-D apparatus and allow it to drain
and cool for at least 10 min.
10.9 Increase the temperature of the hot water bath to 95 to 100
[deg]C. Remove the Synder column and rinse the flask and its lower joint
into the concentrator tube with 1 to 2 mL of 2-propanol. A 5-mL syringe
is recommended for this operation. Attach a two-ball micro-Snyder column
to the concentrator tube and prewet the column by adding about 0.5 mL of
2-propanol to the top. Place the micro-K-D apparatus on the water bath
so that the concentrator tube is partially immersed in the hot water.
Adjust the vertical position of the apparatus and the water temperature
as required to complete
[[Page 83]]
concentration in 5 to 10 min. At the proper rate of distillation the
balls of the column will actively chatter but the chambers will not
flood. When the apparent volume of liquid reaches 2.5 mL, remove the K-D
apparatus and allow it to drain and cool for at least 10 min. Add an
additional 2 mL of 2-propanol through the top of the micro-Snyder column
and resume concentrating as before. When the apparent volume of liquid
reaches 0.5 mL, remove the K-D apparatus and allow it to drain and cool
for at least 10 min.
10.10 Remove the micro-Snyder column and rinse its lower joint into
the concentrator tube with a minimum amount of 2-propanol. Adjust the
extract volume to 1.0 mL. Stopper the concentrator tube and store
refrigerated at 4 [deg]C if further processing will not be performed
immediately. If the extract will be stored longer than two days, it
should be transferred to a Teflon-sealed screw-cap vial. If the sample
extract requires no further cleanup, proceed with FIDGC analysis
(Section 11). If the sample requires further cleanup, proceed to Section
12.
10.11 Determine the original sample volume by refilling the sample
bottle to the mark and transferring the liquid to a 1000-mL graduated
cylinder. Record the sample volume to the nearest 5 mL.
11. Flame Ionization Detector Gas Chromatography
11.1 Table 1 summarizes the recommended operating conditions for the
gas chromatograph. Included in this table are retention times and MDL
that can be achieved under these conditions. An example of the
separations achieved by this column is shown in Figure 1. Other packed
or capillary (open-tubular) columns, chromatographic conditions, or
detectors may be used if the requirements of Section 8.2 are met.
11.2 Calibrate the system daily as described in Section 7.
11.3 If the internal standard calibration procedure is used, the
internal standard must be added to the sample extract and mixed
thoroughly immediately before injection into the gas chromatograph.
11.4 Inject 2 to 5 [micro]L of the sample extract or standard into
the gas chromatograph using the solvent-flush technique.11
Smaller (1.0 [micro]L) volumes may be injected if automatic devices are
employed. Record the volume injected to the nearest 0.05 [micro]L, and
the resulting peak size in area or peak height units.
11.5 Identify the parameters in the sample by comparing the
retention times of the peaks in the sample chromatogram with those of
the peaks in standard chromatograms. The width of the retention time
window used to make identifications should be based upon measurements of
actual retention time variations of standards over the course of a day.
Three times the standard deviation of a retention time for a compound
may be used to calculate a suggested window size; however, the
experience of the analyst should weigh heavily in the interpretation of
chromatograms.
11.6 If the response for a peak exceeds the working range of the
system, dilute the extract and reanalyze.
11.7 If the measurement of the peak response is prevented by the
presence of interferences, an alternative gas chromatographic procedure
is required. Section 12 describes a derivatization and column
chromatographic procedure which has been tested and found to be a
practical means of analyzing phenols in complex extracts.
12. Derivatization and Electron Capture Detector Gas Chromatography
12.1 Pipet a 1.0-mL aliquot of the 2-propanol solution of standard
or sample extract into a glass reaction vial. Add 1.0 mL of derivatizing
reagent (Section 6.11). This amount of reagent is sufficient to
derivatize a solution whose total phenolic content does not exceed 0.3
mg/mL.
12.2 Add about 3 mg of potassium carbonate to the solution and shake
gently.
12.3 Cap the mixture and heat it for 4 h at 80 [deg]C in a hot water
bath.
12.4 Remove the solution from the hot water bath and allow it to
cool.
12.5 Add 10 mL of hexane to the reaction flask and shake vigorously
for 1 min. Add 3.0 mL of distilled, deionized water to the reaction
flask and shake for 2 min. Decant a portion of the organic layer into a
concentrator tube and cap with a glass stopper.
12.6 Place 4.0 g of silica gel into a chromatographic column. Tap
the column to settle the silica gel and add about 2 g of anhydrous
sodium sulfate to the top.
12.7 Preelute the column with 6 mL of hexane. Discard the eluate and
just prior to exposure of the sodium sulfate layer to the air, pipet
onto the column 2.0 mL of the hexane solution (Section 12.5) that
contains the derivatized sample or standard. Elute the column with 10.0
mL of hexane and discard the eluate. Elute the column, in order, with:
10.0 mL of 15% toluene in hexane (Fraction 1); 10.0 mL of 40% toluene in
hexane (Fraction 2); 10.0 mL of 75% toluene in hexane (Fraction 3); and
10.0 mL of 15% 2-propanol in toluene (Fraction 4). All elution mixtures
are prepared on a volume: volume basis. Elution patterns for the
phenolic derivatives are shown in Table 2. Fractions may be combined as
desired, depending upon the specific phenols of interest or level of
interferences.
12.8 Analyze the fractions by ECDGC. Table 2 summarizes the
recommended operating conditions for the gas chromatograph. Included in
this table are retention times and MDL that can be achieved under these
conditions. An example of the separations
[[Page 84]]
achieved by this column is shown in Figure 2.
12.9 Calibrate the system daily with a minimum of three aliquots of
calibration standards, containing each of the phenols of interest that
are derivatized according to Section 7.5.
12.10 Inject 2 to 5 [micro]L of the column fractions into the gas
chromatograph using the solvent-flush technique. Smaller (1.0 [micro]L)
volumes can be injected if automatic devices are employed. Record the
volume injected to the nearest 0.05 [micro]L, and the resulting peak
size in area or peak height units. If the peak response exceeds the
linear range of the system, dilute the extract and reanalyze.
13. Calculations
13.1 Determine the concentration of individual compounds in the
sample analyzed by FIDGC (without derivatization) as indicated below.
13.1.1 If the external standard calibration procedure is used,
calculate the amount of material injected from the peak response using
the calibration curve or calibration factor determined in Section 7.2.2.
The concentration in the sample can be calculated from Equation 2.
[GRAPHIC] [TIFF OMITTED] TC15NO91.098
Equation 2
where:
A=Amount of material injected (ng).
Vi=Volume of extract injected ([micro]L).
Vt=Volume of total extract ([micro]L).
Vs=Volume of water extracted (mL).
13.1.2 If the internal standard calibration procedure is used,
calculate the concentration in the sample using the response factor (RF)
determined in Section 7.3.2 and Equation 3.
[GRAPHIC] [TIFF OMITTED] TC15NO91.099
Equation 3
where:
As=Response for the parameter to be measured.
Ais=Response for the internal standard.
Is=Amount of internal standard added to each extract
([micro]g).
Vo=Volume of water extracted (L).
13.2 Determine the concentration of individual compounds in the
sample analyzed by derivatization and ECDGC according to Equation 4.
[GRAPHIC] [TIFF OMITTED] TC15NO91.100
Equation 4
where:
A=Mass of underivatized phenol represented by area of peak in sample
chromatogram, determined from calibration curve in Section 7.5.3 (ng).
Vi=Volume of eluate injected ([micro]L).
Vt=Total volume of column eluate or combined fractions from
which Vi was taken ([micro]L).
Vs=Volume of water extracted in Section 10.10 (mL).
B=Total volume of hexane added in Section 12.5 (mL).
C=Volume of hexane sample solution added to cleanup column in Section
12.7 (mL).
D=Total volume of 2-propanol extract prior to derivatization (mL).
E=Volume of 2-propanol extract carried through derivatization in Section
12.1 (mL).
13.3 Report results in [micro]g/L without correction for recovery
data. All QC data obtained should be reported with the sample results.
14. Method Performance
14.1 The method detection limit (MDL) is defined as the minimum
concentration of a substance that can be measured and reported with 99%
confidence that the value is above zero.1 The MDL
concentrations listed in Tables 1 and 2 were obtained using reagent
water.12 Similar results were achieved using representative
wastewaters. The MDL actually achieved in a given analysis will vary
depending on instrument sensitivity and matrix effects.
14.2 This method was tested by 20 laboratories using reagent water,
drinking water, surface water, and three industrial wastewaters spiked
as six concentrations over the range 12 to 450 [micro]g/L.\13\ Single
operator precision, overall precision, and method accuracy were found to
be directly related to the concentration of the parameter and
essentially independent of the sample matrix. Linear equations to
describe these relationships for a flame ionization detector are
presented in Table 4.
References
1. 40 CFR part 136, appendix B.
2. ``Determination of Phenols in Industrial and Municipal
Wastewaters,'' EPA 600/4-84-ABC, National Technical Information Service,
PBXYZ, Springfield, Virginia 22161, November 1984.
3. Kawahara, F. K. ``Microdetermination of Derivatives of Phenols
and Mercaptans by
[[Page 85]]
Means of Electron Capture Gas Chromatography,'' Analytical Chemistry,
40, 1009 (1968).
4. ASTM Annual Book of Standards, Part 31, D3694-78. ``Standard
Practices for Preparation of Sample Containers and for Preservation of
Organic Constituents,'' American Society for Testing and Materials,
Philadelphia.
5. ``Carcinogens--Working With Carcinogens,'' Department of Health,
Education, and Welfare, Public Health Service, Center for Disease
Control, National Institute for Occupational Safety and Health,
Publication No. 77-206, August 1977.
6. ``OSHA Safety and Health Standards, General Industry,'' (29 CFR
part 1910), Occupational Safety and Health Administration, OSHA 2206
(Revised, January 1976).
7. ``Safety in Academic Chemistry Laboratories,'' American Chemical
Society Publication, Committee on Chemical Safety, 3rd Edition, 1979.
8. Provost, L. P., and Elder, R. S. ``Interpretation of Percent
Recovery Data,'' American Laboratory, 15, 58-63 (1983). (The value 2.44
used in the equation in Section 8.3.3 is two times the value 1.22
derived in this report.)
9. ASTM Annual Book of Standards, Part 31, D3370-76. ``Standard
Practices for Sampling Water,'' American Society for Testing and
Materials, Philadelphia.
10. ``Methods 330.4 (Titrimetric, DPD-FAS) and 330.5
(Spectrophotometric, DPD) for Chlorine, Total Residual,'' Methmds for
Chemical Analysis of Water and Wastes, EPA-600/4-79-020, U.S.
Environmental Protection Agency, Environmental Monitoring and Support
Laboratory, Cincinnati, Ohio 45268, March 1979.
11. Burke, J. A. ``Gas Chromatography for Pesticide Residue
Analysis; Some Practical Aspects,'' Journal of the Association of
Official Analytical Chemists, 48, 1037 (1965).
12. ``Development of Detection Limits, EPA Method 604, Phenols,''
Special letter report for EPA Contract 68-03-2625, U.S. Environmental
Protection Agency, Environmental Monitoring and Support Laboratory,
Cincinnati, Ohio 45268.
13. ``EPA Method Study 14 Method 604-Phenols,'' EPA 600/4-84-044,
National Technical Information Service, PB84-196211, Springfield,
Virginia 22161, May 1984.
Table 1--Chromatographic Conditions and Method Detection Limits
------------------------------------------------------------------------
Method
Retention detection
Parameter time (min) limit
([micro]g/L)
------------------------------------------------------------------------
2-Chlorophenol................................ 1.70 0.31
2-Nitrophenol................................. 2.00 0.45
Phenol........................................ 3.01 0.14
2,4-Dimethylphenol............................ 4.03 0.32
2,4-Dichlorophenol............................ 4.30 0.39
2,4,6-Trichlorophenol......................... 6.05 0.64
4-Chloro-3-methylphenol....................... 7.50 0.36
2,4-Dinitrophenol............................. 10.00 13.0
2-Methyl-4,6-dinitrophenol.................... 10.24 16.0
Pentachlorophenol............................. 12.42 7.4
4-Nitrophenol................................. 24.25 2.8
------------------------------------------------------------------------
Column conditions: Supelcoport (80/100 mesh) coated with 1% SP-1240DA
packed in a 1.8 m long x 2 mm ID glass column with nitrogen carrier
gas at 30 mL/min flow rate. Column temperature was 80 [deg]C at
injection, programmed immediately at 8 [deg]C/min to 150 [deg]C final
temperature. MDL were determined with an FID.
Table 2--Silica Gel Fractionation and Electron Capture Gas Chromatography of PFBB Derivatives
----------------------------------------------------------------------------------------------------------------
Percent recovery by Method
fraction a Retention detection
Parent compound ---------------------------- time limit
(min) ([micro]g/
1 2 3 4 L)
----------------------------------------------------------------------------------------------------------------
2-Chlorophenol............................................... ..... 90 1 ..... 3.3 0.58
2-Nitrophenol................................................ ..... ..... 9 90 9.1 0.77
Phenol....................................................... ..... 90 10 ..... 1.8 2.2
2,4-Dimethylphenol........................................... ..... 95 7 ..... 2.9 0.63
2,4-Dichlorophenol........................................... ..... 95 1 ..... 5.8 0.68
2,4,6-Trichlorophenol........................................ 50 50 ..... ..... 7.0 0.58
4-Chloro-3-methylphenol...................................... ..... 84 14 ..... 4.8 1.8
Pentachlorophenol............................................ 75 20 ..... ..... 28.8 0.59
4-Nitrophenol................................................ ..... ..... 1 90 14.0 0.70
----------------------------------------------------------------------------------------------------------------
Column conditions: Chromosorb W-AW-DMCS (80/100 mesh) coated with 5% OV-17 packed in a 1.8 m long x 2.0 mm ID
glass column with 5% methane/95% argon carrier gas at 30 mL/min flow rate. Column temperature held isothermal
at 200 [deg]C. MDL were determined with an ECD.
a Eluant composition:
Fraction 1--15% toluene in hexane.
Fraction 2--40% toluene in hexane.
Fraction 3--75% toluene in hexane.
Fraction 4--15% 2-propanol in toluene.
[[Page 86]]
Table 3--QC Acceptance Criteria--Method 604
----------------------------------------------------------------------------------------------------------------
Limit for Range for X
Test conc. s ([micro]g/ Range for
Parameter ([micro]g/ ([micro]g/ L) P, Ps
L) L) (percent)
----------------------------------------------------------------------------------------------------------------
4-Chloro-3-methylphenol....................................... 100 16.6 56.7-113.4 49-122
2-Chlorophenol................................................ 100 27.0 54.1-110.2 38-126
2,4-Dichlorophenol............................................ 100 25.1 59.7-103.3 44-119
2,4-Dimethylphenol............................................ 100 33.3 50.4-100.0 24-118
4,6-Dinitro-2-methylphenol.................................... 100 25.0 42.4-123.6 30-136
2,4-Dinitrophenol............................................. 100 36.0 31.7-125.1 12-145
2-Nitrophenol................................................. 100 22.5 56.6-103.8 43-117
4-Nitrophenol................................................. 100 19.0 22.7-100.0 13-110
Pentachlorophenol............................................. 100 32.4 56.7-113.5 36-134
Phenol........................................................ 100 14.1 32.4-100.0 23-108
2,4,6-Trichlorophenol......................................... 100 16.6 60.8-110.4 53-119
----------------------------------------------------------------------------------------------------------------
s--Standard deviation of four recovery measurements, in [micro]g/L (Section 8.2.4).
X--Average recovery for four recovery measurements, in [micro]g/L (Section 8.2.4).
P, Ps--Percent recovery measured (Section 8.3.2, Section 8.4.2).
Note: These criteria are based directly upon the method performance data in Table 4. Where necessary, the limits
for recovery have been broadened to assure applicability of the limits to concentrations below those used to
develop Table 4.
Table 4--Method Accuracy and Precision as Functions of Concentration--Method 604
----------------------------------------------------------------------------------------------------------------
Accuracy, as Single Analyst Overall
Parameter recovery, X' precision, sr' precision, S'
([micro]g/L) ([micro]g/L) ([micro]g/L)
----------------------------------------------------------------------------------------------------------------
4-Chloro-3-methylphenol................................ 0.87C-1.97 0.11X-0.21 0.16X+1.41
2-Chlorophenol......................................... 0.83C-0.84 0.18X+0.20 0.21X+0.75
2,4-Dichlorophenol..................................... 0.81C+0.48 0.17X-0.02 0.18X+0.62
2,4-Dimethylphenol..................................... 0.62C-1.64 0.30X-0.89 0.25X+0.48
4,6-Dinitro-2-methylphenol............................. 0.84C-1.01 0.15X+1.25 0.19X+5.85
2,4-Dinitrophenol...................................... 0.80C-1.58 0.27X-1.15 0.29X+4.51
2-Nitrophenol.......................................... 0.81C-0.76 0.15X+0.44 0.14X+3.84
4-Nitrophenol.......................................... 0.46C+0.18 0.17X+2.43 0.19X+4.79
Pentachlorophenol...................................... 0.83C+2.07 0.22X-0.58 0.23X+0.57
Phenol................................................. 0.43C+0.11 0.20X-0.88 0.17X+0.77
2,4,6-Trichlorophenol.................................. 0.86C-0.40 0.10X+0.53 0.13X+2.40
----------------------------------------------------------------------------------------------------------------
X'=Expected recovery for one or more measurements of a sample containing a concentration of C, in [micro]g/L.
sr'=Expected single analyst standard deviation of measurements at an average concentration found of X, in
[micro]g/L.
S'=Expected interlaboratory standard deviation of measurements at an average concentration found of X, in
[micro]g/L.
C=True value for the concentration, in [micro]g/L.
X=Average recovery found for measurements of samples containing a concentration of C, in [micro]g/L.
[[Page 87]]
[GRAPHIC] [TIFF OMITTED] TC02JY92.012
[[Page 88]]
[GRAPHIC] [TIFF OMITTED] TC02JY92.013
Method 605--Benzidines
1. Scope and Application
1.1 This method covers the determination of certain benzidines. The
following parameters can be determined by this method:
------------------------------------------------------------------------
Parameter Storet No CAS No.
------------------------------------------------------------------------
Benzidine..................................... 39120 92-87-5
3,3'-Dichlorobenzidine........................ 34631 91-94-1
------------------------------------------------------------------------
1.2 This is a high performance liquid chromatography (HPLC) method
applicable to the determination of the compounds listed above in
municipal and industrial discharges as provided under 40 CFR 136.1. When
this method is used to analyze unfamiliar samples for the compounds
above, identifications should be supported by at least one additional
qualitative technique. This method describes electrochemical conditions
at a second potential which can be used to confirm measurements made
with this method. Method 625 provides gas chromatograph/mass
spectrometer (GC/MS) conditions appropriate for the qualitative and
quantitative confirmation of results for the parameters listed above,
using the extract produced by this method.
1.3 The method detection limit (MDL, defined in Section 14.1)
1 for each parameter is
[[Page 89]]
listed in Table 1. The MDL for a specific wastewater may differ from
those listed, depending upon the nature of the interferences in the
sample matrix.
1.4 Any modification of this method, beyond those expressly
permitted, shall be considered as a major modification subject to
application and approval of alternate test procedures under 40 CFR 136.4
and 136.5.
1.5 This method is restricted to use by or under the supervision of
analysts experienced in the use of HPLC instrumentation and in the
interpretation of liquid chromatograms. Each analyst must demonstrate
the ability to generate acceptable results with this method using the
procedure described in Section 8.2.
2. Summary of Method
2.1 A measured volume of sample, approximately 1-L, is extracted
with chloroform using liquid-liquid extractions in a separatory funnel.
The chloroform extract is extracted with acid. The acid extract is then
neutralized and extracted with chloroform. The final chloroform extract
is exchanged to methanol while being concentrated using a rotary
evaporator. The extract is mixed with buffer and separated by HPLC. The
benzidine compounds are measured with an electrochemical
detector.2
2.2 The acid back-extraction acts as a general purpose cleanup to
aid in the elimination of interferences.
3. Interferences
3.1 Method interferences may be caused by contaminants in solvents,
reagents, glassware, and other sample processing hardware that lead to
discrete artifacts and/or elevated baselines in chromatograms. All of
these materials must be routinely demonstrated to be free from
interferences under the conditions of the analysis by running laboratory
reagent blanks as described in Section 8.1.3.
3.1.1 Glassware must be scrupulously cleaned.3 Clean all
glassware as soon as possible after use by rinsing with the last solvent
used in it. Solvent rinsing should be followed by detergent washing with
hot water, and rinses with tap water and distilled water. The glassware
should then be drained dry, and heated in a muffle furnace at 400 [deg]C
for 15 to 30 min. Some thermally stable materials may not be eliminated
by this treatment. Solvent rinses with acetone and pesticide quality
hexane may be substi tuted for the muffle furnace heating. Vol umetric
ware should not be heated in a muffle furnace. After drying and cooling,
glass ware should be sealed and stored in a clean en vironment to
prevent any accumulation of dust or other contaminants. Store inverted
or capped with aluminum foil.
3.1.2 The use of high purity reagents and solvents helps to minimize
interference problems. Purification of solvents by distillation in all-
glass systems may be required.
3.2 Matrix interferences may be caused by contaminants that are co-
extracted from the sample. The extent of matrix interferences will vary
considerably from source to source, depending upon the nature and
diversity of the industrial complex or municipality being sampled. The
cleanup procedures that are inherent in the extraction step are used to
overcome many of these interfer ences, but unique samples may require
addi tional cleanup approaches to achieve the MDL listed in Table 1.
3.3 Some dye plant effluents contain large amounts of components
with re tention times closed to benzidine. In these cases, it has been
found useful to reduce the electrode potential in order to eliminate
interferences and still detect benzidine. (See Section 12.7.)
4. Safety
4.1 The toxicity or carcinogenicity of each reagent used in this
method has not been precisely defined; however, each chemical compound
should be treated as a potential health harzard. From this viewpoint,
exposure to these chemicals must be reduced to the lowest possible level
by whatever means available. The laboratory is responsible for
maintaining a current awareness file of OSHA regulations regarding the
safe handling of the chemicals specified in this method. A reference
file of material data handling sheets should also be made available to
all personnel involved in the chemical analysis. Additional references
to laboratory safety are available and have been identified
4-6 for the information of the analyst.
4.2 The following parameters covered by this method have been
tentatively classified as known or suspected, human or mammalian
carcinogens: benzidine and 3,3'-dichlorobenzidine. Primary standards of
these toxic compounds should be prepared in a hood. A NIOSH/MESA
approved toxic gas respirator should be worn when the analyst handles
high concentrations of these toxic compounds.
4.3 Exposure to chloroform should be minimized by performing all
extractions and extract concentrations in a hood or other well-
ventiliated area.
5. Apparatus and Materials
5.1 Sampling equipment, for discrete or composite sampling.
5.1.1 Grab sample bottle--1-L or 1-qt, amber glass, fitted with a
screw cap lined with Teflon. Foil may be substituted for Teflon if the
sample is not corrosive. If amber bottles are not available, protect
samples from light. The bottle and cap liner must be washed, rinsed with
acetone or methylene
[[Page 90]]
chloride, and dried before use to minimize contamination.
5.1.2 Automatic sampler (optional)--The sampler must incorporate
glass sample containers for the collection of a minimum of 250 mL of
sample. Sample containers must be kept refrigerated at 4[deg]C and
protected from light during compositing. If the sampler uses a
peristaltic pump, a minimum length of compressible silicone rubber
tubing may be used. Before use, however, the compressible tubing should
be thoroughly rinsed with methanol, followed by repeated rinsings with
distilled water to minimize the potential for contamination of the
sample. An integrating flow meter is required to collect flow
proportional composites.
5.2 Glassware (All specifications are suggested):
5.2.1 Separatory funnels--2000, 1000, and 250-mL, with Teflon
stopcock.
5.2.2 Vials--10 to 15-mL, amber glass, with Teflon-lined screw cap.
5.2.3 Rotary evaporator.
5.2.4 Flasks--Round bottom, 100-mL, with 24/40 joints.
5.2.5 Centrifuge tubes--Conical, graduated, with Teflon-lined screw
caps.
5.2.6 Pipettes--Pasteur, with bulbs.
5.3 Balance--Analytical, capable of accurately weighing 0.0001 g.
5.4 High performance liquid chromatograph (HPLC)--An analytical
system complete with column supplies, high pressure syringes, detector,
and compatible recorder. A data system is recommended for measuring peak
areas and retention times.
5.4.1 Solvent delivery system--With pulse damper, Altex 110A or
equivalent.
5.4.2 Injection valve (optional)--Waters U6K or equivalent.
5.4.3 Electrochemical detector--Bioanalyti cal Systems LC-2A with
glassy carbon electrode, or equivalent. This detector has proven
effective in the analysis of wastewaters for the parameters listed in
the scope (Section 1.1), and was used to develop the method performance
statements in Section 14. Guidelines for the use of alternate detectors
are provided in Section 12.1.
5.4.4 Electrode polishing kit--Princeton Applied Research Model 9320
or equivalent.
5.4.5 Column--Lichrosorb RP-2, 5 micron particle diameter, in a 25
cm x 4.6 mm ID stainless steel column. This column was used to develop
the method performance statements in Section 14. Guidelines for the use
of alternate column packings are provided in Section 12.1.
6. Reagents
6.1 Reagent water--Reagent water is defined as a water in which an
interferent is not observed at the MDL of the parameters of interest.
6.2 Sodium hydroxide solution (5 N)--Dissolve 20 g of NaOH (ACS) in
reagent water and dilute to 100 mL.
6.3 Sodium hydroxide solution (1 M)--Dissolve 40 g of NaOH (ACS) in
reagent water and dilute to 1 L.
6.4 Sodium thiosulfate--(ACS) Granular.
6.5 Sodium tribasic phosphate (0.4 M)--Dissolve 160 g of trisodium
phosphate decahydrate (ACS) in reagent water and dilute to 1 L.
6.6 Sulfuric acid (1+1)--Slowly, add 50 mL of
H2SO4 (ACS, sp. gr. 1.84) to 50 mL of reagent
water.
6.7 Sulfuric acid (1 M)--Slowly, add 58 mL of
H2SO4 (ACS, sp. gr. 1.84) to reagent water and
dilute to 1 L.
6.8 Acetate buffer (0.1 M, pH 4.7)--Dissolve 5.8 mL of glacial
acetic acid (ACS) and 13.6 g of sodium acetate trihydrate (ACS) in
reagent water which has been purified by filtration through a RO-4
Millipore System or equivalent and dilute to 1 L.
6.9 Acetonitrile, chloroform (preserved with 1% ethanol), methanol--
Pesticide quality or equivalent.
6.10 Mobile phase--Place equal volumes of filtered acetonitrile
(Millipore type FH filter or equivalent) and filtered acetate buffer
(Millipore type GS filter or equivalent) in a narrow-mouth, glass
container and mix thoroughly. Prepare fresh weekly. Degas daily by
sonicating under vacuum, by heating an stirring, or by purging with
helium.
6.11 Stock standard solutions (1.00 [micro]g/[micro]L)--Stock
standard solutions may be prepared from pure standard materials or
purchased as certified solutions.
6.11.1 Prepare stock standard solutions by accurately weighing about
0.0100 g of pure material. Dissolve the material in methanol and dilute
to volume in a 10-mL volumetric flask. Larger volumes can be used at the
convenience of the analyst. When compound purity is assayed to be 96% or
greater, the weight can be used without correction to calculate the
concentration of the stock standard. Commercially prepared stock
standards can be used at any concentration if they are certified by the
manufacturer or by an independent source.
6.11.2 Transfer the stock standard solutions into Teflon-sealed
screw-cap bottles. Store at 4 [deg]C and protect from light. Stock
standard solutions should be checked frequently for signs of degradation
or evaporation, especially just prior to preparing calibration standards
from them.
6.11.3 Stock standard solutions must be replaced after six months,
or sooner if comparison with check standards indicates a problem.
6.12 Quality control check sample concentrate--See Section 8.2.1.
[[Page 91]]
7. Calibration
7.1 Establish chromatographic operating conditions equivalent to
those given in Table 1. The HPLC system can be calibrated using the
external standard technique (Section 7.2) or the internal standard
technique (Section 7.3).
7.2 External standard calibration procedure:
7.2.1 Prepare calibration standards at a minimum of three
concentration levels for each parameter of interest by adding volumes of
one or more stock standards to a volumetric flask and diluting to volume
with mobile phase. One of the external standards should be at a
concentration near, but above, the MDL (Table 1) and the other
concentrations should correspond to the expected range of concentrations
found in real samples or should define the working range of the
detector.
7.2.2 Using syringe injections of 5 to 25 [micro]L or a constant
volume injection loop, analyze each calibration standard according to
Section 12 and tabulate peak height or area responses against the mass
injected. The results can be used to prepare a calibration curve for
each compound. Alternatively, if the ratio of response to amount
injected (calibration factor) is a constant over the working range (<10%
relative standard deviation, RSD), linearity through the origin can be
assumed and the average ratio or calibration factor can be used in place
of a calibration curve.
7.3 Internal standard calibration procedure--To use this approach,
the analyst must select one or more internal standards that are similar
in analytical behavior to the compounds of interest. The analyst must
further demonstrate that the measurement of the internal standard is not
affected by method or matrix interferences. Because of these
limitations, no internal standard can be suggested that is applicable to
all samples.
7.3.1 Prepare calibration standards at a minimum of three
concentration levels for each parameter of interest by adding volumes of
one or more stock standards to a volumetric flask. To each calibration
standard, add a known constant amount of one or more internal standards,
and dilute to volume with mobile phase. One of the standards should be
at a concentration near, but above, the MDL and the other concentrations
should correspond to the expected range of concentrations found in real
samples or should define the working range of the detector.
7.3.2 Using syringe injections of 5 to 25 [micro]L or a constant
volume injection loop, analyze each calibration standard according to
Section 12 and tabulate peak height or area responses against
concentration for each compound and internal standard. Calculate
response factors (RF) for each compound using Equation 1.
RF= (As)(Cis) (Ais)(Cs)
----------------------------------------------------------------------------------------------------------------
Equation 1
where:
As=Response for the parameter to be measured.
Ais=Response for the internal standard.
Cis=Concentration of the internal standard ([micro]g/L).
Cs=Concentration of the parameter to be measured ([micro]g/
L).
If the RF value over the working range is a constant (<10% RSD), the
RF can be assumed to be invariant and the average RF can be used for
calculations. Alternatively, the results can be used to plot a
calibration curve of response ratios, As/Ais, vs.
RF.
7.4 The working calibration curve, calibration factor, or RF must be
verified on each working day by the measurement of one or more
calibration standards. If the response for any parameter varies from the
predicted response by more than 15%, a new
calibration curve must be prepared for that compound. If serious loss of
response occurs, polish the electrode and recalibrate.
7.5 Before using any cleanup procedure, the analyst must process a
series of calibration standards through the procedure to validate
elution patterns and the absence of interferences from the reagents.
8. Quality Control
8.1 Each laboratory that uses this method is required to operate a
formal quality control program. The minimum requirements of this program
consist of an initial demonstration of laboratory capability and an
ongoing analysis of spiked samples to evaluate and document data
quality. The laboratory must maintain records to document the quality of
data that is generated. Ongoing data quality checks are compared with
established performance criteria to determine if the results of analyses
meet the performance characteristics of the method. When results of
sample spikes indicate atypical method performance, a quality control
check standard must be analyzed to confirm that the measurements were
performed in an in-control mode of operation.
8.1.1 The analyst must make an initial, one-time, demonstration of
the ability to generate acceptable accuracy and precision with this
method. This ability is established as described in Section 8.2.
8.1.2 In recognition of advances that are occurring in
chromatography, the analyst is permitted certain options (detailed in
Sections 10.9, 11.1, and 12.1) to improve the separations or lower the
cost of measurements. Each time such a modification is made to
[[Page 92]]
the method, the analyst is required to repeat the procedure in Section
8.2.
8.1.3 Before processing any samples, the analyst must analyze a
reagent water blank to demonstrate that interferences from the
analytical system and glassware are under control. Each time a set of
samples is extracted or reagents are changed, a reagent water blank must
be processed as a safeguard against laboratory contamination.
8.1.4 The laboratory must, on an ongoing basis, spike and analyze a
minimum of 10% of all samples to monitor and evaluate laboratory data
quality. This procedure is described in Section 8.3.
8.1.5 The laboratory must, on an ongoing basis, demonstrate through
the analyses of quality control check standards that the operation of
the measurement system is in control. This procedure is described in
Section 8.4. The frequency of the check standard analyses is equivalent
to 10% of all samples analyzed but may be reduced if spike recoveries
from samples (Section 8.3) meet all specified quality control criteria.
8.1.6 The laboratory must maintain performance records to document
the quality of data that is generated. This procedure is described in
Section 8.5.
8.2 To establish the ability to generate acceptable accuracy and
precision, the analyst must perform the following operations.
8.2.1 A quality control (QC) check sample concentrate is required
containing benzidine and/or 3,3'-dichlorobenzidine at a concentration of
50 [micro]g/mL each in methanol. The QC check sample concentrate must be
obtained from the U.S. Environmental Protection Agency, Environmental
Monitoring and Support Laboratory in Cincinnati, Ohio, if available. If
not available from that source, the QC check sample concentrate must be
obtained from another external source. If not available from either
source above, the QC check sample concentrate must be prepared by the
laboratory using stock standards prepared independently from those used
for calibration.
8.2.2 Using a pipet, prepare QC check samples at a concentration of
50 [micro]g/L by adding 1.00 mL of QC check sample concentrate to each
of four 1-L-L aliquots of reagent water.
8.2.3 Analyze the well-mixed QC check samples according to the
method beginning in Section 10.
8.2.4 Calculate the average recovery (X) in [micro]g/L, and the
standard deviation of the recovery (s) in [micro]g/L, for each parameter
using the four results.
8.2.5 For each parameter compare s and X with the corresponding
acceptance criteria for precision and accuracy, respectively, found in
Table 2. If s and X for all parameters of interest meet the acceptance
criteria, the system performance is acceptable and analysis of actual
samples can begin. If any individual s exceeds the precision limit or
any individual X falls outside the range for accuracy, the system
performance is unacceptable for that parameter. Locate and correct the
source of the problem and repeat the test for all parameters of interest
beginning with Section 8.2.2.
8.3 The laboratory must, on an ongoing basis, spike at least 10% of
the samples from each sample site being monitored to assess accuracy.
For laboratories analyzing one to ten samples per month, at least one
spiked sample per month is required.
8.3.1 The concentration of the spike in the sample should be
determined as follows:
8.3.1.1 If, as in compliance monitoring, the concentration of a
specific parameter in the sample is being checked against a regulatory
concentration limit, the spike should be at that limit or 1 to 5 times
higher than the background concentration determined in Section 8.3.2,
whichever concentration would be larger.
8.3.1.2 If the concentration of a specific parameter in the sample
is not being checked against a limit specific to that parameter, the
spike should be at 50 [micro]g/L or 1 to 5 times higher than the
background concentration determined in Section 8.3.2, whichever
concentration would be larger.
8.3.1.3 If it is impractical to determine background levels before
spiking (e.g., maximum holding times will be exceeded), the spike
concentration should be (1) the regulatory concentration limit, if any;
or, if none (2) the larger of either 5 times higher than the expected
background concentration or 50 [micro]g/L.
8.3.2 Analyze one sample aliquot to determine the background
concentration (B) of each parameter. If necessary, prepare a new QC
check sample concentrate (Section 8.2.1) appropriate for the background
concentrations in the sample. Spike a second sample aliquot with 1.0 mL
of the QC check sample concentrate and analyze it to determine the
concentration after spiking (A) of each parameter. Calculate each
percent recovery (P) as 100(A-B)%/T, where T is the known true value of
the spike.
8.3.3 Compare the percent recovery (P) for each parameter with the
corresponding QC acceptance criteria found in Table 2. These acceptance
criteria were calculated to include an allowance for error in
measurement of both the background and spike concentrations, assuming a
spike to background ratio of 5:1. This error will be accounted for to
the extent that the analyst's spike to background ratio approaches
5:1.\7\ If spiking was performed at a concentration lower than 50
[micro]g/L, the analyst must use either the QC acceptance criteria in
Table 2, or optional QC acceptance criteria calculated for the specific
spike concentration. To calculate optional acceptance criteria for the
recovery of a parameter: (1) Calculate accuracy (X') using the equation
in Table 3, substituting
[[Page 93]]
the spike concentration (T) for C; (2) calculate overall precision (S')
using the equation in Table 3, substituting X' for X; (3) calculate the
range for recovery at the spike concentration as (100 X'/T)2.44(100 S'/T)%.\7\
8.3.4 If any individual P falls outside the designated range for
recovery, that parameter has failed the acceptance criteria. A check
standard containing each parameter that failed the criteria must be
analyzed as described in Section 8.4.
8.4 If any parameter fails the acceptance criteria for recovery in
Section 8.3, a QC check standard containing each parameter that failed
must be prepared and analyzed.
Note: The frequency for the required analysis of a QC check standard
will depend upon the number of parameters being simultaneously tested,
the complexity of the sample matrix, and the performance of the
laboratory.
8.4.1 Prepare the QC check standard by adding 1.0 mL of QC check
sample concentrate (Sections 8.2.1 or 8.3.2) to 1 L of reagent water.
The QC check standard needs only to contain the parameters that failed
criteria in the test in Section 8.3.
8.4.2 Analyze the QC check standard to determine the concentration
measured (A) of each parameter. Calculate each percent recovery
(Ps) as 100 (A/T)%, where T is the true value of the standard
concentration.
8.4.3 Compare the percent recovery (Ps) for each
parameter with the corresponding QC acceptance criteria found in Table
2. Only parameters that failed the test in Section 8.3 need to be
compared with these criteria. If the recovery of any such parameter
falls outside the designated range, the laboratory performance for that
parameter is judged to be out of control, and the problem must be
immediately identified and corrected. The analytical result for that
parameter in the unspiked sample is suspect and may not be reported for
regulatory compliance purposes.
8.5 As part of the QC program for the laboratory, method accuracy
for wastewater samples must be assessed and records must be maintained.
After the analysis of five spiked wastewater samples as in Section 8.3,
calculate the average percent recovery (P) and the standard deviation of
the percent recovery (sp). Express the accuracy assessment as
a percent recovery interval from P-2sp to P+2sp.
If P=90% and sp=10%, for example, the accuracy interval is
expressed as 70-110%. Update the accuracy assessment for each parameter
on a regular basis (e.g. after each five to ten new accuracy
measurements).
8.6 It is recommended that the laboratory adopt additional quality
assurance practices for use with this method. The specific practices
that are most productive depend upon the needs of the laboratory and the
nature of the samples. Field duplicates may be analyzed to assess the
precision of the environmental measurements. When doubt exists over the
identification of a peak on the chromatogram, confirmatory techniques
such as HPLC with a dissimilar column, gas chromatography, or mass
spectrometer must be used. Whenever possible, the laboratory should
analyze standard reference materials and participate in relevant
performance evaluation studies.
9. Sample Collection, Preservation, and Handling
9.1 Grab samples must be collected in glass containers. Conventional
sampling practices\8\ should be followed, except that the bottle must
not be prerinsed with sample before collection. Composite samples should
be collected in refrigerated glass containers in accordance with the
requirements of the program. Automatic sampling equipment must be as
free as possible of Tygon tubing and other potential sources of
contamination.
9.2 All samples must be iced or refrigerated at 4[deg]C and stored
in the dark from the time of collection until extraction. Both benzidine
and 3,3'-dichlorobenzidine are easily oxidized. Fill the sample bottles
and, if residual chlorine is present, add 80 mg of sodium thiosulfate
per liter of sample and mix well. EPA Methods 330.4 and 330.5 may be
used for measurement of residual chlorine.\9\ Field test kits are
available for this purpose. After mixing, adjust the pH of the sample to
a range of 2 to 7 with sulfuric acid.
9.3 If 1,2-diphenylhydrazine is likely to be present, adjust the pH
of the sample to 4.0 0.2 to prevent rearrangement
to benzidine.
9.4 All samples must be extracted within 7 days of collection.
Extracts may be held up to 7 days before analysis, if stored under an
inert (oxidant free) atmosphere.\2\ The extract should be protected from
light.
10. Sample Extraction
10.1 Mark the water meniscus on the side of the sample bottle for
later determination of sample volume. Pour the entire sample into a 2-L
separatory funnel. Check the pH of the sample with wide-range pH paper
and adjust to within the range of 6.5 to 7.5 with sodium hydroxide
solution or sulfuric acid.
10.2 Add 100 mL of chloroform to the sample bottle, seal, and shake
30 s to rinse the inner surface. (Caution: Handle chloroform in a well
ventilated area.) Transfer the solvent to the separatory funnel and
extract the sample by shaking the funnel for 2 min with periodic venting
to release excess pressure. Allow the organic layer to separate from the
water phase for a minimum of 10 min. If the emulsion interface between
layers is more than one-third the volume of the solvent layer, the
analyst must employ mechanical techniques to complete the phase
separation. The optimum technique depends upon the sample, but may
include stirring, filtration of the emulsion through glass
[[Page 94]]
wool, centrifugation, or other physical methods. Collect the chloroform
extract in a 250-mL separatory funnel.
10.3 Add a 50-mL volume of chloroform to the sample bottle and
repeat the extraction procedure a second time, combining the extracts in
the separatory funnel. Perform a third extraction in the same manner.
10.4 Separate and discard any aqueous layer remaining in the 250-mL
separatory funnel after combining the organic extracts. Add 25 mL of 1 M
sulfuric acid and extract the sample by shaking the funnel for 2 min.
Transfer the aqueous layer to a 250-mL beaker. Extract with two
additional 25-mL portions of 1 M sulfuric acid and combine the acid
extracts in the beaker.
10.5 Place a stirbar in the 250-mL beaker and stir the acid extract
while carefully adding 5 mL of 0.4 M sodium tribasic phosphate. While
monitoring with a pH meter, neutralize the extract to a pH between 6 and
7 by dropwise addition of 5 N sodium hydroxide solution while stirring
the solution vigorously. Approximately 25 to 30 mL of 5 N sodium
hydroxide solution will be required and it should be added over at least
a 2-min period. Do not allow the sample pH to exceed 8.
10.6 Transfer the neutralized extract into a 250-mL separatory
funnel. Add 30 mL of chloroform and shake the funnel for 2 min. Allow
the phases to separate, and transfer the organic layer to a second 250-
mL separatory funnel.
10.7 Extract the aqueous layer with two additional 20-mL aliquots of
chloroform as before. Combine the extracts in the 250-mL separatory
funnel.
10.8 Add 20 mL of reagent water to the combined organic layers and
shake for 30 s.
10.9 Transfer the organic extract into a 100-mL round bottom flask.
Add 20 mL of methanol and concentrate to 5 mL with a rotary evaporator
at reduced pressure and 35 [deg]C. An aspirator is recommended for use
as the source of vacuum. Chill the receiver with ice. This operation
requires approximately 10 min. Other concentration techniques may be
used if the requirements of Section 8.2 are met.
10.10 Using a 9-in. Pasteur pipette, transfer the extract to a 15-
mL, conical, screw-cap centrifuge tube. Rinse the flask, including the
entire side wall, with 2-mL portions of methanol and combine with the
original extract.
10.11 Carefully concentrate the extract to 0.5 mL using a gentle
stream of nitrogen while heating in a 30 [deg]C water bath. Dilute to 2
mL with methanol, reconcentrate to 1 mL, and dilute to 5 mL with acetate
buffer. Mix the extract thoroughly. Cap the centrifuge tube and store
refrigerated and protected from light if further processing will not be
performed immediately. If the extract will be stored longer than two
days, it should be transferred to a Teflon-sealed screw-cap vial. If the
sample extract requires no further cleanup, proceed with HPLC analysis
(Section 12). If the sample requires further cleanup, proceed to Section
11.
10.12 Determine the original sample volume by refilling the sample
bottle to the mark and transferring the liquid to a 1,000-mL graduated
cylinder. Record the sample volume to the nearest 5 mL.
11. Cleanup and Separation
11.1 Cleanup procedures may not be necessary for a relatively clean
sample matrix. If particular circumstances demand the use of a cleanup
procedure, the analyst first must demonstrate that the requirements of
Section 8.2 can be met using the method as revised to incorporate the
cleanup procedure.
12. High Performance Liquid Chromatography
12.1 Table 1 summarizes the recommended operating conditions for the
HPLC. Included in this table are retention times, capacity factors, and
MDL that can be achieved under these conditions. An example of the
separations achieved by this HPLC column is shown in Figure 1. Other
HPLC columns, chromatographic conditions, or detectors may be used if
the requirements of Section 8.2 are met. When the HPLC is idle, it is
advisable to maintain a 0.1 mL/min flow through the column to prolong
column life.
12.2 Calibrate the system daily as described in Section 7.
12.3 If the internal standard calibration procedure is being used,
the internal standard must be added to the sample extract and mixed
thoroughly immediately before injection into the instrument.
12.4 Inject 5 to 25 [micro]L of the sample extract or standard into
the HPLC. If constant volume injection loops are not used, record the
volume injected to the nearest 0.05 [micro]L, and the resulting peak
size in area or peak height units.
12.5 Identify the parameters in the sample by comparing the
retention times of the peaks in the sample chromatogram with those of
the peaks in standard chromatograms. The width of the retention time
window used to make identifications should be based upon measurements of
actual retention time variations of standards over the course of a day.
Three times the standard deviation of a retention time for a compound
can be used to calculate a suggested window size; however, the
experience of the analyst should weigh heavily in the interpretation of
chromatograms.
12.6 If the response for a peak exceeds the working range of the
system, dilute the extract with mobile phase and reanalyze.
12.7 If the measurement of the peak response for benzidine is
prevented by the presence of interferences, reduce the electrode
[[Page 95]]
potential to +0.6 V and reanalyze. If the benzidine peak is still
obscured by interferences, further cleanup is required.
13. Calculations
13.1 Determine the concentration of individual compounds in the
sample.
13.1.1 If the external standard calibration procedure is used,
calculate the amount of material injected from the peak response using
the calibration curve or calibration factor determined in Section 7.2.2.
The concentration in the sample can be calculated from Equation 2.
[GRAPHIC] [TIFF OMITTED] TC15NO91.101
Equation 2
where:
A=Amount of material injected (ng).
Vi=Volume of extract injected ([micro]L).
Vt=Volume of total extract ([micro]L).
Vs=Volume of water extracted (mL).
13.1.2 If the internal standard calibration procedure is used,
calculate the concentration in the sample using the response factor (RF)
determined in Section 7.3.2 and Equation 3.
[GRAPHIC] [TIFF OMITTED] TC15NO91.102
Equation 3
where:
As=Response for the parameter to be measured.
Ais=Response for the internal standard.
Is=Amount of internal standard added to each extract
([micro]g).
Vo=Volume of water extracted (L).
13.2 Report results in [micro]g/L without correction for recovery
data. All QC data obtained should be reported with the sample results.
14. Method Performance
14.1 The method detection limit (MDL) is defined as the minimum
concentration of a substance that can be measured and reported with 99%
confidence that the value is above zero.\1\ The MDL concentrations
listed in Table 1 were obtained using reagent water.\10\ Similar results
were achieved using representative wastewaters. The MDL actually
achieved in a given analysis will vary depending on instrument
sensitivity and matrix effects.
14.2 This method has been tested for linearity of spike recovery
from reagent water and has been demonstrated to be applicable over the
concentration range from 7xMDL to 3000xMDL.\10\
14.3 This method was tested by 17 laboratories using reagent water,
drinking water, surface water, and three industrial wastewaters spiked
at six concentrations over the range 1.0 to 70 [micro]g/L.\11\ Single
operator precision, overall precision, and method accuracy were found to
be directly related to the concentration of the parameter and
essentially independent of the sample matrix. Linear equations to
describe these relationships are presented in Table 3.
References
1. 40 CFR part 136, appendix B.
2. ``Determination of Benzidines in Industrial and Muncipal
Wastewaters,'' EPA 600/4-82-022, National Technical Information Service,
PB82-196320, Springfield, Virginia 22161, April 1982.
3. ASTM Annual Book of Standards, Part 31, D3694-78. ``Standard
Practices for Preparation of Sample Containers and for Preservation of
Organic Constituents,'' American Society for Testing and Materials,
Philadelphia.
4. ``Carcinogens--Working With Carcinogens,'' Department of Health,
Education, and Welfare, Public Health Service, Center for Disease
Control, National Institute for Occupational Safety and Health,
Publication No. 77-206, August 1977.
5. ``OSHA Safety and Health Standards, General Industry,'' (29 CFR
part 1910), Occupational Safety and Health Administration, OSHA 2206
(Revised, January 1976).
6. ``Safety in Academic Chemistry Laboratories,'' American Chemical
Society Publication, Committee on Chemical Safety, 3rd Edition, 1979.
7. Provost, L.P., and Elder, R.S. ``Interpretation of Percent
Recovery Data,'' American Laboratory, 15, 58-63 (1983). (The value 2.44
used in the equation in Section 8.3.3 is two times the value 1.22
derived in this report.)
8. ASTM Annual Book of Standards, Part 31, D3370-76. ``Standard
Practices for Sampling Water,'' American Society for Testing and
Materials, Philadelphia.
9. ``Methods 330.4 (Titrimetric, DPD-FAS) and 330.5
(Spectrophotometric, DPD) for Chlorine Total Residual,'' Methods for
Chemical Analysis of Water and Wastes, EPA-600/4-79-020, U.S.
Environmental Protection Agency, Environmental Monitoring and Support
Laboratory, Cincinnati, Ohio 45268, March 1979.
10. ``EPA Method Study 15, Method 605 (Benzidines),'' EPA 600/4-84-
062, National Technical Information Service, PB84-211176, Springfield,
Virginia 22161, June 1984.
11. ``EPA Method Validation Study 15, Method 605 (Benzidines),''
Report for EPA Contract 68-03-2624 (In preparation).
[[Page 96]]
Table 1--Chromatographic Conditions and Method Detection Limits
------------------------------------------------------------------------
Method
Column detection
Parameter Retention capacity limit
time (min) factor (k') ([micro]g/
L)
------------------------------------------------------------------------
Benzidine........................ 6.1 1.44 0.08
3,3'-Dichlorobenzidine........... 12.1 3.84 0.13
------------------------------------------------------------------------
HPLC Column conditions: Lichrosorb RP-2, 5 micron particle size, in a 25
cmx4.6 mm ID stainless steel column. Mobile Phase: 0.8 mL/min of 50%
acetonitrile/50% 0.1M pH 4.7 acetate buffer. The MDL were determined
using an electrochemical detector operated at +0.8 V.
Table 2--QC Acceptance Criteria--Method 605
----------------------------------------------------------------------------------------------------------------
Limit for Range for
Test conc. s X Range for
Parameter ([micro]g/ ([micro]g/ ([micro]g/ P, Ps
L) L) L) (percent)
----------------------------------------------------------------------------------------------------------------
Benzidine........................................................ 50 18.7 9.1-61.0 D-140
3.3'-Dichlorobenzidine........................................... 50 23.6 18.7-50.0 5-128
----------------------------------------------------------------------------------------------------------------
s=Standard deviation of four recovery measurements, in [micro]g/L (Section 8.2.4).
X=Average recovery for four recovery measurements, in [micro]g/L (Section 8.2.4).
P, Ps=Percent recovery measured (Section 8.3.2, Section 8.4.2).
D=Detected; result must be greater than zero.
Note: These criteria are based directly upon the method performance data in Table 3. Where necessary, the limits
for recovery have been broadened to assure applicability of the limits to concentrations below those used to
develop Table 3.
Table 3--Method Accuracy and Precision as Functions of Concentration--Method 605
----------------------------------------------------------------------------------------------------------------
Accuracy, as Single analyst Overall
Parameter recovery, precision, sr' precision, S'
X'([micro]g/L) ([micro]g/L) ([micro]g/L)
----------------------------------------------------------------------------------------------------------------
Benzidine....................................................... 0.70C+0.06 0.28X+0.19 0.40X+0.18
3,3'-Dichlorobenzidine.......................................... 0.66C+0.23 0.39X-0.05 0.38X+0.02
----------------------------------------------------------------------------------------------------------------
X'=Expected recovery for one or more measurements of a sample containing a concentration of C, in [micro]g/L.
sr'=Expected single analyst standard deviation of measurements at an average concentration found of X, in
[micro]g/L.
S'=Expected interlaboratory standard deviation of measurements at an average concentration found of X, in
[micro]g/L.
C=True value for the concentration, in [micro]g/L.
X=Average recovery found for measurements of samples containing a concentration of C, in [micro]g/L.
[[Page 97]]
[GRAPHIC] [TIFF OMITTED] TC02JY92.014
[[Page 98]]
Method 606--Phthalate Ester
1. Scope and Application
1.1 This method covers the determination of certain phthalate
esters. The following parameters can be determined by this method:
------------------------------------------------------------------------
STORET
Parameter No. CAS No.
------------------------------------------------------------------------
Bis(2-ethylhexyl) phthalate........................ 39100 117-81-7
Butyl benzyl phthalate............................. 34292 85-68-7
Di-n-butyl phthalate............................... 39110 84-74-2
Diethyl phthalate.................................. 34336 84-66-2
Dimethyl phthalate................................. 34341 131-11-3
Di-n-octyl phthalate............................... 34596 117-84-0
------------------------------------------------------------------------
1.2 This is a gas chromatographic (GC) method applicable to the
determination of the compounds listed above in municipal and industrial
discharges as provided under 40 CFR 136.1. When this method is used to
analyze unfamiliar samples for any or all of the compounds above,
compound identifications should be supported by at least one additional
qualitative technique. This method describes analytical conditions for a
second gas chromatographic column that can be used to confirm
measurements made with the primary column. Method 625 provides gas
chromatograph/mass spectrometer (GC/MS) conditions appropriate for the
qualitative and quantitative confirmation of results for all of the
parameters listed above, using the extract produced by this method.
1.3 The method detection limit (MDL, defined in Section 14.1)\1\ for
each parameter is listed in Table 1. The MDL for a specific wastewater
may differ from those listed, depending upon the nature of interferences
in the sample matrix.
1.4 The sample extraction and concentration steps in this method are
essentially the same as in Methods 608, 609, 611, and 612. Thus, a
single sample may be extracted to measure the parameters included in the
scope of each of these methods. When cleanup is required, the
concentration levels must be high enough to permit selecting aliquots,
as necessary, to apply appropriate cleanup procedures. The analyst is
allowed the latitude, under Section 12, to select chromatographic
conditions appropriate for the simultaneous measurement of combinations
of these parameters.
1.5 Any modification of this method, beyond those expressly
permitted, shall be considered as a major modification subject to
application and approval of alternate test procedures under 40 CFR 136.4
and 136.5.
1.6 This method is restricted to use by or under the supervision of
analysts experienced in the use of a gas chromatograph and in the
interpretation of gas chromatograms. Each analyst must demonstrate the
ability to generate acceptable results with this method using the
procedure described in Section 8.2.
2. Summary of Method
2.1 A measured volume of sample, approximately 1-L, is extracted
with methylene chloride using a separatory funnel. The methylene
chloride extract is dried and exchanged to hexane during concentration
to a volume of 10 mL or less. The extract is separated by gas
chromatography and the phthalate esters are then measured with an
electron capture detector.\2\
2.2 Analysis for phthalates is especially complicated by their
ubiquitous occurrence in the environment. The method provides Florisil
and alumina column cleanup procedures to aid in the elimination of
interferences that may be encountered.
3. Interferences
3.1 Method interferences may be caused by contaminants in solvents,
reagents, glassware, and other sample processing hardware that lead to
discrete artifacts and/or elevated baselines in gas chromatograms. All
of these materials must be routinely demonstrated to be free from
interferences under the conditions of the analysis by running laboratory
reagent blanks as described in Section 8.1.3.
3.1.1 Glassware must be scrupulously cleaned.\3\ Clean all glassware
as soon as possible after use by rinsing with the last solvent used in
it. Solvent rinsing should be followed by detergent washing with hot
water, and rinses with tap water and distilled water. The glassware
should then be drained dry, and heated in a muffle furnace at 400 [deg]C
for 15 to 30 min. Some thermally stable materials, such as PCBs, may not
be eliminated by this treatment. Solvent rinses with acetone and
pesticide quality hexane may be substituted for the muffle furnace
heating. Thorough rinsing with such solvents usually eliminates PCB
interference. Volumetric ware should not be heated in a muffle furnace.
After drying and cooling, glassware should be sealed and stored in a
clean environment to prevent any accumulation of dust or other
contaminants. Store inverted or capped with aluminum foil.
3.1.2 The use of high purity reagents and solvents helps to minimize
interference problems. Purification of solvents by distillation in all-
glass systems may be required.
3.2 Phthalate esters are contaminants in many products commonly
found in the laboratory. It is particularly important to avoid the use
of plastics because phthalates are commonly used as plasticizers and are
easily extracted from plastic materials. Serious phthalate contamination
can result at any time, if consistent quality control is not practiced.
Great care must be experienced to prevent such contamination. Exhaustive
cleanup of reagents and glassware may be required to eliminate
background phthalate contamination.4, 5
[[Page 99]]
3.3 Matrix interferences may be caused by contaminants that are co-
extracted from the sample. The extent of matrix interferences will vary
considerably from source to source, depending upon the nature and
diversity of the industrial complex or municipality being sampled. The
cleanup procedures in Section 11 can be used to overcome many of these
interferences, but unique samples may require additional cleanup
approaches to achieve the MDL listed in Table 1.
4. Safety
4.1 The toxicity or carcinogenicity of each reagent used in this
method has not been precisely defined; however, each chemical compound
should be treated as a potential health hazard. From this viewpoint,
exposure to these chemicals must be reduced to the lowest possible level
by whatever means available. The laboratory is responsible for
maintaining a current awareness file of OSHA regulations regarding the
safe handling of the chemicals specified in this method. A reference
file of material data handling sheets should also be made available to
all personnel involved in the chemical analysis. Additional references
to laboratory safety are available and have been identified
6-8 for the information of the analyst.
5. Apparatus and Materials
5.1 Sampling equipment, for discrete or composite sampling.
5.1.1 Grab sample bottle--1-L or 1-qt, amber glass, fitted with a
screw cap lined with Teflon. Foil may be substituted for Teflon if the
sample is not corrosive. If amber bottles are not available, protect
samples from light. The bottle and cap liner must be washed, rinsed with
acetone or methylene chloride, and dried before use to minimize
contamination.
5.1.2 Automatic sampler (optional)--The sampler must incorporate
glass sample containers for the collection of a minimum of 250 mL of
sample. Sample containers must be kept refrigerated at 4 [deg]C and
protected from light during compositing. If the sampler uses a
peristaltic pump, a minimum length of compressible silicone rubber
tubing may be used. Before use, however, the compressible tubing should
be thoroughly rinsed with methanol, followed by repeated rinsings with
distilled water to minimize the potential for contamination of the
sample. An integrating flow meter is required to collect flow
proportional composites.
5.2 Glassware (All specifications are suggested. Catalog numbers are
included for illustration only).
5.2.1 Separatory funnel--2-L, with Teflon stopcock.
5.2.2 Drying column--Chromatographic column, approximately 400 mm
long x 19 mm ID, with coarse frit filter disc.
5.2.3 Chromatographic column--300 mm long x 10 mm ID, with Teflon
stopcock and coarse frit filter disc at bottom (Kontes K-420540-0213 or
equivalent).
5.2.4 Concentrator tube, Kuderna-Danish--10-mL, graduated (Kontes K-
570050-1025 or equivalent). Calibration must be checked at the volumes
employed in the test. Ground glass stopper is used to prevent
evaporation of extracts.
5.2.5 Evaporative flask, Kuderna-Danish--500-mL (Kontes K-570001-
0500 or equivalent). Attach to concentrator tube with springs.
5.2.6 Snyder column, Kuderna-Danish--Three-ball macro (Kontes K-
503000-0121 or equivalent).
5.2.7 Snyder column, Kuderna-Danish--Two-ball micro (Kontes K-
569001-0219 or equivalent).
5.2.8 Vials--10 to 15-mL, amber glass, with Teflon-lined screw cap.
5.3 Boiling chips--Approximately 10/40 mesh. Heat to 400 [deg]C for
30 min or Soxhlet extract with methylene chloride.
5.4 Water bath--Heated, with concentric ring cover, capable of
temperature control (2 [deg]C). The bath should be
used in a hood.
5.5 Balance--Analytical, capable of accurately weighing 0.0001 g.
5.6 Gas chromatograph--An analytical system complete with gas
chromatograph suitable for on-column injection and all required
accessories including syringes, analytical columns, gases, detector, and
strip-chart recorder. A data system is recommended for measuring peak
areas.
5.6.1 Column 1--1.8 m long x 4 mm ID glass, packed with 1.5% SP-
2250/1.95% SP-2401 Supelcoport (100/120 mesh) or equivalent. This column
was used to develop the method performance statemelts in Section 14.
Guidelines for the use of alternate column packings are provided in
Section 12.1.
5.6.2 Column 2--1.8 m long x 4 mm ID glass, packed with 3% OV-1 on
Supelcoport (100/120 mesh) or equivalent.
5.6.3 Detector--Electron capture detector. This detector has proven
effective in the analysis of wastewaters for the parameters listed in
the scope (Section 1.1), and was used to develop the method performance
statements in Section 14. Guidelines for the use of alternate detectors
are provided in Section 12.1.
6. Reagents
6.1 Reagent water--Reagent water is defined as a water in which an
interferent is not observed at the MDL of the parameters of interest.
6.2 Acetone, hexane, isooctane, methylene chloride, methanol--
Pesticide quality or equivalent.
6.3 Ethyl ether--nanograde, redistilled in glass if necessary.
6.3.1 Ethyl ether must be shown to be free of peroxides before it is
used as indicated by
[[Page 100]]
EM Laboratories Quant test strips. (Available from Scientific Products
Co., Cat. No. P1126-8, and other suppliers.)
6.3.2 Procedures recommended for removal of peroxides are provided
with the test strips. After cleanup, 20 mL of ethyl alcohol preservative
must be added to each liter of ether.
6.4 Sodium sulfate--(ACS) Granular, anhydrous. Several levels of
purification may be required in order to reduce background phthalate
levels to an acceptable level: 1) Heat 4 h at 400 [deg]C in a shallow
tray, 2) Heat 16 h at 450 to 500 [deg]C in a shallow tray, 3) Soxhlet
extract with methylene chloride for 48 h.
6.5 Florisil--PR grade (60/100 mesh). Purchase activated at 1250
[deg]F and store in the dark in glass containers with ground glass
stoppers or foil-lined screw caps. To prepare for use, place 100 g of
Florisil into a 500-mL beaker and heat for approximately 16 h at 40
[deg]C. After heating transfer to a 500-mL reagent bottle. Tightly seal
and cool to room temperature. When cool add 3 mL of reagent water. Mix
thoroughly by shaking or rolling for 10 min and let it stand for at
least 2 h. Keep the bottle sealed tightly.
6.6 Alumina--Neutral activity Super I, W200 series (ICN Life
Sciences Group, No. 404583). To prepare for use, place 100 g of alumina
into a 500-mL beaker and heat for approximately 16 h at 400 [deg]C.
After heating transfer to a 500-mL reagent bottle. Tightly seal and cool
to room temperature. When cool add 3 mL of reagent water. Mix thoroughly
by shaking or rolling for 10 min and let it stand for at least 2 h. Keep
the bottle sealed tightly.
6.7 Stock standard solutions (1.00 [micro]g/[micro]L)--Stock
standard solutions can be prepared from pure standard materials or
purchased as certified solutions.
6.7.1 Prepare stock standard solutions by accurately weighing about
0.0100 g of pure material. Dissolve the material in isooctane and dilute
to volume in a 10-mL volumetric flask. Larger volumes can be used at the
convenience of the analyst. When compound purity is assayed to be 96% or
greater, the weight can be used without correction to calculate the
concentration of the stock standard. Commercially prepared stock
standards can be used at any concentration if they are certified by the
manufacturer or by an independent source.
6.7.2 Transfer the stock standard solutions into Teflon-sealed
screw-cap bottles. Store at 4 [deg]C and protect from light. Stock
standard solutions should be checked frequently for signs of degradation
or evaporation, especially just prior to preparing calibration standards
from them.
6.7.3 Stock standard solutions must be replaced after six months, or
sooner if comparison with check standards indicates a problem.
6.8 Quality control check sample concentrate--See Section 8.2.1.
7. Calibration
7.1 Establish gas chromatograph operating conditions equivalent to
those given in Table 1. The gas chromatographic system can be calibrated
using the external standard technique (Section 7.2) or the internal
standard technique (Section 7.3).
7.2 External standard calibration procedure:
7.2.1 Prepared calibration standards at a minimum of three
concentration levels for each parameter of interest by adding volumes of
one or more stock standards to a volumetric flask and diluting to volume
with isooctane. One of the external standards should be at a
concentration near, but above, the MDL (Table 1) and the other
concentrations should correspond to the expected range of concentrations
found in real samples or should define the working range of the
detector.
7.2.2 Using injections of 2 to 5 [micro]L, analyze each calibration
standard according to Section 12 and tabulate peak height or area
responses against the mass injected. The results can be used to prepare
a calibration curve for each compound. Alternatively, if the ratio of
response to amount injected (calibration factor) is a constant over the
working range (<10% relative standard deviation, RSD), linearity through
the origin can be assumed and the average ratio or calibration factor
can be used in place of a calibration curve.
7.3 Internal standard calibration procedure--To use this approach,
the analyst must select one or more internal standards that are similar
in analytical behavior to the compounds of interest. The analyst must
further demonstrate that the measurement of the internal standard is not
affected by method or matrix interferences. Because of these
limitations, no internal standard can be suggested that is applicable to
all samples.
7.3.1 Prepare calibration standards at a minimum of three
concentration levels for each parameter of interest by adding volumes of
one or more stock standards to a volumetric flash. To each calibration
standard, add a known constant amount of one or more internal standards,
and dilute to volume with isooctane. One of the standards should be at a
concentraton near, but above, the MDL and the other concentrations
should correspond to the expected range of concentrations found in real
samples or should define the working range of the detector.
[[Page 101]]
7.3.2 Using injections of 2 to 5 [micro]L, analyze each calibration
standard according to Section 12 and tabulate peak height or area
responses against concentration for each compound and internal standard.
Calculate response factors (RF) for each compound using Equation 1.
RF= (As)(Cis) (Ais)(Cs)
----------------------------------------------------------------------------------------------------------------
Equation 1
where:
As=Response for the parameter to be measured.
Ais=Response for the internal standard.
Cis=Concentration of the internal standard ([micro]g/L).
Cs=Concentration of the parameter to be measured ([micro]g/
L).
If the RF value over the working range is a constant (<10% RSD), the
RF can be assumed to be invariant and the average RF can be used for
calculations. Alternatively, the results can be used to plot a
calibration curve of response ratios, As/Ais, vs.
RF.
7.4 The working calibration curve, calibration factor, or RF must be
verified on each working day by the measurement of one or more
calibration standards. If the response for any parameter varies from the
predicted response by more than 15%, a new
calibration curve must be prepared for that compound.
7.5 Before using any cleanup procedure, the analyst must process a
series of calibration standards through the procedure to validate
elution patterns and the absence of interferences from the reagents.
8. Quality Control
8.1 Each laboratory that uses this method is required to operate a
formal quality control program. The minimum requirements of this program
consist of an initial demonstration of laboratory capability and an
ongoing analysis of spiked samples to evaluate and document data
quality. The laboratory must maintain records to document the quality of
data that is generated. Ongoing data quality checks are compared with
established performance criteria to determine if the results of analyses
meet the performance characteristics of the method. When results of
sample spikes indicate atypical method performance, a quality control
check standard must be analyzed to confirm that the measurements were
performed in an in-control mode of operation.
8.1.1 The analyst must make an initial, one-time, demonstration of
the ability to generate acceptable accuracy and precision with this
method. This ability is established as described in Section 8.2.
8.1.2 In recognition of advances that are occurring in
chromatography, the analyst is permitted certain options (detailed in
Sections 10.4, 11.1, and 12.1) to improve the separations or lower the
cost of measurements. Each time such a modification is made to the
method, the analyst is required to repeat the procedure in Section 8.2.
8.1.3 Before processing any samples, the analyst must analyze a
reagent water blank to demonstrate that interferences from the
analytical system and glassware are under control. Each time a set of
samples is extracted or reagents are changed, a reagent water blank must
be processed as a safeguard against laboratory contamination.
8.1.4 The laboratory must, on an ongoing basis, spike and analyze a
minimum of 10% of all samples to monitor and evaluate laboratory data
quality. This procedure is described in Section 8.3.
8.1.5 The laboratory must, on an ongoing basis, demonstrate through
the analyses of quality control check standards that the operation of
the measurement system is in control. This procedure is described in
Section 8.4. The frequency of the check standard analyses is equivalent
to 10% of all samples analyzed but may be reduced if spike recoveries
from samples (Section 8.3) meet all specified quality control criteria.
8.1.6 The laboratory must maintain performance records to document
the quality of data that is generated. This procedure is described in
Section 8.5.
8.2 To establish the ability to generate acceptable accuracy and
precision, the analyst must perform the following operations.
8.2.1 A quality contrml (QC) check sample concentrate is required
containing each parameter of interest at the following concentrations in
acetone: butyl benzyl phthalate, 10 [micro]g/mL; bis(2-ethylhexyl)
phthalate, 50 [micro]g/mL; di-n-octyl phthalate, 50 [micro]g/mL; any
other phthlate, 25 [micro]g/mL. The QC check sample concentrate must be
obtained from the U.S. Environmental Protection Agancy, Environmental
Monitoring and Support Laboratory in Cincinnati, Ohio, if available. If
not available from that source, the QC check sample concentrate must be
obtained from another external source. If not available from either
source above, the QC check sample concentrate must be prepared by the
laboratory using stock standards prepared independently from those used
for calibration.
8.2.2 Using a pipet, prepare QC check samples at the test
concentrations shown in Table 2 by adding 1.00 mL of QC check sample
concentrate to each of four 1-L aliquots of reagent water.
8.2.3 Analyze the well-mixed QC check samples according to the
method beginning in Section 10.
8.2.4 Calculate the average recovery (X) in [micro]g/L, and the
standard deviation of the recovery (s) in [micro]g/L, for each parameter
using the four results.
[[Page 102]]
8.2.5 For each parameter compare s and X with the corresponding
acceptance criteria for precision and accuracy, respectively, found in
Table 2. If s and X for all parameters of interest meet the acceptance
criteria, the system performance is acceptable and analysis of actual
samples can begin. If any individual s exceeds the precision limit or
any individual X falls outside the range for accuracy, the system
performance is unacceptable for that parameter. Locate and correct the
source of the problem and repeat the test for all parameters of interest
beginning with Section 8.2.2.
8.3 The laboratory must, on an ongoing basis, spike at least 10% of
the samples from each sample site being monitored to assess accuracy.
For laboratories analyzing one to ten samples per month, at least one
spiked sample per month is required.
8.3.1 The concentration of the spike in the sample should be
determined as follows:
8.3.1.1 If, as in compliance monitoring, the concentration of a
specific parameter in the sample is being checked against a regulatory
concentration limit, the spike should be at that limit or 1 to 5 times
higher than the background concentration determined in Section 8.3.2,
whichever concentration would be larger.
8.3.1.2 If the concentration of a specific parameter in the sample
is not being checked against a limit specific to that parameter, the
spike should be at the test concentration in Section 8.2.2 or 1 to 5
times higher than the background concentration determined in Section
8.3.2, whichever concentration would be larger.
8.3.1.3 If it is impractical to determine background levels before
spiking (e.g., maximum holding times will be exceeded), the spike
concentration should be (1) the regulatory concentration limit, if any;
or, if none (2) the larger of either 5 times higher than the expected
background concentration or the test concentration in Section 8.2.2.
8.3.2 Analyze one sample aliquot to determine the background
concentration (B) of each parameter. If necessary, prepare a new QC
check sample concentrate (Section 8.2.1) appropriate for the background
concentrations in the sample. Spike a second sample aliquot with 1.0 mL
of the QC check sample concentrate and analyze it to determine the
concentration after spiking (A) of each parameter. Calculate each
percent recovery (P) as 100(A-B)%/T, where T is the known true value of
the spike.
8.3.3 Compare the percent recovery (P) for each parameter with the
corresponding QC acceptance criteria found in Table 2. These acceptance
criteria were calculated to include an allowance for error in
measurement of both the background and spike concentrations, assuming a
spike to background ratio of 5:1. This error will be accounted for to
the extent that the analyst's spike to background ratio approaches
5:1.\9\ If spiking was performed at a concentration lower than the test
concentration in Section 8.2.2, the analyst must use either the QC
acceptance criteria in Table 2, or optional QC acceptance criteria
calculated for the specific spike concentration. To calculate optional
acceptance criteria for the recovery of a parameter: (1) Calculate
accuracy (X') using the equation in Table 3, substituting the spike
concentration (T) for C; (2) calculate overall precision (S') using the
equation in Table 3, substituting X' for X; (3) calculate the range for
recovery at the spike concentration as (100 X'/T)2.44(100 S'/T)%.\9\
8.3.4 If any individual P falls outside the designated range for
recovery, that parameter has failed the acceptance criteria. A check
standard containing each parameter that failed the criteria must be
analyzed as described in Section 8.4.
8.4 If any parameter fails the acceptance criteria for recovery in
Section 8.3, a QC check standard containing each parameter that failed
must be prepared and analyzed.
Note: The frequency for the required analysis of a QC check standard
will depend upon the number of parameters being simultaneously tested,
the complexity of the sample matrix, and the performance of the
laboratory.
8.4.1 Prepare the QC check standard by adding 1.0 mL of QC check
sample concentrate (Section 8.2.1 or 8.3.2) to 1 L of reagent water. The
QC check standard needs only to contain the parameters that failed
criteria in the test in Section 8.3.
8.4.2 Analyze the QC check standard to determine the concentration
measured (A) of each parameter. Calculate each percent recovery
(Ps) as 100 (A/T)%, where T is the true value of the standard
concentration.
8.4.3 Compare the percent recovery (Ps) for each
parameter with the corresponding QC acceptance criteria found in Table
2. Only parameters that failed the test in Section 8.3 need to be
compared with these criteria. If the recovery of any such parameter
falls outside the designated range, the laboratory performance for that
parameter is judged to be out of control, and the problem must be
immediately identified and corrected. The analytical result for that
parameter in the unspiked sample is suspect and may not be reported for
regulatory compliance purposes.
8.5 As part of the QC program for the laboratory, method accuracy
for wastewater samples must be assessed and records must be maintained.
After the analysis of five spiked wastewater samples as in Section 8.3,
calculate the average percent recovery (P) and the standard deviation of
the percent recovery (sp). Express the accuracy assessment as
a percent recovery interval from P-2sp to P+2sp.
If P=90% and sp=10%, for example, the accuracy interval is
expressed as 70-110%.
[[Page 103]]
Update the accuracy assessment for each parameter on a regular basis
(e.g. after each five to ten new accuracy measurements).
8.6 It is recommended that the laboratory adopt additional quality
assurance practices for use with this method. The specific practices
that are most productive depend upon the needs of the laboratory and the
nature of the samples. Field duplicates may be analyzed to assess the
precision of the environmental measurements. When doubt exists over the
identification of a peak on the chromatogram, confirmatory techniques
such as gas chromatography with a dissimilar column, specific element
detector, or mass spectrometer must be used. Whenever possible, the
laboratory should analyze standard reference materials and participate
in relevant performance evaluation studies.
9. Sample Collection, Preservation, and Handling
9.1 Grab samples must be collected in glass containers. Conventional
sampling practices\10\ should be followed, except that the bottle must
not be prerinsed with sample before collection. Composite samples should
be collected in refrigerated glass containers in accordance with the
requirements of the program. Automatic sampling equipment must be as
free as possible of Tygon tubing and other potential sources of
contamination.
9.2 All samples must be iced or refrigerated at 4 [deg]C from the
time of collection until extraction.
9.3 All samples must be extracted within 7 days of collection and
completely analyzed within 40 days of extraction.\2\
10. Sample Extraction
10.1 Mark the water meniscus on the side of the sample bottle for
later determination of sample volume. Pour the entire sample into a 2-L
separatory funnel.
10.2 Add 60 mL of methylene chloride to the sample bottle, seal, and
shake 30 s to rinse the inner surface. Transfer the solvent to the
separatory funnel and extract the sample by shaking the funnel for 2
min. with periodic venting to release excess pressure. Allow the organic
layer to separate from the water phase for a minimum of 10 min. If the
emulsion interface between layers is more than one-third the volume of
the solvent layer, the analyst must employ mechanical techniques to
complete the phrase separation. The optimum technique depends upon the
sample, but may include stirring, filtration of the emulsion through
glass wool, centrifugation, or other physical methods. Collect the
methylene chloride extract in a 250-mL Erlenmeyer flask.
10.3 Add a second 60-mL volume of methylene chloride to the sample
bottle and repeat the extraction procedure a second time, combining the
extracts in the Erlenmeyer flask. Perform a third extraction in the same
manner.
10.4 Assemble a Kuderna-Danish (K-D) concentrator by attaching a 10-
mL concentrator tube to a 500-mL evaporative flask. Other concentrator
devices or techniques may be used in place of the K-D concentrator if
the requirements of Section 8.2 are met.
10.5 Pour the combined extract through a solvent-rinsed drying
column containing about 10 cm of anhydrous sodium sulfate, and collect
the extract in the K-D concentrator. Rinse the Erlenmeyer flask and
column with 20 to 30 mL of methylene chloride to complete the
quantitative transfer.
10.6 Add one or two clean boiling chips to the evaporative flask and
attach a three-ball Snyder column. Prewet the Snyder column by adding
about 1 mL of methylene chloride to the top. Place the K-D apparatus on
a hot water bath (60 to 65 [deg]C) so that the concentrator tube is
partially immersed in the hot water, and the entire lower rounded
surface of the flask is bathed with hot vapor. Adjust the vertical
position of the apparatus and the water temperature as required to
complete the concentration in 15 to 20 min. At the proper rate of
distillation the balls of the column will actively chatter but the
chambers will not flood with condensed solvent. When the apparent volume
of liquid reaches 1 mL, remove the K-D apparatus and allow it to drain
and cool for at least 10 min.
10.7 Increase the temperature of the hot water bath to about 80
[deg]C. Momentarily remove the Snyder column, add 50 mL of hexane and a
new boiling chip, and reattach the Snyder column. Concentrate the
extract as in Section 10.6, except use hexane to prewet the column. The
elapsed time of concentration should be 5 to 10 min.
10.8 Remove the Snyder column and rinse the flask and its lower
joint into the concentrator tube with 1 to 2 mL of hexane. A 5-mL
syringe is recommended for this operation. Adjust the extract volume to
10 mL. Stopper the concentrator tube and store refrigerated if further
processing will not be performed immediately. If the extract will be
stored longer than two days, it should be transferred to a Teflon-sealed
screw-cap vial. If the sample extract requires no further cleanup,
proceed with gas chromatographic analysis (Section 12). If the sample
requires further cleanup, proceed to Section 11.
10.9 Determine the original sample volume by refilling the sample
bottle to the mark and transferring the liquid to a 1000-mL graduated
cylinder. Record the sample volume to the nearest 5 mL.
11. Cleanup and Separation
11. Cleanup procedures may not be necessary for a relatively clean
sample matrix. If particular circumstances demand the use of a cleanup
procedure, the analyst may use
[[Page 104]]
either procedure below or any other appropriate procedure. However, the
analyst first must demonstrate that the requirements of Section 8.2 can
be met using the method as revised to incorporate the cleanup procedure.
11.2 If the entire extract is to be cleaned up by one of the
following procedures, it must be concentrated to 2.0 mL. To the
concentrator tube in Section 10.8, add a clean boiling chip and attach a
two-ball micro-Snyder column. Prewet the column by adding about 0.5 mL
of hexane to the top. Place the micro-K-D apparatus on a hot water bath
(80 [deg]C) so that the concentrator tube is partially immersed in the
hot water. Adjust the vertical position of the apparatus and the water
temperature as required to complete the concentration in 5 to 10 min. At
the proper rate of distillation the balls of the column will actively
chatter but the chambers will not flood. When the apparent volume of
liquid reaches about 0.5 mL, remove the K-D apparatus and allow it to
drain and cool for at least 10 min. Remove the micro-Snyder column and
rinse its lower joint into the concentrator tube with 0.2 mL of hexane.
Adjust the final volume to 2.0 mL and proceed with one of the following
cleanup procedures.
11.3 Florisil column cleanup for phthalate esters:
11.3.1 Place 10 g of Florisil into a chromatographic column. Tap the
column to settle the Florisil and add 1 cm of anhydrous sodium sulfate
to the top.
11.3.2 Preelute the column with 40 mL of hexane. The rate for all
elutions should be about 2 mL/min. Discard the eluate and just prior to
exposure of the sodium sulfate layer to the air, quantitatively transfer
the 2-mL sample extract onto the column using an additional 2 mL of
hexane to complete the transfer. Just prior to exposure of the sodium
sulfate layer to the air, add 40 mL of hexane and continue the elution
of the column. Discard this hexane eluate.
11.3.3 Next, elute the column with 100 mL of 20% ethyl ether in
hexane (V/V) into a 500-mL K-D flask equipped with a 10-mL concentrator
tube. Concentrate the collected fraction as in Section 10.6. No solvent
exchange is necessary. Adjust the volume of the cleaned up extract to 10
mL in the concentrator tube and analyze by gas chromatography (Section
12).
11.4 Alumina column cleanup for phthalate esters:
11.4.1 Place 10 g of alumina into a chromatographic column. Tap the
column to settle the alumina and add 1 cm of anhydrous sodium sulfate to
the top.
11.4.2 Preelute the column with 40 mL of hexane. The rate for all
elutions should be about 2 mL/min. Discard the eluate and just prior to
exposure of the sodium sulfate layer to the air, quantitatively transfer
the 2-mL sample extract onto the column using an additional 2 mL of
hexane to complete the transfer. Just prior to exposure of the sodium
sulfate layer to the air, add 35 mL of hexane and continue the elution
of the column. Discard this hexane eluate.
11.4.3 Next, elute the column with 140 mL of 20% ethyl ether in
hexane (V/V) into a 500-mL K-D flask equipped with a 10-mL concentrator
type. Concentrate the collected fraction as in Section 10.6. No solvent
exchange is necessary. Adjust the volume of the cleaned up extract to 10
mL in the concentrator tube and analyze by gas chromatography (Section
12).
12. Gas Chromatography
12.1 Table 1 summarizes the recommended operating conditions for the
gas chromatograph. Included in this table are retention times and MDL
that can be achieved under these conditions. Examples of the separations
achieved by Column 1 are shown in Figures 1 and 2. Other packed or
capillary (open-tubular) columns, chromatographic conditions, or
detectors may be used if the requirements of Section 8.2 are met.
12.2 Calibrate the system daily as described in Section 7.
12.3 If the internal standard calibration procedure is being used,
the internal staldard must be added to the sample extract and mixed
thoroughly immediately before injection into the gas chromatograph.
12.4 Inject 2 to 5 [micro]L of the sample extract or standard into
the gas-chromatograph using the solvent-flush technique.\11\ Smaller
(1.0 [micro]L) volumes may be injected if automatic devices are
employed. Record the volume injected to the nearest 0.05 [micro]L, and
the resulting peak size in area or peak height units.
12.5 Identify the parameters in the sample by comparing the
retention times of the peaks in the sample chromatogram with those of
the peaks in standard chromatograms. The width of the retention time
window used to make identifications should be based upon measurements of
actual retention time variations of standards over the course of a day.
Three times the standard deviation of a retention time for a compound
can be used to calculate a suggested window size; however, the
experience of the analyst should weigh heavily in the interpretation of
chromatograms.
12.6 If the response for a peak exceeds the working range of the
system, dilute the extract and reanalyze.
12.7 If the measurement of the peak response is prevented by the
presence of interferences, further cleanup is required.
13. Calculations
13.1 Determine the concentration of individual compounds in the
sample.
[[Page 105]]
13.1.1 If the external standard calibration procedure is used,
calculate the amount of material injected from the peak response using
the calibration curve or calibration factor determined in Section 7.2.2.
The concentration in the sample can be calculated from Equation 2.
[GRAPHIC] [TIFF OMITTED] TC15NO91.103
Equation 2
where:
A=Amount of material injected (ng).
Vi=Volume of extract injected ([micro]L).
Vt=Volume of total extract ([micro]L).
Vs=Volume of water extracted (mL).
13.1.2 If the internal standard calibration procedure is used,
calculate the concentration in the sample using the response factor (RF)
determined in Section 7.3.2 and Equation 3.
[GRAPHIC] [TIFF OMITTED] TC15NO91.104
Equation 3
where:
As=Response for the parameter to be measured.
Ais=Response for the internal standard.
Is=Amount of internal standard added to each extract
([micro]g).
Vo=Volume of water extracted (L).
13.2 Report results in [micro]g/L without correction for recovery
data. All QC data obtained should be reported with the sample results.
14. Method Performance
14.1 The method detection limit (MDL) is defined as the minimum
concentration of a substance that can be measured and reported with 99%
confidence that the value is above zero.\1\ The MDL concentrations
listed in Table 1 were obtained using reagent water.\12\ Similar results
were achieved using representative wastewaters. The MDL actually
achieved in a given analysis will vary depending on instrument
sensitivity and matrix effects.
14.2 This method has been tested for linearity of spike recovery
from reagent water and has been demonstrated to be applicable over the
concentration range from 5 x MDL to 1000 x MDL with the following
exceptions: dimethyl and diethyl phthalate recoveries at 1000 x MDL were
low (70%); bis-2-ethylhexyl and di-n-octyl phthalate recoveries at 5 x
MDL were low (60%).\12\
14.3 This method was tested by 16 laboratories using reagent water,
drinking water, surface water, and three industrial wastewaters spiked
at six concentrations over the range 0.7 to 106 [micro]g/L.\13\ Single
operator precision, overall precision, and method accuracy were found to
be directly related to the concentration of the parameter and
essentially independent of the sample matrix. Linear equations to
describe these relationships are presented in Table 3.
References
1. 40 CFR part 136, appendix B.
2. ``Determination of Phthalates in Industrial and Muncipal
Wastewaters,'' EPA 600/4-81-063, National Technical Information Service,
PB81-232167, Springfield, Virginia 22161, July 1981.
3. ASTM Annual Book of Standards, Part 31, D3694-78. ``Standard
Practices for Preparation of Sample Containers and for Preservation of
Organic Constituents,'' American Society for Testing and Materials,
Philadelphia.
4. Giam, C.S., Chan, H.S., and Nef, G.S. ``Sensitive Method for
Determination of Phthalate Ester Plasticizers in Open-Ocean Biota
Samples,'' Analytical Chemistry, 47, 2225 (1975).
5. Giam, C.S., and Chan, H.S. ``Control of Blanks in the Analysis of
Phthalates in Air and Ocean Biota Samples,'' U.S. National Bureau of
Standards, Special Publication 442, pp. 701-708, 1976.
6. ``Carcinogens--Working with Carcinogens,'' Department of Health,
Education, and Welfare, Public Health Service, Center for Disease
Control, National Institute for Occupational Safety and Health,
Publication No. 77-206, August 1977.
7. ``OSHA Safety and Health Standards, General Industry,'' (29 CFR
part 1910), Occupational Safety and Health Administration, OSHA 2206
(Revised, January 1976).
8. ``Safety in Academic Chemistry Laboratories,'' American Chemical
Society Publication, Committee on Chemical Safety, 3rd Edition, 1979.
9. Provost L.P., and Elder, R.S. ``Interpretation of Percent
Recovery Data,'' American Laboratory, 15, 58-63 (1983). (The value 2.44
used in the equation in Section 8.3.3 is two times the value 1.22
derived in this report.)
10. ASTM Annual Book of Standards, Part 31, D3370-76. ``Standard
Practices for Sampling Water,'' American Society for Testing and
Materials, Philadelphia.
11. Burke, J.A. ``Gas Chromatography for Pesticide Residue Analysis;
Some Practical Aspects,'' Journal of the Association of Official
Analytical Chemists, 48, 1037 (1965).
12. ``Method Detection Limit and Analytical Curve Studies, EPA
Methods 606, 607, and 608,'' Special letter report for EPA Contract 68-
03-2606, U.S. Environmental Protection Agency, Environmental Monitoring
and Support Laboratory, Cincinnati, Ohio 45268, June 1980.
[[Page 106]]
13. ``EPA Method Study 16 Method 606 (Phthalate Esters),'' EPA 600/
4-84-056, National Technical Information Service, PB84-211275,
Springfield, Virginia 22161, June 1984.
Table 1--Chromatographic Conditions and Method Detection Limits
------------------------------------------------------------------------
Retention time (min) Method
---------------------------- detection
Parameter limit
Column 1 Column 2 ([micro]g/L)
------------------------------------------------------------------------
Dimethyl phthalate............ 2.03 0.95 0.29
Diethyl phthalate............. 2.82 1.27 0.49
Di-n-butyl phthalate.......... 8.65 3.50 0.36
Butyl benzyl phthalate........ a 6.94 a 5.11 0.34
Bis(2-ethylhexyl) phthalate... a 8.92 a 10.5 2.0
Di-n-octyl phthalate.......... a 16.2 a 18.0 3.0
------------------------------------------------------------------------
Column 1 conditions: Supelcoport (100/120 mesh) coated with 1.5% SP-2250/
1.95% SP-2401 packed in a 1.8 m long x 4 mm ID glass column with 5%
methane/95% argon carrier gas at 60 mL/min flow rate. Column
temperature held isothermal at 180[deg]C, except where otherwise
indicated.
Column 2 conditions: Supelcoport (100/120 mesh) coated with 3% OV-1
packed in a 1.8 m long x 4 mm ID glass column with 5% methane/95%
argon carrier gas at 60 mL/min flow rate. Column temperature held
isothermal at 200 [deg]C, except where otherwise indicated.
a 220 [deg]C column temperature.
Table 2--QC Acceptance Criteria--Method 606
----------------------------------------------------------------------------------------------------------------
Limit for Range for
Test conc. s X Range for
Parameter ([micro]g/ ([micro]g/ ([micro]g/ P, Ps
L) L) L) (percent)
----------------------------------------------------------------------------------------------------------------
Bis(2-ethylhexyl) phthalate...................................... 50 38.4 1.2-55.9 D-158
Butyl benzyl phthalate........................................... 10 4.2 5.7-11.0 30-136
Di-n-butyl phthalate............................................. 25 8.9 10.3-29.6 23-136
Diethyl phthalate................................................ 25 9.0 1.9-33.4 D-149
Dimethyl phathalate.............................................. 25 9.5 1.3-35.5 D-156
Di-n-octyl phthalate............................................. 50 13.4 D-50.0 D-114
----------------------------------------------------------------------------------------------------------------
s=Standard deviation of four recovery measurements, in [micro]g/L (Section 8.2.4).
X=Average recovery for four recovery measurements, in [micro]g/L (Section 8.2.4).
P, Ps=Percent recovery measured (Section 8.3.2, Section 8.4.2).
D=Detected; result must be greater than zero.
Note: These criteria are based directly upon the method performance data in Table 3. Where necessary, the limits
for recovery have been broadened to assure applicability of the limits to concentrations below those used to
develop Table 3.
Table 3--Method Accuracy and Precision as Functions of Concentration--Method 606
----------------------------------------------------------------------------------------------------------------
Accuracy, as Single analyst Overall
Parameter recovery, X' precision, sr' precision, S'
([micro]g/L) ([micro]g/L) ([micro]g/L)
----------------------------------------------------------------------------------------------------------------
Bis(2-ethylhexyl) phthalate..................................... 0.53C+2.02 0.80X-2.54 0.73X-0.17
Butyl benzyl phthalate.......................................... 0.82C+0.13 0.26X+0.04 0.25X+0.07
Di-n-butyl phthalate............................................ 0.79C+0.17 0.23X+0.20 0.29X+0.06
Diethyl phthalate............................................... 0.70C+0.13 0.27X+0.05 0.45X+0.11
Dimethyl phthalate.............................................. 0.73C+0.17 0.26X+0.14 0.44X+0.31
Di-n-octyl phthalate............................................ 0.35C-0.71 0.38X+0.71 0.62X+0.34
----------------------------------------------------------------------------------------------------------------
X'=Expected recovery for one or more measurements of a sample containing a concentration of C, in [micro]g/L.
sr'=Expected single analyst standard deviation of measurements at an average concentration found of X, in
[micro]g/L.
S'=Expected interlaboratory standard deviation of measurements at an average concentration found of X, in
[micro]g/L.
C=True value for the concentration, in [micro]g/L.
X=Average recovery found for measurements of samples containing a concentration of C, in [micro]g/L.
[[Page 107]]
[GRAPHIC] [TIFF OMITTED] TC02JY92.015
[[Page 108]]
[GRAPHIC] [TIFF OMITTED] TC02JY92.016
[[Page 109]]
Method 607--Nitrosamines
1. Scope and Application
1.1 This method covers the determination of certain nitrosamines.
The following parameters can be determined by this method:
------------------------------------------------------------------------
Parameter Storet No. CAS No.
------------------------------------------------------------------------
N-Nitrosodimethylamine........................ 34438 62-75-9
N-Nitrosodiphenylamine........................ 34433 86-30-6
N-Nitrosodi-n-propylamine..................... 34428 621-64-7
------------------------------------------------------------------------
1.2 This is a gas chromatographic (GC) method applicable to the
determination of the parameters listed above in municipal and industrial
discharges as provided under 40 CFR 136.1. When this method is used to
analyze unfamiliar samples for any or all of the compmunds above,
compound identifications should be supported by at least one additional
qualitative technique. This method describes analytical conditimns for a
second gas chromatographic column that can be used to confirm
measurements made with the primary column. Method 625 provides gas
chromatograph/mass spectrometer (GC/MS) conditions appropriate for the
qualitative and quantitative confirmation of results for N-nitrosodi-n-
propylamine. In order to confirm the presence of N-nitrosodiphenylamine,
the cleanup procedure specified in Section 11.3 or 11.4 must be used. In
order to confirm the presence of N-nitrosodimethylamine by GC/MS, Column
1 of this method must be substituted for the column recommended in
Method 625. Confirmation of these parameters using GC-high resolution
mass spectrometry or a Thermal Energy Analyzer is also recommended.
1, 2
1.3 The method detection limit (MDL, defined in Section
14.1)3 for each parameter is listed in Table 1. The MDL for a
specific wastewater may differ from those listed, depending upon the
nature of interferences in the sample matrix.
1.4 Any modification of this method, beyond those expressly
permitted, shall be considered as a major modification subject to
application and approval of alternate test procedures under 40 CFR 136.4
and 136.5.
1.5 This method is restricted to use by or under the supervision of
analysts experienced in the use of a gas chromatograph and in the
interpretation of gas chromatograms. Each analyst must demonstrate the
ability to generate acceptable results with this method using the
procedure described in Section 8.2.
2. Summary of Method
2.1 A measured volume of sample, approximately 1-L, is extracted
with methylene chloride using a separatory funnel. The methylene
chloride extract is washed with dilute hydrochloric acid to remove free
amines, dried, and concentrated to a volume of 10 mL or less. After the
extract has been exchanged to methanol, it is separated by gas
chromatography and the parameters are then measured with a nitrogen-
phosphorus detector.4
2.2 The method provides Florisil and alumina column cleanup
procedures to separate diphenylamine from the nitrosamines and to aid in
the elimination of interferences that may be encountered.
3. Interferences
3.1 Method interferences may be caused by contaminants in solvents,
reagents, glassware, and other sample processing hardware that lead to
discrete artifacts and/or elevated baselines in gas chromatograms. All
of these materials must be routinely demonstrated to be free from
interferences under the conditions of the analysis by running laboratory
reagent blanks as described in Section 8.1.3.
3.1.1 Glassware must be scrupulously cleaned.5 Clean all
glassware as soon as possible after use by rinsing with the last solvent
used in it. Solvent rinsing should be followed by detergent washing with
hot water, and rinses with tap water and distilled water. The glassware
should then be drained dry, and heated in a muffle furnace at 400 [deg]C
for 15 to 30 min. Solvent rinses with acetone and pesticide quality
hexane may be substituted for the muffle furnace heating. Volumetric
ware should not be heated in a muffle furnace. After drying and cooling,
glassware should be sealed and stored in a clean environment to prevent
any accumulation of dust or other contaminants. Store inverted or capped
with aluminum foil.
3.1.2 The use of high purity reagents and solvents helps to minimize
interference problems. Purification of solvents by distillation in all-
glass systems may be required.
3.2 Matrix interferences may be caused by contaminants that are co-
extracted from the sample. The extent of matrix interferences will vary
considerably from source to source, depending upon the nature and
diversity of the industrial complex or municipality being sampled. The
cleanup procedures in Section 11 can be used to overcome many of these
interferences, but unique samples may require additional cleanup
approaches to achieve the MDL listed in Table 1.
3.3 N-Nitrosodiphenylamine is reported6-9 to undergo
transnitrosation reactions. Care must be exercised in the heating or
concentrating of solutions containing this compound in the presence of
reactive amines.
3.4 The sensitive and selective Thermal Energy Analyzer and the
reductive Hall detector may be used in place of the nitrogen-phosphorus
detector when interferences are encountered. The Thermal Energy Analyzer
offers the highest selectivity of the non-MS detectors.
[[Page 110]]
4. Safety
4.1 The toxicity or carcinogenicity of each reagent used in this
method has not been precisely defined; however, each chemical compound
should be treated as a potential health hazard. From this viewpoint,
exposure to these chemicals must be reduced to the lowest possible level
by whatever means available. The laboratory is responsible for
maintaining a current awareness file of OSHA regulations regarding the
safe handling of the chemicals specified in this method. A reference
file of material data handling sheets should also be made available to
all personnel involved in the chemical analysis. Additional references
to laboratory safety are available and have been identified
10-12 for the information of the analyst.
4.2 These nitrosamines are known carcinogens 13-17,
therefore, utmost care must be exercised in the handling of these
materials. Nitrosamine reference standards and standard solutions should
be handled and prepared in a ventilated glove box within a properly
ventilated room.
5. Apparatus and Materials
5.1 Sampling equipment, for discrete or composite sampling.
5.1.1 Grab sample bottle--1-L or 1-qt, amber glass, fitted with a
screw cap lined with Teflon. Foil may be substituted for Teflon if the
sample is not corrosive. If amber bottles are not available, protect
samples from light. The bottle and cap liner must be washed, rinsed with
acetone or methylene chloride, and dried before use to minimize
contamination.
5.1.2 Automatic sampler (optional)--The sampler must incorporate
glass sample containers for the collection of a minimum of 250 mL of
sample. Sample containers must be kept refrigerated at 4 [deg]C and
protected from light during compositing. If the sampler uses a
peristaltic pump, a minimum length of compressible silicone rubber
tubing may be used. Before use, however, the compressible tubing should
be thoroughly rinsed with methanol, followed by repeated rinsings with
distilled water to minimize the potential for contamination of the
sample. An integrating flowmeter is required to collect flow
proportional composites.
5.2 Glassware (All specifications are suggested. Catalog numbers are
included for illustration only.):
5.2.1 Separatory funnels--2-L and 250-mL, with Teflon stopcock.
5.2.2 Drying column--Chromatographic column, approximately 400 mm
long x 19 mm ID, with coarse frit filter disc.
5.2.3 Concentrator tube, Kuderna-Danish--10-mL, graduated (Kontes K-
570050-1025 or equivalent). Calibration must be checked at the volumes
employed in the test. Ground glass stopper is used to prevent
evaporation of extracts.
5.2.4 Evaporative flask, Kuderna-Danish--500-mL (Kontes K-570001-
0500 or equivalent). Attach to concentrator tube with springs.
5.2.5 Snyder column, Kuderna-Danish--Three-ball macro (Kontes K-
503000-0121 or equivalent).
5.2.6 Snyder column, Kuderna-Danish--Two-ball micro (Kontes K-
569001-0219 or equivalent).
5.2.7 Vials--10 to 15-mL, amber glass, with Teflon-lined screw cap.
5.2.8 Chromatographic column--Approximately 400 mm long x 22 mm ID,
with Teflon stopcock and coarse frit filter disc at bottom (Kontes K-
420540-0234 or equivalent), for use in Florisil column cleanup
procedure.
5.2.9 Chromatographic column--Approximately 300 mm long x 10 mm ID,
with Teflon stopcock and coarse frit filter disc at bottom (Kontes K-
420540-0213 or equivalent), for use in alumina column cleanup procedure.
5.3 Boiling chips--Approximately 10/40 mesh. Heat to 400 [deg]C for
30 min or Soxhlet extract with methylene chloride.
5.4 Water bath--Heated, with concentric ring cover, capable of
temperature control (2 [deg]C). The bath should be
used in a hood.
5.5 Balance--Analytical, capable of accurately weighing 0.0001 g.
5.6 Gas chromatograph--An analytical system complete with gas
chromatograph suitable for on-column injection and all required
accessories including syringes, analytical columns, gases, detector, and
strip-chart recorder. A data system is recommended for measuring peak
areas.
5.6.1 Column 1--1.8 m long x 4 mm ID glass, packed with 10% Carbowax
20 M/2% KOH on Chromosorb W-AW (80/100 mesh) or equivalent. This column
was used to develop the method performance statements in Section 14.
Guidelines for the use of alternate column packings are provided in
Section 12.2.
5.6.2 Column 2--1.8 m long x 4 mm ID glass, packed with 10% SP-2250
on Supel- coport (100/120 mesh) or equivalent.
5.6.3 Detector--Nitrogen-phosphorus, reductive Hall, or Thermal
Energy Analyzer detector. 1, 2 These detectors have proven
effective in the analysis of wastewaters for the parameters listed in
the scope (Section 1.1). A nitrogen-phosphorus detector was used to
develop the method performance statements in Section 14. Guidelines for
the use of alternate detectors are provided in Section 12.2.
6. Reagents
6.1 Reagent water--Reagent water is defined as a water in which an
interferent is not observed at the MDL of the parameters of interest.
6.2 Sodium hydroxide solution (10 N)--Dissolve 40 g of NaOH (ACS) in
reagent water and dilute to 100 ml.
[[Page 111]]
6.3 Sodium thiosulfate--(ACS) Granular.
6.4 Sulfuric acid (1+1)--Slowly, add 50 mL of
H2SO4 (ACS, sp. gr. 1.84) to 50 mL of reagent
water.
6.5 Sodium sulfate--(ACS) Granular, anhydrous. Purify by heating at
400 [deg]C for 4 h in a shallow tray.
6.6 Hydrochloric acid (1+9)--Add one volume of concentrated HCl
(ACS) to nine volumes of reagent water.
6.7 Acetone, methanol, methylene chloride, pentane--Pesticide
quality or equivalent.
6.8 Ethyl ether--Nanograde, redistilled in glass if necessary.
6.8.1 Ethyl ether must be shown to be free of peroxides before it is
used as indicated by EM Laboratories Quant test strips. (Available from
Scientific Products Co., Cat No. P1126-8, and other suppliers.)
6.8.2 Procedures recommended for removal of peroxides are provided
with the test strips. After cleanup, 20 mL of ethyl alcohol preservative
must be added to each liter of ether.
6.9 Florisil--PR grade (60/100 mesh). Purchase activated at 1250
[deg]F and store in the dark in glass containers with ground glass
stoppers or foil-lined screw caps. Before use, activate each batch at
least 16 h at 130 [deg]C in a foil-covered glass container and allow to
cool.
6.10 Alumina--Basic activity Super I, W200 series (ICN Life Sciences
Group, No. 404571, or equivalent). To prepare for use, place 100 g of
alumina into a 500-mL reagent bottle and add 2 mL of reagent water. Mix
the alumina preparation thoroughly by shaking or rolling for 10 min and
let it stand for at least 2 h. The preparation should be homogeneous
before use. Keep the bottle sealed tightly to ensure proper activity.
6.11 Stock standard solutions (1.00 [micro]g/[micro]L)--Stock
standard solutions can be prepared from pure standard materials or
purchased as certified solutions.
6.11.1 Prepare stock standard solutions by accurately weighing about
0.0100 g of pure material. Dissolve the material in methanol and dilute
to volume in a 10-mL volumetric flask. Larger volumes can be used at the
convenience of the analyst. When compound purity is assayed to be 96% or
greater, the weight can be used without correction to calculate the
concentration of the stock standard. Commercially prepared stock
standards can be used at any concentration if they are certified by the
manufacturer or by an independent source.
6.11.2 Transfer the stock standard solutions into Teflon-sealed
screw-cap bottles. Store at 4 [deg]C and protect from light. Stock
standard solutions should be checked frequently for signs of degradation
or evaporation, especially just prior to preparing calibration standards
from them.
6.11.3 Stock standard solutions must be replaced after six months,
or sooner if comparison with check standards indicates a problem.
6.12 Quality control check sample concentrate--See Section 8.2.1.
7. Calibration
7.1 Establish gas chromatographic operating conditions equivalent to
those given in Table 1. The gas chromatographic system can be calibrated
using the external standard technique (Section 7.2) or the internal
standard technique (Section 7.3).
7.2 External standard calibration procedure:
7.2.1 Prepare calibration standards at a minimum of three
concentration levels for each parameter of interest by adding volumes of
one or more stock standards to a volumetric flask and diluting to volume
with methanol. One of the external standards should be at a concentraton
near, but above, the MDL (Table 1) and the other concentrations should
correspond to the expected range of concentrations found in real samples
or should define the working range of the detector.
7.2.2 Using injections of 2 to 5 [micro]L, analyze each calibration
standard according to Section 12 and tabulate peak height or area
responses against the mass injected. The results can be used to prepare
a calibration curve for each compound. Alternatively, if the ratio of
response to amount injected (calibration factor) is a constant over the
working range (<10% relative standard deviation, RSD), linearity through
the origin can be assumed and the average ratio or calibration factor
can be used in place of a calibration curve.
7.3 Internal standard calibration procedure--To use this approach,
the analyst must select one or more internal standards that are similar
in analytical behavior to the compounds of interest. The analyst must
further demonstrate that the measurement of the internal standard is not
affected by method or matrix interferences. Because of these
limitations, no internal standard can be suggested that is applicable to
all samples.
7.3.1 Prepare calibration standards at a minimum of three
concentration levels for each parameter of interest by adding volumes of
one or more stock standards to a volumetric flask. To each calibration
standard, add a known constant amount of one or more internal standards,
and dilute to volume with methanol. One of the standards should be at a
concentration near, but above, the MDL and the other concentrations
should correspond to the expected range of concentrations found in real
samples or should define the working range of the detector.
[[Page 112]]
7.3.2 Using injections of 2 to 5 [micro]L, analyze each calibration
standard according to Section 12 and tabulate peak height or area
responses against concentration for each compound and internal standard.
Calculate response factors (RF) for each compound using Equation 1.
RF= (As)(Cis) (Ais)(Cs)
----------------------------------------------------------------------------------------------------------------
Equation 1
where:
As=Response for the parameter to be measured.
Ais=Response for the internal standard.
Cis=Concentration of the internal standard ([micro]g/L).
Cs=Concentration of the parameter to be measured ([micro]g/
L).
If the RF value over the working range is a constant (<10% RSD), the
RF can be assumed to be invariant and the average RF can be used for
calculations. Alternatively, the results can be used to plot a
calibration curve of response ratios, As/Ais, vs.
RF.
7.4 The working calibration curve, calibration factor, or RF must be
verified on each working day by the measurement of one or more
calibration standards. If the response for any parameter varies from the
predicted response by more than 15%, a new
calibration curve must be prepared for that compound.
7.5 Before using any cleanup procedure, the analyst must process a
series of calibration standards through the procedure to validate
elution patterns and the absence of interferences from the reagents.
8. Quality Control
8.1 Each laboratory that uses this method is required to operate a
formal quality control program. The minimum requirements of this program
consist of an initial demonstration of laboratory capability and an
ongoing analysis of spiked samples to evaluate and document data
quality. The laboratory must maintain records to document the quality of
data that is generated. Ongoing data quality checks are compared with
established performance criteria to determine if the results of analyses
meet the performance characteristics of the method. When results of
sample spikes indicate atypical method performance, a quality control
check standard must be analyzed to confirm that the measurements were
performed in an in-control mode of operation.
8.1.1 The analyst must make an initial, one-time, demonstration of
the ability to generate acceptable accuracy and precision with this
method. This ability is established as described in Section 8.2.
8.1.2 In recognition of advances that are occurring in
chromatography, the analyst is permitted certain options (detailed in
Sections 10.4, 11.1, and 12.2) to improve the separations or lower the
cost of measurements. Each time such a modification is made to the
method, the analyst is required to repeat the procedure in Section 8.2.
8.1.3 Before processing any samples, the analyst must analyze a
reagent water blank to demonstrate that interferences from the
analytical system and glassware are under control. Each time a set of
samples is extracted or reagents are changed, a reagent water blank must
be processed as a safeguard against laboratory contamination.
8.1.4 The laboratory must, on an ongoing basis, spike and analyze a
minimum of 10% of all samples to monitor and evaluate laboratory data
quality. This procedure is described in Section 8.3.
8.1.5 The laboratory must, on an ongoing basis, demonstrate through
the analyses of quality control check standards that the operation of
the measurement system is in control. This procedure is described in
Section 8.4. The frequency of the check standard analyses is equivalent
to 10% of all samples analyzed but may be reduced if spike recoveries
from samples (Section 8.3) meet all specified quality control criteria.
8.1.6 The laboratory must maintain performance records to document
the quality of data that is generated. This procedure is described in
Section 8.5.
8.2 To establish the ability to generate acceptable accuracy and
precision, the analyst must perform the following operations.
8.2.1 A quality control (QC) check sample concentrate is required
containing each parameter of interest at a concentration of 20 [micro]g/
mL in methanol. The QC check sample concentrate must be obtained from
the U.S. Environmental Protection Agency, Environmental Monitoring and
Support Laboratory in Cincinnati, Ohio, if available. If not available
from that source, the QC check sample concentrate must be obtained from
another external source. If not available from either source above, the
QC check sample concentrate must be prepared by the laboratory using
stock standards prepared independently from those used for calibration.
8.2.2 Using a pipet, prepare QC check samples at a concentration of
20 [micro]g/L by adding 1.00 mL of QC check sample concentrate to each
of four 1-L aliquots of reagent water.
8.2.3 Analyze the well-mixed QC check samples according to the
method beginning in Section 10.
8.2.4 Calculate the average recovery (X) in [micro]g/L, and the
standard deviation of the recovery (s) in [micro]g/L, for each parameter
using the four results.
8.2.5 For each parameter compare s and X with the corresponding
acceptance criteria for precision and accuracy, respectively,
[[Page 113]]
found in Table 2. If s and X for all parameters of interest meet the
acceptance criteria, the system performance is acceptable and analysis
of actual samples can begin. If any individual s exceeds the precision
limit or any individual X falls outside the range for accuracy, the
system performance is unacceptable for that parameter. Locate and
correct the source of the problem and repeat the test for all parameters
of interest beginning with Section 8.2.2.
8.3 The laboratory must, on an ongoing basis, spike at least 10% of
the samples from each sample site being monitored to assess accuracy.
For laboratories analyzing one to ten samples per month, at least one
spiked sample per month is required.
8.3.1 The concentration of the spike in the sample should be
determined as follows:
8.3.1.1 If, as in compliance monitoring, the concentration of a
specific parameter in the sample is being checked against a regulatory
concentration limit, the spike should be at that limit or 1 to 5 times
higher than the background concentration determined in Section 8.3.2,
whichever concentration would be larger.
8.3.1.2 If the concentration of a specific parameter in the sample
is not being checked against a limit specific to that parameter, the
spike should be at 20 [micro]g/L or 1 to 5 times higher than the
background concentration determined in Section 8.3.2, whichever
concentration would be larger.
8.3.1.3 If it is impractical to determine background levels before
spiking (e.g., maximum holding times will be exceeded), the spike
concentration should be (1) the regulatory concentration limit, if any;
or, if none (2) the larger of either 5 times higher than the expected
background concentration or 20 [micro]g/L.
8.3.2 Analyze one sample aliquot to determine the background
concentration (B) of each parameter. If necessary, prepare a new QC
check sample concentrate (Section 8.2.1) appropriate for the background
concentrations in the sample. Spike a second sample aliquot with 1.0 mL
of the QC check sample concentrate and analyze it to determine the
concentration after spiking (A) of each parameter. Calculate each
percent recovery (P) as 100(A-B)%/T, where T is the known true value of
the spike.
8.3.3 Compare the percent recovery (P) for each parameter with the
corresponding QC acceptance criteria found in Table 2. These acceptance
criteria were caluclated to include an allowance for error in
measurement of both the background and spike concentrations, assuming a
spike to background ratio of 5:1. This error will be accounted for to
the extent that the analyst's spike to background ratio approaches
5:1.\18\ If spiking was performed at a concentration lower than 20
[micro]g/L, the analyst must use either the QC acceptance criteria in
Table 2, or optional QC acceptance criteria caluclated for the specific
spike concentration. To calculate optional acceptance crtieria for the
recovery of a parameter: (1) Calculate accuracy (X') using the equation
in Table 3, substituting the spike concentration (T) for C; (2)
calculate overall precision (S') using the equation in Table 3,
substituting X' for X; (3) calculate the range for recovery at the spike
concentration as (100 X'/T) 2.44(100 S'/T)%.\18\
8.3.4 If any individual P falls outside the designated range for
recovery, that parameter has failed the acceptance criteria. A check
standard containing each parameter that failed the criteria must be
analyzed as described in Section 8.4.
8.4 If any parameter fails the acceptance criteria for recovery in
Section 8.3, a QC check standard containing each parameter that failed
must be prepared and analyzed.
Note: The frequency for the required analysis of a QC check standard
will depend upon the number of parameters being simultaneously tested,
the complexity of the sample matrix, and the performance of the
laboratory.
8.4.1 Prepare the QC check standard by adding 1.0 mL of QC check
sample concentrate (Section 8.2.1 or 8.3.2) to 1 L of reagent water. The
QC check standard needs only to contain the parameters that failed
criteria in the test in Section 8.3.
8.4.2 Analyze the QC check standard to determine the concentration
measured (A) of each parameter. Calculate each percent recovery
(Ps) as 100 (A/T)%, where T is the true value of the standard
concentration.
8.4.3 Compare the percent recovery (Ps) for each
parameter with the corresponding QC acceptance criteria found in Table
2. Only parameters that failed the test in Section 8.3 need to be
compared with these criteria. If the recovery of any such parameter
falls outside the designated range, the laboratory performance for that
parameter is judged to be out of control, and the problem must be
immediately identified and corrected. The analytical result for that
parameter in the unspiked sample is suspect and may not be reported for
regulatory compliance purposes.
8.5 As part of the QC program for the laboratory, method accuracy
for wastewater samples must be assessed and records must be maintained.
After the analysis of five spiked wastewater samples as in Section 8.3,
calculate the average percent recovery (P) and the standard deviation of
the percent recovery (sp). Express the accuracy assessment as
a percent recovery interval from P-2sp to P+2sp.
If P=90% and sp=10%, for example, the accuracy interval is
expressed as 70-110%. Update the accuracy assessment for each parameter
on a regular basis (e.g. after each five to ten new accuracy
measurements).
8.6 It is recommended that the laboratory adopt additional quality
assurance practices
[[Page 114]]
for use with this method. The specific practices that are most
productive depend upon the needs of the laboratory and the nature of the
samples. Field duplicates may be analyzed to assess the precision of the
environmental measurements. When doubt exists over the identification of
a peak on the chromatogram, confirmatory techniques such as gas
chromatography with a dissimilar column, specific element detector, or
mass spectrometer must be used. Whenever possible, the laboratory should
analyze standard reference materials and participate in relevant
performance evaluation studies.
9. Sample Collection, Preservation, and Handling
9.1 Grab samples must be collected in glass containers. Conven
tional sampling practices \19\ should be followed, except that the
bottle must not be pre rinsed with sample before collection. Composite
sam ples should be collected in refrigerated glass containers in
accordance with the requirements of the program. Automatic sampling
equipment must be as free as possible of Tygon tubing and other
potential sources of contamination.
9.2 All samples must be iced or refrigerated at 4 [deg]C from the
time of collection until extraction. Fill the sample bottles and, if
residual chlorine is present, add 80 mg of sodium thiosulfate per liter
of sample and mix well. EPA Methods 330.4 and 330.5 may be used for
measurement of residual chlorine.\20\ Field test kits are available for
this purpose. If N-nitrosodiphenylamine is to be determined, adjust the
sample pH to 7 to 10 with sodium hydroxide solution or sulfuric acid.
9.3 All samples must be extracted within 7 days of collection and
completely analyzed within 40 days of extraction.\4\
9.4 Nitrosamines are known to be light sen sitive.\7\ Samples should
be stored in amber or foil-wrapped bottles in order to minimize
photolytic decomposition.
10. Sample Extraction
10.1 Mark the water meniscus on the side of the sample bottle for
later determination of sample volume. Pour the entire sample into a 2-L
separatory funnel. Check the pH of the sample with wide-range pH paper
and adjust to within the range of 5 to 9 with sodium hydroxide solution
or sulfuric acid.
10.2 Add 60 mL of methylene chloride to the sample bottle, seal, and
shake 30 s to rinse the inner surface. Transfer the solvent to the
separatory funnel and extract the sample by shaking the funnel for 2 min
with periodic venting to release excess pressure. Allow the organic
layer to separate from the water phase for a minimum of 10 min. If the
emulsion interface between layers is more than one-third the volume of
the solvent layer, the analyst must employ mechanical techniques to
complete the phase separation. The optimum technique depends upon the
sample, but may include stirring, filtration of the emulsion through
glass wool, centrifugation, or other physical methods. Collect the
methylene chloride extract in a 250-mL Erlenmeyer flask.
10.3 Add a second 60-mL volume of methylene chloride to the sample
bottle and repeat the extraction procedure a second time, combining the
extracts in the Erlenmeyer flask. Perform a third extraction in the same
manner.
10.4 Assemble a Kuderna-Danish (K-D) con centrator by attaching a
10-mL concentra tor tube to a 500-mL evaporative flask. Other
concentration devices or techniques may be used in place of the K-D
concentrator if the requirements of Section 8.2 are met.
10.5 Add 10 mL of hydrochloric acid to the combined extracts and
shake for 2 min. Allow the layers to separate. Pour the combined extract
through a solvent-rinsed drying column containing about 10 cm of
anhydrous sodium sulfate, and collect the extract in the K-D
concentrator. Rinse the Erlenmeyer flask and column with 20 to 30 mL of
methylene chloride to complete the quantitative transfer.
10.6 Add one or two clean boiling chips to the evaporative flask and
attach a three-ball Snyder column. Prewet the Snyder column by adding
about 1 mL of methylene chloride to the top. Place the K-D apparatus on
a hot water bath (60 to 65[deg]C) so that the concentrator tube is
partially immersed in the hot water, and the entire lower rounded
surface of the flask is bathed with hot vapor. Adjust the vertical
position of the apparatus and the water temperature as required to
complete the concentration in 15 to 20 min. At the proper rate of
distillation the balls of the column will actively chatter but the
chambers will not flood with condensed solvent. When the apparent volume
of liquid reaches 1 mL, remove the K-D apparatus and allow it to drain
and cool for at least 10 min.
10.7 Remove the Snyder column and rinse the flask and its lower
joint into the concentrator tube with 1 to 2 mL of methylene chloride. A
5-mL syringe is recommended for this operation. Stopper the concentrator
tube and store refrigerated if further processing will not be performed
immediately. If the extract will be stored longer than two days, it
should be transferred to a Teflon-sealed screw-cap vial. If N-nitro sodi
phe nylamine is to be measured by gas chromatography, the analyst must
first use a cleanup column to eliminate diphenylamine interference
(Section 11). If N-nitrosodiphenylamine is of no interest, the analyst
may proceed directly with gas chromatographic analysis (Section 12).
[[Page 115]]
10.8 Determine the original sample volume by refilling the sample
bottle to the mark and transferring the liquid to a 1000-
mL graduated cylinder. Record the sample volume to the nearest 5 mL.
11. Cleanup and Separation
11.1 Cleanup procedures may not be necessary for a relatively clean
sample matrix. If particular circumstances demand the use of a cleanup
procedure, the analyst may use either procedure below or any other
appropriate procedure. However, the analyst first must demonstrate that
the requirements of Section 8.2 can be met using the method as revised
to incorporate the cleanup procedure. Diphenylamine, if present in the
original sample extract, must be separated from the nitrosamines if N-
nitrosodiphenylamine is to be determined by this method.
11.2 If the entire extract is to be cleaned up by one of the
following procedures, it must be concentrated to 2.0 mL. To the
concentrator tube in Section 10.7, add a clean boiling chip and attach a
two-ball micro-Snyder column. Prewet the column by adding about 0.5 mL
of methylene chloride to the top. Place the micr-K-D apparatus on a hot
water bath (60 to 65 [deg]C) so that the concentrator tube is partially
immersed in the hot water. Adjust the vertical position of the apparatus
and the water temperature as required to complete the concentration in 5
to 10 min. At the proper rate of distillation the balls of the column
will actively chatter but the chambers will not flood. When the apparent
volume of liquid reaches about 0.5 mL, remove the K-D apparatus and
allow it to drain and cool for at least 10 min. Remove the micro-Snyder
column and rinse its lower joint into the concentrator tube with 0.2 mL
of methylene chloride. Adjust the final volume to 2.0 mL and proceed
with one of the following cleanup procedures.
11.3 Florisil column cleanup for nitro samines:
11.3.1 Place 22 g of activated Florisil into a 22-mm ID
chromatographic column. Tap the column to settle the Florisil and add
about 5 mm of anhydrous sodium sulfate to the top.
11.3.2 Preelute the column with 40 mL of ethyl ether/pentane
(15+85)(V/V). Discard the eluate and just prior to exposure of the
sodium sulfate layer to the air, quantitatively transfer the 2-mL sample
extract onto the column using an additional 2 mL of pentane to complete
the transfer.
11.3.3 Elute the column with 90 mL of ethyl ether/pentane (15+85)(V/
V) and discard the eluate. This fraction will contain the diphenylamine,
if it is present in the extract.
11.3.4 Next, elute the column with 100 mL of acetone/ethyl ether
(5+95)(V/V) into a 500-mL K-D flask equipped with a 10-mL concentrator
tube. This fraction will contain all of the nitrosamines listed in the
scope of the method.
11.3.5 Add 15 mL of methanol to the collected fraction and
concentrate as in Section 10.6, except use pentane to prewet the column
and set the water bath at 70 to 75 [deg]C. When the apparatus is cool,
remove the Snyder column and rinse the flask and its lower joint into
the concentrator tube with 1 to 2 mL of pentane. Analyze by gas
chromatography (Section 12).
11.4 Alumina column cleanup for nitro samines:
11.4.1 Place 12 g of the alumina preparation (Section 6.10) into a
10-mm ID chromatographic column. Tap the column to settle the alumina
and add 1 to 2 cm of anhydrous sodium sulfate to the top.
11.4.2 Preelute the column with 10 mL of ethyl ether/pentane
(3+7)(V/V). Discard the eluate (about 2 mL) and just prior to exposure
of the sodium sulfate layer to the air, quantitatively transfer the 2 mL
sample extract onto the column using an additional 2 mL of pentane to
complete the transfer.
11.4.3 Just prior to exposure of the sodium sulfate layer to the
air, add 70 mL of ethyl ether/pentane (3+7)(V/V). Discard the first 10
mL of eluate. Collect the remainder of the eluate in a 500-mL K-D flask
equipped with a 10 mL concentrator tube. This fraction contains N-
nitrosodiphenylamine and probably a small amount of N-nitrosodi-n-
propylamine.
11.4.4 Next, elute the column with 60 mL of ethyl ether/pentane
(1+1)(V/V), collecting the eluate in a second K-D flask equipped with a
10-mL concentrator tube. Add 15 mL of methanol to the K-D flask. This
fraction will contain N-nitrosodimethylamine, most of the N-nitrosodi-n-
propylamine and any diphenylamine that is present.
11.4.5 Concentrate both fractions as in Section 10.6, except use
pentane to prewet the column. When the apparatus is cool, remove the
Snyder column and rinse the flask and its lower joint into the
concentrator tube with 1 to 2 mL of pentane. Analyze the fractions by
gas chromatography (Section 12).
12. Gas Chromatography
12.1 N-nitrosodiphenylamine completely reacts to form diphenylamine
at the normal operating temperatures of a GC injection port (200 to 250
[deg]C). Thus, N-nitro sodi phenylamine is chromatographed and detected
as di phe nyla mine. Accurate determination depends on removal of di phe
nyla mine that may be present in the original extract prior to GC
analysis (See Section 11).
12.2 Table 1 summarizes the recommended operating conditions for the
gas chromatograph. Included in this table are retention times and MDL
that can be achieved under these conditions. Examples of the separations
achieved by Column 1 are shown in Figures 1 and 2. Other packed or
capillary
[[Page 116]]
(open-tubular) columns, chromatographic conditions, or detectors may be
used if the requirements of Section 8.2 are met.
12.3 Calibrate the system daily as described in Section 7.
12.4 If the extract has not been subjected to one of the cleanup
procedures in Section 11, it is necessary to exchange the solvent from
methylene chloride to methanol before the thermionic detector can be
used. To a 1 to 10-mL volume of methylene chloride extract in a
concentrator tube, add 2 mL of methanol and a clean boiling chip. Attach
a two-ball micro-Snyder column to the concentrator tube. Prewet the
column by adding about 0.5 mL of methylene chloride to the top. Place
the micro-K-D apparatus on a boiling (100 [deg]C) water bath so that the
concentrator tube is partially immersed in the hot water. Adjust the
vertical position of the apparatus and the water temperature as required
to complete the concentration in 5 to 10 min. At the proper rate of
distillation the balls of the column will actively chatter but the
chambers will not flood. When the apparent volume of liquid reaches
about 0.5 mL, remove the K-D apparatus and allow it to drain and cool
for at least 10 min. Remove the micro-Snyder column and rinse its lower
joint into the concentrator tube with 0.2 mL of methanol. Adjust the
final volume to 2.0 mL.
12.5 If the internal standard calibration procedure is being used,
the internal standard must be added to the sample extract and mixed
thoroughly immediately before injection into the gas chromatograph.
12.6 Inject 2 to 5 [micro]L of the sample extract or standard into
the gas chromatograph using the solvent-flush technique.\21\ Smaller
(1.0 [micro]L) volumes may be injected if automatic devices are
employed. Record the volume injected to the nearest 0.05 [micro]L, and
the resulting peak size in area or peak height units.
12.7 Identify the parameters in the sample by comparing the
retention times of the peaks in the sample chromatogram with those of
the peaks in standard chromatograms. The width of the retention time
window used to make identifications should be based upon measurements of
actual retention time variations of standards over the course of a day.
Three times the standard deviation of a retention time for a compound
can be used to calculate a suggested window size; however, the
experience of the analyst should weigh heavily in the interpretation of
chromatograms.
12.8 If the response for a peak exceeds the working range of the
system, dilute the extract and reanalyze.
12.9 If the measurement of the peak response is prevented by the
presence of interferences, further cleanup is required.
13. Calculations
13.1 Determine the concentration of individual compounds in the
sample.
13.1.1 If the external standard calibration procedure is used,
calculate the amount of material injected from the peak response using
the calibration curve or calibration factor determined in Section 7.2.2.
The concentration in the sample can be calculated from Equation 2.
[GRAPHIC] [TIFF OMITTED] TC15NO91.105
Equation 2
where:
A=Amount of material injected (ng).
Vi=Volume of extract injected ([micro]L).
Vt=Volume of total extract ([micro]L).
Vs=Volume of water extracted (mL).
13.1.2 If the internal standard calibration procedure is used,
calculate the concentration in the sample using the response factor (RF)
determined in Section 7.3.2 and Equation 3.
[GRAPHIC] [TIFF OMITTED] TC15NO91.106
Equation 3
where:
As=Response for the parameter to be measured.
Ais=Response for the internal standard.
Is=Amount of internal standard added to each extract
([micro]g).
Vo=Volume of water extracted (L).
13.2 Report results in [micro]g/L without correction for recovery
data. All QC data obtained should be reported with the sample results.
14. Method Performance
14.1 The method detection limit (MDL) is defined as the minimum
concentration of a substance that can be measured and reported with 99%
confidence that the value is above zero.\3\ The MDL concentrations
listed in Table 1 were obtained using reagent water.\22\ Similar results
were achieved using representative wastewaters. The MDL actually
achieved in a given analysis will vary depending on instrument
sensitivity and matrix effects.
14.2 This method has been tested for linearity of spike recovery
from reagent water and has been demonstrated to be applicable over the
concentration range from 4 x MDL to 1000 x MDL.\22\
14.3 This method was tested by 17 laboratories using reagent water,
drinking water, surface water, and three industrial wastewaters spiked
at six concentrations
[[Page 117]]
over the range 0.8 to 55 [micro]g/L.\23\ Single operator precision,
overall precision, and method accuracy were found to be directly related
to the concentration of the parameter and essentially independent of the
sample matrix. Linear equations to describe these relationships are
presented in Table 3.
References
1. Fine, D.H., Lieb, D., and Rufeh, R. ``Principle of Operation of
the Thermal Energy Analyzer for the Trace Analysis of Volatile and Non-
volatile N-nitroso Compounds,'' Journal of Chromatography, 107, 351
(1975).
2. Fine, D.H., Hoffman, F., Rounbehler, D.P., and Belcher, N.M.
``Analysis of N-nitroso Compounds by Combined High Performance Liquid
Chromatography and Thermal Energy Analysis,'' Walker, E.A., Bogovski, P.
and Griciute, L., Editors, N-nitroso Compounds--Analysis and Formation,
Lyon, International Agency for Research on Cancer (IARC Scientific
Publications No. 14), pp. 43-50 (1976).
3. 40 CFR part 136, appendix B.
4. ``Determination of Nitrosamines in Industrial and Municipal
Wastewaters,'' EPA 600/4-82-016, National Technical Information Service,
PB82-199621, Springfield, Virginia 22161, April 1982.
5. ASTM Annual Book of Standards, Part 31, D3694-78. ``Standard
Practices for Preparation of Sample Containers and for Preservation of
Organic Constituents,'' American Society for Testing and Materials,
Philadelphia.
6. Buglass, A.J., Challis, B.C., and Osborn, M.R. ``Transnitrosation
and Decomposition of Nitrosamines,'' Bogovski, P. and Walker, E.A.,
Editors, N-nitroso Compounds in the Environment, Lyon, International
Agency for Research on Cancer (IARC Scientific Publication No. 9), pp.
94-100 (1974).
7. Burgess, E.M., and Lavanish, J.M. ``Photochemical Decomposition
of N-nitrosamines,'' Tetrahedon Letters, 1221 (1964)
8. Druckrey, H., Preussmann, R., Ivankovic, S., and Schmahl, D.
``Organotrope Carcinogene Wirkungen bei 65 Verschiedenen N-
NitrosoVerbindungen an BD-Ratten,'' Z. Krebsforsch., 69, 103 (1967).
9. Fiddler, W. ``The Occurrence and Determination of N-nitroso
Compounds,'' Toxicol. Appl. Pharmacol., 31, 352 (1975).
10. ``Carcinogens--Working With Carcinogens,'' Department of Health,
Education, and Welfare, Public Health Service, Center for Disease
Control, National Institute for Occupational Safety and Health,
Publication No. 77-206, August 1977.
11. ``OSHA Safety and Health Standards, General Industry,'' (29 CFR
Part 1910), Occupational Safety and Health Administration, OSHA 2206
(Revised, January 1976).
12. ``Safety in Academic Chemistry Laboratories,'' American Chemical
Society Publication, Committee on Chemical Safety, 3rd Edition, 1979.
13. Lijinsky, W. ``How Nitrosamines Cause Cancer,'' New Scientist,
73, 216 (1977).
14. Mirvish, S.S. ``N-Nitroso compounds: Their Chemical and in vivo
Formation and Possible Importance as Environmental Carcinogens,'' J.
Toxicol. Environ. Health, 3, 1267 (1977).
15. ``Reconnaissance of Environmental Levels of Nitrosamines in the
Central United States,'' EPA-330/1-77-001, National Enforcement
Investigations Center, U.S. Environmental Protection Agency (1977).
16. ``Atmospheric Nitrosamine Assessment Report,'' Office of Air
Quality Planning and Standards, U.S. Environmental Protection Agency,
Research Triangle Park, North Carolina (1976).
17. ``Scientific and Technical Assessment Report on Nitrosamines,''
EPA-660/6-7-001, Office of Research and Development, U.S. Environmental
Protection Agency (1976).
18. Provost, L.P., and Elder, R.S. ``Interpretation of Percent
Recovery Data,'' American Laboratory, 15, 58-63 (1983). (The value 2.44
used in the equation in Section 8.3.3 is two times the value of 1.22
derived in this report.)
19. ASTM Annual Book of Standards, Part 31, D3370-76. ``Standard
Practices for Sampling Water,'' American Society for Testing and
Materials, Philadelphia.
20. ``Methods 330.4 (Titrimetric, DPD-FAS) and 330.5
(Spectrophotometric, DPD) for Chlorine, Total Residual,'' Methods for
Chemical Analysis of Water and Wastes, EPA-600/4-79-020, U.S.
Environmental Protection Agency, Environmental Monitoring and Support
Laboratory, Cincinnati, Ohio 45268, March 1979.
21. Burke, J. A. ``Gas Chromatography for Pesticide Residue
Analysis; Some Practical Aspects,'' Journal of the Association of
Official Analytical Chemists, 48, 1037 (1965).
22. ``Method Detection Limit and Analytical Curve Studies EPA
Methods 606, 607, and 608,'' Special letter report for EPA Contract 68-
03-2606, U.S. Environmental Protection Agency, Environmental Monitoring
and Support Laboratory, Cincinnati, Ohio 45268, June 1980.
23. ``EPA Method Study 17 Method 607--Nitrosamines,'' EPA 600/4-84-
051, National Technical Information Service, PB84-207646, Springfield,
Virginia 22161, June 1984.
[[Page 118]]
Table 1--Chromatographic Conditions and Method Detection Limits
------------------------------------------------------------------------
Retention time (min) Method
-------------------------- detection
Parameter limit
Column 1 Column 2 ([micro]g/
L)
------------------------------------------------------------------------
N-Nitrosodimethylamine........... 4.1 0.88 0.15
N-Nitrosodi-n-propylamine........ 12.1 4.2 .46
N-Nitrosodiphenylamine \a\....... \b\ 12.8 \c\ 6.4 .81
------------------------------------------------------------------------
Column 1 conditions: Chromosorb W-AW (80/100 mesh) coated with 10%
Carbowax 20 M/2% KOH packed in a 1.8 m long x 4mm ID glass column with
helium carrier gas at 40 mL/min flow rate. Column temperature held
isothermal at 110 [deg]C, except where otherwise indicated.
Column 2 conditions: Supelcoport (100/120 mesh) coated with 10% SP-2250
packed in a 1.8 m long x 4 mm ID glass column with helium carrier gas
at 40 mL/min flow rate. Column temperature held isothermal at 120
[deg]C, except where otherwise indicated.
\a\ Measured as diphenylamine.
\b\ 220 [deg]C column temperature.
\c\ 210 [deg]C column temperature.
Table 2--QC Acceptance Criteria--Method 607
----------------------------------------------------------------------------------------------------------------
Range for X
Test conc. Limit for s ([micro]g/ Range for
Parameter ([micro]g/ ([micro]g/ L) P, Ps
L) L) (percent)
----------------------------------------------------------------------------------------------------------------
N-Nitrosodimethylamine...................................... 20 3.4 4.6-20.0 13-109
N-Nitrosodiphenyl........................................... 20 6.1 2.1-24.5 D-139
N-Nitrosodi-n-propylamine................................... 20 5.7 11.5-26.8 45-146
----------------------------------------------------------------------------------------------------------------
s=Standard deviation for four recovery measurements, in [micro]g/L (Section 8.2.4).
X=Average recovery for four recovery measurements, in [micro]g/L (Section 8.2.4).
P, Ps=Percent recovery measured (Section 8.3.2, Section 8.4.2).
D=Detected; result must be greater than zero.
Note: These criteria are based directly upon the method performance data in Table 3. Where necessary, the limits
for recovery have been broadened to assure applicability of the limits to concentrations below those used to
develop Table 3.
Table 3--Method Accuracy and Precision as Functions of Concentration--Method 607
----------------------------------------------------------------------------------------------------------------
Accuracy, as Single analyst Overall
Parameter recovery, X' precision, sr' precision, S'
([micro]g/L) ([micro]g/L) ([micro]g/L)
----------------------------------------------------------------------------------------------------------------
N-Nitrosodimethylamine.......................................... 0.37C+0.06 0.25X-0.04 0.25X+0.11
N-Nitrosodiphenylamine.......................................... 0.64C+0.52 0.36X-1.53 0.46X-0.47
N-Nitrosodi-n-propylamine....................................... 0.96C-0.07 0.15X+0.13 0.21X+0.15
----------------------------------------------------------------------------------------------------------------
X'=Expected recovery for one or more measurements of a sample containing a concentration of C, in [micro]g/L.
sr'=Expected single analyst standard deviation of measurements at an average concentration found of X, in
[micro]g/L.
S'=Expected interlaboratory standard deviation of measurements at an average concentration found of X, in
[micro]g/L.
C=True value for the concentration, in [micro]g/L.
X=Average recovery found for measurements of samples containing a concentration of C, in [micro]g/L.
[[Page 119]]
[GRAPHIC] [TIFF OMITTED] TC02JY92.017
[[Page 120]]
[GRAPHIC] [TIFF OMITTED] TC02JY92.018
[[Page 121]]
Method 608--Organochlorine Pesticides and PCBs
1. Scope and Application
1.1 This method covers the determination of certain organochlorine
pesticides and PCBs. The following parameters can be determined by this
method:
------------------------------------------------------------------------
Parameter STORET No. CAS No.
------------------------------------------------------------------------
Aldrin...................................... 39330 309-00-2
[alpha]-BHC................................. 39337 319-84-6
[beta]-BHC.................................. 39338 319-85-7
[delta]-BHC................................. 34259 319-86-8
[gamma]-BHC................................. 39340 58-89-9
Chlordane................................... 39350 57-74-9
4,4'-DDD.................................... 39310 72-54-8
4,4'-DDE.................................... 39320 72-55-9
4,4'-DDT.................................... 39300 50-29-3
Dieldrin.................................... 39380 60-57-1
Endosulfan I................................ 34361 959-98-8
Endosulfan II............................... 34356 33212-65-9
Endosulfan sulfate.......................... 34351 1031-07-8
Eldrin...................................... 39390 72-20-8
Endrin aldehyde............................. 34366 7421-93-4
Heptachlor.................................. 39410 76-44-8
Heptachlor epoxide.......................... 39420 1024-57-3
Toxaphene................................... 39400 8001-35-2
PCB-1016.................................... 34671 12674-11-2
PCB-1221.................................... 39488 1104-28-2
PCB-1232.................................... 39492 11141-16-5
PCB-1242.................................... 39496 53469-21-9
PCB-1248.................................... 39500 12672-29-6
PCB-1254.................................... 39504 11097-69-1
PCB-1260.................................... 39508 11096-82-5
------------------------------------------------------------------------
1.2 This is a gas chromatographic (GC) method applicable to the
determination of the compounds listed above in municipal and industrial
discharges as provided under 40 CFR 136.1. When this method is used to
analyze unfamiliar samples for any or all of the compounds above,
compound identifications should be supported by at least one additional
qualitative technique. This method describes analytical conditions for a
second gas chromatographic column that can be used to confirm
measurements made with the primary column. Method 625 provides gas
chromatograph/mass spectrometer (GC/MS) conditions appropriate for the
qualitative and quantitative confirmation of results for all of the
parameters listed above, using the extract produced by this method.
1.3 The method detection limit (MDL, defined in Section 14.1)\1\ for
each parameter is listed in Table 1. The MDL for a specific wastewater
may differ from those listed, depending upon the nature of interferences
in the sample matrix.
1.4 The sample extraction and concentration steps in this method are
essentially the same as in Methods 606, 609, 611, and 612. Thus, a
single sample may be extracted to measure the parameters included in the
scope of each of these methods. When cleanup is required, the
concentration levels must be high enough to permit selecting aliquots,
as necessary, to apply appropriate cleanup procedures. The analyst is
allowed the latitude, under Section 12, to select chromatographic
conditions appropriate for the simultaneous measurement of combinations
of these parameters.
1.5 Any modification of this method, beyond those expressly
permitted, shall be considered as a major modification subject to
application and approval of alternate test procedures under 40 CFR 136.4
and 136.5.
1.6 This method is restricted to use by or under the supervision of
analysts experienced in the use of a gas chromatograph and in the
interpretation of gas chromatograms. Each analyst must demonstrate the
ability to generate acceptable results with this method using the
procedure described in Section 8.2.
2. Summary of Method
2.1 A measured volume of sample, approximately 1-L, is extracted
with methylene chloride using a separatory funnel. The methylene
chloride extract is dried and exchanged to hexane during concentration
to a volume of 10 mL or less. The extract is separated by gas
chromatography and the parameters are then measured with an electron
capture detector.\2\
2.2 The method provides a Florisil column cleanup procedure and an
elemental sulfur removal procedure to aid in the elimination of
interferences that may be encountered.
3. Interferences
3.1 Method interferences may be caused by contaminants in solvents,
reagents, glassware, and other sample processing hardware that lead to
discrete artifacts and/or elevated baselines in gas chromatograms. All
of these materials must be routinely demonstrated to be free from
interferences under the conditions of the analysis by running laboratory
reagent blanks as described in Section 8.1.3.
3.1.1 Glassware must be scrupulously cleaned.\3\ Clean all glassware
as soon as possible after use by rinsing with the last solvent used in
it. Solvent rinsing should be followed by detergent washing with hot
water, and rinses with tap water and distilled water. The glassware
should then be drained dry, and heated in a muffle furnace at 400 [deg]C
for 15 to 30 min. Some thermally stable materials, such as PCBs, may not
be eliminated by this treatment. Solvent rinses with acetone and
pesticide quality hexane may be substituted for the muffle furnace
heating. Thorough rinsing with such solvents usually eliminates PCB
interference. Volumetric ware should not be heated in a muffle furnace.
After drying and cooling, glassware should be sealed and stored in a
clean environment to prevent any accumulation of dust or other
contaminants. Store inverted or capped with aluminum foil.
[[Page 122]]
3.1.2 The use of high purity reagents and solvents helps to minimize
interference problems. Purification of solvents by distillation in all-
glass systems may be required.
3.2 Interferences by phthalate esters can pose a major problem in
pesticide analysis when using the electron capture detector. These
compounds generally appear in the chromatogram as large late eluting
peaks, especially in the 15 and 50% fractions from Florisil. Common
flexible plastics contain varying amounts of phthalates. These
phthalates are easily extracted or leached from such materials during
laboratory operations. Cross contamination of clean glassware routinely
occurs when plastics are handled during extraction steps, especially
when solvent-wetted surfaces are handled. Interferences from phthalates
can best be minimized by avoiding the use of plastics in the laboratory.
Exhaustive cleanup of reagents and glassware may be required to
eliminate background phthalate contamination.4, 5 The
interferences from phthalate esters can be avoided by using a
microcoulometric or electrolytic conductivity detector.
3.3 Matrix interferences may be caused by contaminants that are co-
extracted from the sample. The extent of matrix interferences will vary
considerably from source to source, depending upon the nature and
diversity of the industrial complex or municipality being sampled. The
cleanup procedures in Section 11 can be used to overcome many of these
interferences, but unique samples may require additional cleanup
approaches to achieve the MDL listed in Table 1.
4. Safety
4.1 The toxicity or carcinogenicity of each reagent used in this
method has not been precisely defined; however, each chemical compound
should be treated as a potential health hazard. From this viewpoint,
exposure to these chemicals must be reduced to the lowest possible level
by whatever means available. The laboratory is responsible for
maintaining a current awareness file of OSHA regulations regarding the
safe handling of the chemicals specified in this method. A reference
file of material data handling sheets should also be made available to
all personnel involved in the chemical analysis. Additional references
to laboratory safety are available and have been identified
6-8 for the information of the analyst.
4.2 The following parameters covered by this method have been
tentatively classified as known or suspected, human or mammalian
carcinogens: 4,4'-DDT, 4,4'-DDD, the BHCs, and the PCBs. Primary
standards of these toxic compounds should be prepared in a hood. A
NIOSH/MESA approved toxic gas respirator should be worn when the analyst
handles high concentrations of these toxic compounds.
5. Apparatus and Materials
5.1 Sampling equipment, for discrete or composite sampling.
5.1.1 Grab sample bottle--1-L or 1-qt, amber glass, fitted with a
screw cap lined with Teflon. Foil may be substituted for Teflon if the
sample is not corrosive. If amber bottles are not available, protect
samples from light. The bottle and cap liner must be washed, rinsed with
acetone or methylene chloride, and dried before use to minimize
contamination.
5.1.2 Automatic sampler (optional)--The sampler must incorporate
glass sample containers for the collection of a minimum of 250 mL of
sample. Sample containers must be kept refrigerated at 4 [deg]C and
protected from light during composting. If the sampler uses a
peristaltic pump, a minimum length of compressible silicone rubber
tubing may be used. Before use, however, the compressible tubing should
be thoroughly rinsed with methanol, followed by repeated rinsings with
distilled water to minimize the potential for contamination of the
sample. An integrating flow meter is required to collect flow
proportional composites.
5.2. Glassware (All specifications are suggested. Catalog numbers
are included for illustration only.):
5.2.1 Separatory funnel--2-L, with Teflon stopcock.
5.2.2 Drying column--Chromatographic column, approximately 400 mm
long x 19 mm ID, with coarse frit filter disc.
5.2.3 Chromatographic column--400 mm long x 22 mm ID, with Teflon
stopcock and coarse frit filter disc (Kontes K-42054 or equivalent).
5.2.4 Concentrator tube, Kuderna-Danish--10-mL, graduated (Kontes K-
570050-1025 or equivalent). Calibration must be checked at the volumes
employed in the test. Ground glass stopper is used to prevent
evaporation of extracts.
5.2.5 Evaporative flask, Kuderna-Danish--500-mL (Kontes K-570001-
0500 or equivalent). Attach to concentrator tube with springs.
5.2.6 Snyder column, Kuderna/Danish--Three-ball macro (Kontes K-
503000-0121 or equivalent).
5.2.7 Vials--10 to 15-mL, amber glass, with Teflon-lined screw cap.
5.3 Boiling chips--Approximately 10/40 mesh. Heat to 400 [deg]C for
30 min or Soxhlet extract with methylene chloride.
5.4 Water bath--Heated, with concentric ring cover, capable of
temperature control (2 [deg]C). The bath should be
used in a hood.
5.5 Balance--Analytical, capable of accurately weighing 0.0001 g.
5.6 Gas chromatograph--An analytical system complete with gas
chromatograph suitable for on-column injection and all required
accessories including syringes, analytical columns, gases, detector, and
strip-
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chart recorder. A data system is recommended for measuring peak areas.
5.6.1 Column 1--1.8 m long x 4 mm ID glass, packed with 1.5% SP-
2250/1.95% SP-2401 on Supelcoport (100/120 mesh) or equivalent. This
column was used to develop the method performance statements in Section
14. Guidelines for the use of alternate column packings are provided in
Section 12.1.
5.6.2 Column 2--1.8 m long x 4 mm ID glass, packed with 3% OV-1 on
Supelcoport (100/120 mesh) or equivalent.
5.6.3 Detector--Electron capture detector. This detector has proven
effective in the analysis of wastewaters for the parameters listed in
the scope (Section 1.1), and was used to develop the method performance
statements in Section 14. Guidelines for the use of alternate detectors
are provided in Section 12.1.
6. Reagents
6.1 Reagent water--Reagent water is defined as a water in which an
interferent is not observed at the MDL of the parameters of interest.
6.2 Sodium hydroxide solution (10 N)--Dissolve 40 g of NaOH (ACS) in
reagent water and dilute to 100 mL.
6.3 Sodium thiosulfate--(ACS) Granular.
6.4 Sulfuric acid (1+1)--Slowly, add 50 mL to
H2SO4 (ACS, sp. gr. 1.84) to 50 mL of reagent
water.
6.5 Acetone, hexane, isooctane, methylene chloride--Pesticide
quality or equivalent.
6.6 Ethyl ether--Nanograde, redistilled in glass if necessary.
6.6.1 Ethyl ether must be shown to be free of peroxides before it is
used as indicated by EM Laboratories Quant test strips. (Available from
Scientific Products Co., Cat. No. P1126-8, and other suppliers.)
6.6.2 Procedures recommended for removal of peroxides are provided
with the test strips. After cleanup, 20 mL of ethyl alcohol preservative
must be added to each liter of ether.
6.7 Sodium sulfate--(ACS) Granular, anhydrous. Purify by heating at
400 [deg]C for 4 h in a shallow tray.
6.8 Florisil--PR grade (60/100 mesh). Purchase activated at 1250
[deg]F and store in the dark in glass containers with ground glass
stoppers or foil-lined screw caps. Before use, activate each batch at
least 16 h at 130 [deg]C in a foil-covered glass container and allow to
cool.
6.9 Mercury--Triple distilled.
6.10 Copper powder--Activated.
6.11 Stock standard solutions (1.00 [micro]g/[micro]L)--Stock
standard solutions can be prepared from pure standard materials or
purchased as certified solutions.
6.11.1 Prepare stock standard solutions by accurately weighing about
0.0100 g of pure material. Dissolve the material in isooctane and dilute
to volume in a 10-mL volumetric flask. Larger volumes can be used at the
convenience of the analyst. When compound purity is assayed to be 96% or
greater, the weight can be used without correction to calculate the
concentration of the stock standard. Commercially prepared stock
standards can be used at any concentration if they are certified by the
manufacturer or by an independent source.
6.11.2 Transfer the stock standard solutions into Teflon-sealed
screw-cap bottles. Store at 4 [deg]C and protect from light. Stock
standard solutions should be checked frequently for signs of degradation
or evaporation, especially just prior to preparing calibration standards
from them.
6.11.3 Stock standard solutions must be replaced after six months,
or sooner if comparison with check standards indicates a problem.
6.12 Quality control check sample concentrate--See Section 8.2.1.
7. Calibration
7.1 Establish gas chromatographic operating conditions equivalent to
those given in Table 1. The gas chromatographic system can be calibrated
using the external standard technique (Section 7.2) or the internal
standard technique (Section 7.3).
7.2 External standard calibration procedure:
7.2.1 Prepare calibration standards at a minimum of three
concentration levels for each parameter of interest by adding volumes of
one or more stock standards to a volumetric flask and diluting to volume
with isooctane. One of the external standards should be at a
concentration near, but above, the MDL (Table 1) and the other
concentrations should correspond to the expected range of concentrations
found in real samples or should define the working range of the
detector.
7.2.2 Using injections of 2 to 5 [micro]L, analyze each calibration
standard according to Section 12 and tabulate peak height or area
responses against the mass injected. The results can be used to prepare
a calibration curve for each compound. Alternatively, if the ratio of
response to amount injected (calibration factor) is a constant over the
working range (<10% relative standard deviation, RSD), linearity through
the origin can be assumed and the average ratio or calibration factor
can be used in place of a calibration curve.
7.3 Internal standard calibration procedure--To use this approach,
the analyst must select one or more internal standards that are similar
in analytical behavior to the compounds of interest. The analyst must
further demonstrate that the measurement of the internal standard is not
affected by method or matrix interferences. Because of these
limitations, no internal standard can
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be suggested that is applicable to all samples.
7.3.1 Prepare calibration standards at a minimum of three
concentration levels for each parameter of interest by adding volumes of
one or more stock standards to a volumetric flask. To each calibration
standard, add a known constant amount of one or more internal standards,
and dilute to volume with isooctane. One of the standards should be at a
concentration near, but above, the MDL and the other concentrations
should correspond to the expected range of concentrations found in real
samples or should define the working range of the detector.
7.3.2 Using injections of 2 to 5 [micro]L, analyze each calibration
standard according to Section 12 and tabulate peak height or area
responses against concentration for each compound and internal standard.
Calculate response factors (RF) for each compound using Equation 1.
[GRAPHIC] [TIFF OMITTED] TC15NO91.107
Equation 1
where:
As=Response for the parameter to be measured.
Ais=Response for the internal standard.
Cis=Concentration of the internal standard ([micro]g/L).
Cs=Concentraton of the parameter to be measured ([micro]g/L).
If the RF value over the working range is a constant (<10% RSD), the
RF can be assumed to be invariant and the average RF can be used for
calculations. Alternatively, the results can be used to plot a
calibration curve of response ratios, As/Ais, vs.
RF.
7.4 The working calibration curve, calibration factor, or RF must be
verified on each working day by the measurement of one or more
calibration standards. If the response for any parameter varies from the
predicted response by more than 15%, the test must
be repeated using a fresh calibration standard. Alternatively, a new
calibration curve must be prepared for that compound.
7.5 The cleanup procedure in Section 11 utilizes Florisil column
chromatography. Florisil from different batches or sources may vary in
adsorptive capacity. To standardize the amount of Florisil which is
used, the use of lauric acid value \9\ is suggested. The referenced
procedure determines the adsorption from hexane solution of lauric acid
(mg) per g of Florisil. The amount of Florisil to be used for each
column is calculated by dividing 110 by this ratio and multiplying by 20
g.
7.6 Before using any cleanup procedure, the analyst must process a
series of calibration standards through the procedure to validate
elution patterns and the absence of interferences from the reagents.
8. Quality Control
8.1 Each laboratory that uses this method is required to operate a
formal quality control program. The minimum requirements of this program
consist of an initial demonstration of laboratory capability and an
ongoing analysis of spiked samples to evaluate and document data
quality. The laboratory must maintain records to document the quality of
data that is generated. Ongoing data quality checks are compared with
established performance criteria to determine if the results of analyses
meet the performance characteristics of the method. When results of
sample spikes indicate atypical method performance, a quality control
check standard must be analyzed to confirm that the measurements were
performed in an in-control mode of operation.
8.1.1 The analyst must make an initial, one-time, demonstration of
the ability to generate acceptable accuracy and precision with this
method. This ability is established as described in Section 8.2.
8.1.2 In recognition of advances that are occurring in
chromatography, the analyst is permitted certain options (detailed in
Sections 10.4, 11.1, and 12.1) to improve the separations or lower the
cost of measurements. Each time such a modification is made to the
method, the analyst is required to repeat the procedure in Section 8.2.
8.1.3 Before processing any samples, the analyst must analyze a
reagent water blank to demonstrate that interferences from the
analytical system and glassware are under control. Each time a set of
samples is extracted or reagents are changed, a reagent water blank must
be processed as a safeguard against laboratory contamination.
8.1.4 The laboratory must, on an ongoing basis, spike and analyze a
minimum of 10% of all samples to monitor and evaluate laboratory data
quality. This procedure is described in Section 8.3.
8.1.5 The laboratory must, on an ongoing basis, demonstrate through
the analyses of quality control check standards that the operation of
the measurement system is in control. This procedure is described in
Section 8.4. The frequency of the check standard analyses is equivalent
to 10% of all samples analyzed but may be reduced if spike recoveries
from samples (Section 8.3) meet all specified quality control criteria.
8.1.6 The laboratory must maintain performance records to document
the quality of data that is generated. This procedure is described in
Section 8.5.
8.2 To establish the ability to generate acceptable accuracy and
precision, the analyst must perform the following operations.
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8.2.1 A quality control (QC) check sample concentrate is required
containing each single-component parameter of interest at the following
concentrations in acetone: 4,4'-DDD, 10 [micro]g/mL; 4,4'-DDT, 10
[micro]g/mL; endosulfan II, 10 [micro]g/mL; endosulfan sulfate, 10
[micro]g/mL; endrin, 10 [micro]g/mL; any other single-component
pesticide, 2 [micro]g/mL. If this method is only to be used to analyze
for PCBs, chlordane, or toxaphene, the QC check sample concentrate
should contain the most representative multicomponent parameter at a
concentration of 50 [micro]g/mL in acetone. The QC check sample
concentrate must be obtained from the U.S. Environmental Protection
Agency, Environmental Monitoring and Support Laboratory in Cincinnati,
Ohio, if available. If not available from that source, the QC check
sample concentrate must be obtained from another external source. If not
available from either source above, the QC check sample concentrate must
be prepared by the laboratory using stock standards prepared
independently from those used for calibration.
8.2.2 Using a pipet, prepare QC check samples at the test
concentrations shown in Table 3 by adding 1.00 mL of QC check sample
concentrate to each of four 1-L aliquots of reagent water.
8.2.3 Analyze the well-mixed QC check samples according to the
method beginning in Section 10.
8.2.4 Calculate the average recovery (X) in [micro]g/mL; and the
standard deviation of the recovery (s) in [micro]g/mL, for each
parameter using the four results.
8.2.5 For each parameter compare s and X with the corresponding
acceptance criteria for precision and accuracy, respectively, found in
Table 3. If s and X for all parameters of interest meet the acceptance
criteria, the system performance is acceptable and analysis of actual
samples can begin. If any individual s exceeds the precision limit or
any individual X falls outside the range for accuracy, the system
performance is unacceptable for that parameter.
Note: The large number of parameters in Table 3 present a
substantial probability that one or more will fail at least one of the
acceptance criteria when all parameters are analyzed.
8.2.6 When one or more of the parameters tested fail at least one of
the acceptance criteria, the analyst must proceed according to Section
8.2.6.1 or 8.2.6.2.
8.2.6.1 Locate and correct the source of the problem and repeat the
test for all parameters of interest beginning with Section 8.2.2.
8.2.6.2 Beginning with Section 8.2.2, repeat the test only for those
parameters that failed to meet criteria. Repeated failure, however, will
confirm a general problem with the measurement system. If this occurs,
locate and correct the source of the problem and repeat the test for all
compmunds of interest beginning with Section 8.2.2.
8.3 The laboratory must, on an ongoing basis, spike at least 10% of
the samples from each sample site being monitored to assess accuracy.
For laboratories analyzing one to ten samples per month, at least one
spiked sample per month is required.
8.3.1 The concentration of the spike in the sample should be
determined as follows:
8.3.1.1 If, as in compliance monitoring, the concentration of a
specific parameter in the sample is being checked against a regulatory
concentration limit, the spike should be at that limit or 1 to 5 times
higher than the background concentration determined in Section 8.3.2,
whichever concentration would be larger.
8.3.1.2 If the concentration of a specific parameter in the sample
is not being checked against a limit specific to that parameter, the
spike should be at the test concentration in Section 8.2.2 or 1 to 5
times higher than the background concentration determined in Section
8.3.2, whichever concentration would be larger.
8.3.1.3 If it is impractical to determine background levels before
spiking (e.g., maximum holding times will be exceeded), the spike
concentration should be (1) the regulatory concentration limit, if any;
or, if none (2) the larger of either 5 times higher than the expected
background concentration or the test concentration in Section 8.2.2.
8.3.2 Analyze one sample aliquot to determine the background
concentration (B) of each parameter. If necessary, prepare a new QC
check sample concentrate (Section 8.2.1) appropriate for the background
concentrations in the sample. Spike a second sample aliquot with 1.0 mL
of the QC check sample concentrate and analyze it to determine the
concentration after spiking (A) of each parameter. Calculate each
percent recovery (P) as 100(A-B)%/T, where T is the known true value of
the spike.
8.3.3 Compare the percent recovery (P) for each parameter with the
corresponding QC acceptance criteria found in Table 3. These acceptance
criteria were calculated to include an allowance for error in
measurement of both the background and spike concentrations, assuming a
spike to background ratio of 5:1. This error will be accounted for to
the extent that the analyst's spike to background ratio approaches
5:1.\10\ If spiking was performed at a concentration lower than the test
concentration in Section 8.2.2, the analyst must use either the QC
acceptance criteria in Table 3, or optional QC acceptance criteria
calculated for the specific spike concentration. To calculate optional
acceptance criteria for the recovery of a parameter: (1) Calculate
accuracy (X') using the equation in Table 4, substituting the spike
concentration (T) for C; (2) calculate overall precision (S') using the
equation in Table 4, substituting X'
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for X; (3) calculate the range for recovery at the spike concentration
as (100 X'/T)2.44(100 S'/T)%.\10\
8.3.4 If any individual P falls outside the designated range for
recovery, that parameter has failed the acceptance criteria. A check
standard containing each parameter that failed the criteria must be
analyzed as described in Section 8.4.
8.4 If any parameter fails the acceptance criteria for recovery in
Section 8.3, a QC check standard containing each parameter that failed
must be prepared and analyzed.
Note: The frequency for the required analysis of a QC check standard
will depend upon the number of parameters being simultaneously tested,
the complexity of the sample matrix, and the performance of the
laboratory. If the entire list of parameters in Table 3 must be measured
in the sample in Section 8.3, the probability that the analysis of a QC
check standard will be required is high. In this case the QC check
standard should be routinely analyzed with the spike sample.
8.4.1 Prepare the QC check standard by adding 1.0 mL of QC check
sample concentrate (Section 8.2.1 or 8.3.2) to 1 L of reagent water. The
QC check standard needs only to contain the parameters that failed
criteria in the test in Section 8.3.
8.4.2 Analyze the QC check standards to determine the concentration
measured (A) of each parameter. Calculate each percent recovery
(Ps) as 100 (A/T)%, where T is the true value of the standard
concentration.
8.4.3 Compare the percent recovery (Ps) for each
parameter with the corresponding QC acceptance criteria found in Table
3. Only parameters that failed the test in Section 8.3 need to be
compared with these criteria. If the recovery of any such parameter
falls outside the designated range, the laboratory performance for that
parameter is judged to be out of control, and the problem must be
immediately identified and corrected. The analytical result for that
parameter in the unspiked sample is suspect and may not be reported for
regulatory compliance purposes.
8.5 As part of the QC program for the laboratory, method accuracy
for wastewater samples must be assessed and records must be maintained.
After the analysis of five spiked wastewater samples as in Section 8.3,
calculate the average percent recovery (P) and the standard deviation of
the percent recovery (sp). Express the accuracy assessment as
a percent recovery interval from P-2 sp to P+2 sp.
If P=90% and sp=10%, for example, the accuracy interval is
expressed as 70-110%. Update the accuracy assessment for each parameter
on a regular basis (e.g. after each five to ten new accuracy
measurements).
8.6 It is recommended that the laboratory adopt additional quality
assurance practices for use with this method. The specific practices
that are most productive depend upon the needs of the laboratory and the
nature of the samples. Field duplicates may be analyzed to assess the
precision of the environmental measurements. When doubt exists over the
identification of a peak on the chromatogram, confirmatory techniques
such as gas chromatography with a dissimilar column, specific element
detector, or mass spectrometer must be used. Whenever possible, the
laboratory should analyze standard reference materials and participate
in relevant performance evaluation studies.
9. Sample Collection, Preservation, and Handling
9.1 Grab samples must be collected in glass containers. Conventional
sampling practices \11\ should be followed, except that the bottle must
not be prerinsed with sample before collection. Composite samples should
be collected in refrigerated glass containers in accordance with the
requirements of the program. Automatic sampling equipment must be as
free as possible of Tygon tubing and other potential sources of
contamination.
9.2 All samples must be iced or refrigerated at 4 [deg]C from the
time of collection until extraction. If the samples will not be
extracted within 72 h of collection, the sample should be adjusted to a
pH range of 5.0 to 9.0 with sodium hydroxide solution or sulfuric acid.
Record the volume of acid or base used. If aldrin is to be determined,
add sodium thiosulfate when residual chlorine is present. EPA Methods
330.4 and 330.5 may be used for measurement of residual chlorine.\12\
Field test kits are available for this purpose.
9.3 All samples must be extracted within 7 days of collection and
completely analyzed within 40 days of extraction.\2\
10. Sample Extraction
10.1 Mark the water meniscus on the side of the sample bottle for
later determination of sample volume. Pour the entire sample into a 2-L
separatory funnel.
10.2 Add 60 mL of methylene chloride to the sample bottle, seal, and
shake 30 s to rinse the inner surface. Transfer the solvent to the
separatory funnel and extract the sample by shaking the funnel for 2
min. with periodic venting to release excess pressure. Allow the organic
layer to separate from the water phase for a minimum of 10 min. If the
emulsion interface between layers is more than one-third the volume of
the solvent layer, the analyst must employ mechanical techniques to
complete the phase separation. The optium technique depends upon the
sample, but may include stirring, filtration of the emulsion through
glass wool, centrifugation, or other physical methods. Collect the
methylene chloride extract in a 250-mL Erlenmeyer flask.
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10.3 Add a second 60-mL volume of methylene chloride to the sample
bottle and repeat the extraction procedure a second time, combining the
extracts in the Erlenmeyer flask. Perform a third extraction in the same
manner.
10.4 Assemble a Kuderna-Danish (K-D) concentrator by attaching a 10-
mL concentrator tube to a 500-mL evaporative flask. Other concentration
devices or techniques may be used in place of the K-D concentrator if
the requirements of Section 8.2 are met.
10.5 Pour the combined extract through a solvent-rinsed drying
column containing about 10 cm of anhydrous sodium sulfate, and collect
the extract in the K-D concentrator. Rinse the Erlenmeyer flask and
column with 20 to 30 mL of methylene chloride to complete the
quantitative transfer.
10.6 Add one or two clean boiling chips to the evaporative flask and
attach a three-ball Snyder column. Prewet the Snyder column by adding
about 1 mL of methylene chloride to the top. Place the K-D apparatus on
a hot water bath (60 to 65 [deg]C) so that the concentrator tube is
partially immersed in the hot water, and the entire lower rounded
surface of the flask is bathed with hot vapor. Adjust the vertical
position of the apparatus and the water temperature as required to
complete the concentration in 15 to 20 min. At the proper rate of
distillation the balls of the column will actively chatter but the
chambers will not flood with condensed solvent. When the apparent volume
of liquid reaches 1 mL, remove the K-D apparatus and allow it to drain
and cool for at least 10 min.
10.7 Increase the temperature of the hot water bath to about 80
[deg]C. Momeltarily remove the Snyder column, add 50 mL of hexane and a
new boiling chip, and reattach the Snyder column. Concentrate the
extract as in Section 10.6, except use hexane to prewet the column. The
elapsed time of concentration should be 5 to 10 min.
10.8 Remove the Snyder column and rinse the flask and its lower
joint into the concentrator tube with 1 to 2 mL of hexane. A 5-mL
syringe is recommended for this operation. Stopper the concentrator tube
and store refrigerated if further processing will not be performed
immediately. If the extract will be stored longer than two days, it
should be transferred to a Teflon-sealed screw-cap vial. If the sample
extract requires no further cleanup, proceed with gas chroma tographic
analysis (Section 12). If the sample requires further cleanup, proceed
to Sec tion 11.
10.9 Determine the original sample volume by refilling the sample
bottle to the mark and transferring the liquid to a 1000-mL graduated
cylinder. Record the sample volume to the nearest 5 mL.
11. Cleanup and Separation
11.1 Cleanup procedures may not be necessary for a relatively clean
sample matrix. If particular circumstances demand the use of a cleanup
procedure, the analyst may use either procedure below or any other
appropriate procedure. However, the analyst first must demonstrate that
the requirements of Section 8.2 can be met using the method as revised
to incorporate the cleanup procedure. The Florisil column allows for a
select fractionation of the compounds and will eliminate polar
interferences. Elemental sulfur, which interferes with the electron
capture gas chromatography of certain pesticides, can be removed by the
technique described in Section 11.3.
11.2 Florisil column cleanup:
11.2.1 Place a weight of Florisil (nominally 20 g) predetermined by
calibration (Section 7.5), into a chromatographic column. Tap the column
to settle the Florisil and add 1 to 2 cm of anhydrous sodium sulfate to
the top.
11.2.2 Add 60 mL of hexane to wet and rinse the sodium sulfate and
Florisil. Just prior to exposure of the sodium sulfate layer to the air,
stop the elution of the hexane by closing the stopcock on the
chromatographic column. Discard the eluate.
11.2.3 Adjust the sample extract volume to 10 mL with hexane and
transfer it from the K-D concentrator tube onto the column. Rinse the
tube twice with 1 to 2 mL of hexane, adding each rinse to the column.
11.2.4 Place a 500-mL K-D flask and clean concentrator tube under
the chroma tographic column. Drain the column into the flask until the
sodium sulfate layer is nearly exposed. Elute the column with 200 mL of
6% ethyl ether in hexane (V/V) (Fraction 1) at a rate of about 5 mL/min.
Remove the K-D flask and set it aside for later concentration. Elute the
column again, using 200 mL of 15% ethyl ether in hexane (V/V) (Fraction
2), into a second K-D flask. Perform the third elution using 200 mL of
50% ethyl ether in hexane (V/V) (Fraction 3). The elution patterns for
the pesticides and PCBs are shown in Table 2.
11.2.5 Concentrate the fractions as in Section 10.6, except use
hexane to prewet the column and set the water bath at about 85 [deg]C.
When the apparatus is cool, remove the Snyder column and rinse the flask
and its lower joint into the concentrator tube with hexane. Adjust the
volume of each fraction to 10 mL with hexane and analyze by gas
chromatography (Section 12).
11.3 Elemental sulfur will usually elute entirely in Fraction 1 of
the Florisil column cleanup. To remove sulfur interference from this
fraction or the original extract, pipet 1.00 mL of the concentrated
extract into a clean concentrator tube or Teflon-sealed vial. Add one to
three drops of mercury and seal.\13\ Agitate the contents of the vial
for 15 to 30 s. Prolonged shaking (2 h) may be required. If so, this may
be accomplished with a reciprocal shaker. Alternatively, activated
[[Page 128]]
copper powder may be used for sulfur removal.\14\ Analyze by gas
chromatography.
12. Gas Chromatography
12.1 Table 1 summarizes the recommended operating conditions for the
gas chromatograph. Included in this table are retention times and MDL
that can be achieved under these conditions. Examples of the separations
achieved by Column 1 are shown in Figures 1 to 10. Other packed or
capillary (open-tubular) columns, chromatographic conditions, or
detectors may be used if the requirements of Section 8.2 are met.
12.2 Calibrate the system daily as described in Section 7.
12.3 If the internal standard calibration procedure is being used,
the internal standard must be added to the sample extract and mixed
thoroughly immediately before injection into the gas chromatograph.
12.4 Inject 2 to 5 [micro]L of the sample extract or standard into
the gas chromatograph using the solvent-flush technique.\15\ Smaller
(1.0 uL) volumes may be injected if automatic devices are employed.
Record the volume injected to the nearest 0.05 [micro]L, the total
extract volume, and the resulting peak size in area or peak height
units.
12.5 Identify the parameters in the sample by comparing the
retention times of the peaks in the sample chromatogram with those of
the peaks in standard chromatograms. The width of the retention time
window used to make identifications should be based upon measurements of
actual retention time variations of standards over the course of a day.
Three times the standard deviation of a retention time for a compound
can be used to calculate a suggested window size; however, the
experience of the analyst should weigh heavily in the interpretation of
chromatograms.
12.6 If the response for a peak exceeds the working range of the
system, dilute the extract and reanalyze.
12.7 If the measurement of the peak response is prevented by the
presence of interferences, further cleanup is required.
13. Calculations
13.1 Determine the concentration of individual compounds in the
sample.
13.1.1 If the external standard calibration procedure is used,
calculate the amount of material injected from the peak response using
the calibration curve or calibration factor determined in Section 7.2.2.
The concentration in the sample can be calculated from Equation 2.
[GRAPHIC] [TIFF OMITTED] TC15NO91.108
Equation 2
where:
A=Amount of material injected (ng).
Vi=Volume of extract injected ([micro]L).
Vt=Volume of total extract ([micro]L).
Vs=Volume of water extracted (mL).
13.1.2 If the internal standard calibration procedure is used,
calculate the concentration in the sample using the response factor (RF)
determined in Section 7.3.2 and Equation 3.
[GRAPHIC] [TIFF OMITTED] TC15NO91.109
Equation 3
where:
As=Response for the parameter to be measured.
Ais=Response for the internal standard.
Is=Amount of internal standard added to each extract
([micro]g).
Vo=Volume of water extracted (L).
13.2 When it is apparent that two or more PCB (Aroclor) mixtures are
present, the Webb and McCall procedure \16\ may be used to identify and
quantify the Aroclors.
13.3 For multicomponent mixtures (chlordane, toxaphene, and PCBs)
match retention times of peaks in the standards with peaks in the
sample. Quantitate every identifiable peak unless interference with
individual peaks persist after cleanup. Add peak height or peak area of
each identified peak in the chromatogram. Calculate as total response in
the sample versus total response in the standard.
13.4 Report results in [micro]g/L without correction for recovery
data. All QC data obtained should be reported with the sample results.
14. Method Performance
14.1 The method detection limit (MDL) is defined as the minimum
concentration of a substance that can be measured and reported with 99%
confidence that the value is above zero.\1\ The MDL concentrations
listed in Table 1 were obtained using reagent water.\17\ Similar results
were achieved using representative wastewaters. The MDL actually
achieved in a given analysis will vary depending on instrument
sensitivity and matrix effects.
14.2 This method has been tested for linearity of spike recovery
from reagent water and has been demonstrated to be applicable over the
concentration range from 4xMDL to 1000xMDL with the following
exceptions: Chlordane recovery at 4xMDL was low (60%); Toxaphene
recovery was demonstrated linear over the range of 10xMDL to
1000xMDL.\17\
14.3 This method was tested by 20 laboratories using reagent water,
drinking water, surface water, and three industrial
[[Page 129]]
wastewaters spiked at six concentrations.\18\ Concentrations used in the
study ranged from 0.5 to 30 [micro]g/L for single-component pesticides
and from 8.5 to 400 [micro]g/L for multicomponent parameters. Single
operator precision, overall precision, and method accuracy were found to
be directly related to the concentration of the parameter and
essentially independent of the sample matrix. Linear equations to
describe these relationships are presented in Table 4.
References
1. 40 CFR part 136, appendix B.
2. ``Determination of Pesticides and PCBs in Industrial and
Municipal Wastewaters,'' EPA 600/4-82-023, National Technical
Information Service, PB82-214222, Springfield, Virginia 22161, April
1982.
3. ASTM Annual Book of Standards, Part 31, D3694-78. ``Standard
Practices for Preparation of Sample Containers and for Preservation of
Organic Constituents,'' American Society for Testing and Materials,
Philadelphia.
4. Giam, C.S., Chan, H.S., and Nef, G.S., ``Sensitive Method for
Determination of Phthalate Ester Plasticizers in Open-Ocean Biota
Samples,'' Analytical Chemistry, 47, 2225 (1975).
5. Giam, C.S., Chan, H.S. ``Control of Blanks in the Analysis of
Phthalates in Air and Ocean Biota Samples,'' U.S. National Bureau of
Standards, Special Publication 442, pp. 701-708, 1976.
6. ``Carcinogens--Working With Carcinogens,'' Department of Health,
Education, and Welfare, Public Health Service, Center for Disease
Control, National Institute for Occupational Safety and Health,
Publication No. 77-206, August 1977.
7. ``OSHA Safety and Health Standards, General Industry,'' (29 CFR
part 1910), Occupational Safety and Health Administration, OSHA 2206
(Revised, January 1976).
8. ``Safety in Academic Chemistry Laboratories,'' American Chemical
Society Publication, Committee on Chemical Safety, 3rd Edition, 1979.
9. Mills, P.A. ``Variation of Florisil Activity: Simple Method for
Measuring Absorbent Capacity and Its Use in Standardizing Florisil
Columns,'' Journal of the Association of Official Analytical Chemists,
51, 29, (1968).
10. Provost, L.P., and Elder, R.S. ``Interpretation of Percent
Recovery Data,'' American Laboratory, 15, 58-63 (1983). (The value 2.44
used in the equation in Section 8.3.3 is two times the value 1.22
derived in this report.)
11. ASTM Annual Book of Standards, Part 31, D3370-76. ``Standard
Practices for Sampling Water,'' American Society for Testing and
Materials, Philadelphia.
12. ``Methods 330.4 (Titrimetric, DPD-FAS) and 330.5
(Spectrophotometric, DPD) for Chlorine, Total Residual,'' Methods for
Chemical Analysis of Water and Wastes, EPA-600/4-79-020, U.S.
Environmental Protection Agency, Environmental Monitoring and Support
Laboratory, Cincinnati, Ohio 45268, March 1979.
13. Goerlitz, D.F., and Law, L.M. Bulletin for Environmental
Contamination and Toxicology, 6, 9 (1971).
14. ``Manual of Analytical Methods for the Analysis of Pesticides in
Human and Environmental Samples,'' EPA-600/8-80-038, U.S. Environmental
Protection Agency, Health Effects Research Laboratory, Research Triangle
Park, North Carolina.
15. Burke, J.A. ``Gas Chromatography for Pesticide Residue Analysis;
Some Practical Aspects,'' Journal of the Association of Official
Analytical Chemists, 48, 1037 (1965).
16. Webb, R.G., and McCall, A.C. ``Quantitative PCB Standards for
Election Capture Gas Chromatography,'' Journal of Chromatographic
Science, 11, 366 (1973).
17. ``Method Detection Limit and Analytical Curve Studies, EPA
Methods 606, 607, and 608,'' Special letter report for EPA Contract 68-
03-2606, U.S. Environmental Protection Agency, Environmental Monitoring
and Support Laboratory, Cincinnati, Ohio 45268, June 1980.
18. ``EPA Method Study 18 Method 608--Organochlorine Pesticides and
PCBs,'' EPA 600/4-84-061, National Technical Information Service, PB84-
211358, Springfield, Virginia 22161, June 1984.
Table 1--Chromatographic Conditions and Method Detection Limits
------------------------------------------------------------------------
Retention time (min) Method
-------------------------- detection
Parameter limit
Col. 1 Col. 2 ([micro]g/L)
------------------------------------------------------------------------
[alpha]-BHC.................... 1.35 1.82 0.003
[gamma]-BHC.................... 1.70 2.13 0.004
[beta]-BHC..................... 1.90 1.97 0.006
Heptachlor..................... 2.00 3.35 0.003
[delta]-BHC.................... 2.15 2.20 0.009
Aldrin......................... 2.40 4.10 0.004
Heptachlor epoxide............. 3.50 5.00 0.083
Endosulfan I................... 4.50 6.20 0.014
4,4'-DDE....................... 5.13 7.15 0.004
Dieldrin....................... 5.45 7.23 0.002
Endrin......................... 6.55 8.10 0.006
[[Page 130]]
4,4'-DDD....................... 7.83 9.08 0.011
Endosulfan II.................. 8.00 8.28 0.004
4,4'-DDT....................... 9.40 11.75 0.012
Endrin aldehyde................ 11.82 9.30 0.023
Endosulfan sulfate............. 14.22 10.70 0.066
Chlordane...................... mr mr 0.014
Toxaphene...................... mr mr 0.24
PCB-1016....................... mr mr nd
PCB-1221....................... mr mr nd
PCB-1232....................... mt mr nd
PCB-1242....................... mr mr 0.065
PCB-1248....................... mr mr nd
PCB-1254....................... mr mr nd
PCB-1260....................... mr mr nd
------------------------------------------------------------------------
AColumn 1 conditions: Supelcoport (100/120 mesh) coated with 1.5% SP-
2250/1.95% SP-2401 packed in a 1.8 m long x 4 mm ID glass column with
5% methane/95% argon carrier gas at 60 mL/min flow rate. Column
temperature held isothermal at 200 [deg]C, except for PCB-1016 through
PCB-1248, should be measured at 160 [deg]C.
AColumn 2 conditions: Supelcoport (100/120 mesh) coated with 3% OV-1
packed in a 1.8 m long x 4 mm ID glass column with 5% methane/95%
argon carrier gas at 60 mL/min flow rate. Column temperature held
isothermal at 200 [deg]C for the pesticides; at 140 [deg]C for PCB-
1221 and 1232; and at 170 [deg]C for PCB-1016 and 1242 to 1268.
Amr=Multiple peak response. See Figures 2 thru 10.
And=Not determined.
Table 2--Distribution of Chlorinated Pesticides and PCBs into Florisil
Column Fractions 2
------------------------------------------------------------------------
Percent recovery by fraction \a\
Parameter --------------------------------------
1 2 3
------------------------------------------------------------------------
Aldrin........................... 100 ........... ...........
[alpha]-BHC...................... 100 ........... ...........
[beta]-BHC....................... 97 ........... ...........
[delta]-BHC...................... 98 ........... ...........
[gamma]-BHC...................... 100 ........... ...........
Chlordane........................ 100 ........... ...........
4,4'-DDD......................... 99 ........... ...........
4,4'-DDE......................... 98 ........... ...........
4,4'-DDT......................... 100 ........... ...........
Dieldrin......................... 0 100 ...........
Endosulfan I..................... 37 64 ...........
Endosulfan II.................... 0 7 91
Endosulfan sulfate............... 0 0 106
Endrin........................... 4 96 ...........
Endrin aldehyde.................. 0 68 26
Heptachlor....................... 100 ........... ...........
Heptachlor epoxide............... 100 ........... ...........
Toxaphene........................ 96 ........... ...........
PCB-1016......................... 97 ........... ...........
PCB-1221......................... 97 ........... ...........
PCB-1232......................... 95 4 ...........
PCB-1242......................... 97 ........... ...........
PCB-1248......................... 103 ........... ...........
PCB-1254......................... 90 ........... ...........
PCB-1260......................... 95 ........... ...........
------------------------------------------------------------------------
\a\ Eluant composition:
Fraction 1-6% ethyl ether in hexane.
Fraction 2-15% ethyl ether in hexane.
Fraction 3-50% ethyl ether in hexane.
Table 3--QC Acceptance Criteria--Method 608
----------------------------------------------------------------------------------------------------------------
Range for
Test conc. Limit for s X Range for
Parameter ([micro]g/ ([micro]g/L) ([micro]g/ P, Ps(%)
L) L)
----------------------------------------------------------------------------------------------------------------
Aldrin...................................................... 2.0 0.42 1.08-2.24 42-122
[alpha]-BHC................................................. 2.0 0.48 0.98-2.44 37-134
[beta]-BHC.................................................. 2.0 0.64 0.78-2.60 17-147
[delta]-BHC................................................. 2.0 0.72 1.01-2.37 19-140
[gamma]-BHC................................................. 2.0 0.46 0.86-2.32 32-127
[[Page 131]]
Chlordane................................................... 50 10.0 27.6-54.3 45-119
4,4 '-DDD................................................... 10 2.8 4.8-12.6 31-141
4,4 '-DDE................................................... 2.0 0.55 1.08-2.60 30-145
4,4'-DDT.................................................... 10 3.6 4.6-13.7 25-160
Dieldrin.................................................... 2.0 0.76 1.15-2.49 36-146
Endosulfan I................................................ 2.0 0.49 1.14-2.82 45-153
Endosulfan II............................................... 10 6.1 2.2-17.1 D-202
Endosulfan Sulfate.......................................... 10 2.7 3.8-13.2 26-144
Endrin...................................................... 10 3.7 5.1-12.6 30-147
Heptachlor.................................................. 2.0 0.40 0.86-2.00 34-111
Heptachlor epoxide.......................................... 2.0 0.41 1.13-2.63 37-142
Toxaphene................................................... 50.0 12.7 27.8-55.6 41-126
PCB-1016.................................................... 50 10.0 30.5-51.5 50-114
PCB-1221.................................................... 50 24.4 22.1-75.2 15-178
PCB-1232.................................................... 50 17.9 14.0-98.5 10-215
PCB-1242.................................................... 50 12.2 24.8-69.6 39-150
PCB-1248.................................................... 50 15.9 29.0-70.2 38-158
PCB-1254.................................................... 50 13.8 22.2-57.9 29-131
PCB-1260.................................................... 50 10.4 18.7-54.9 8-127
----------------------------------------------------------------------------------------------------------------
s=Standard deviation of four recovery measurements, in [micro]g/L (Section 8.2.4).
X=Average recovery for four recovery measurements, in [micro]g/L (Section 8.2.4).
P, Ps=Percent recovery measured (Section 8.3.2, Section 8.4.2).
D=Detected; result must be greater than zero.
Note: These criteria are based directly upon the method performance data in Table 4. Where necessary, the limits
for recovery have been broadened to assure applicability of the limits to concentrations below those used to
develop Table 4.
Table 4--Method Accuracy and Precision as Functions of Concentration--Method 608
----------------------------------------------------------------------------------------------------------------
Accuracy, as Single analyst
Parameter recovery, X' precision, sr' Overall precision,
([micro]g/L) ([micro]g/L) S' ([micro]g/L)
----------------------------------------------------------------------------------------------------------------
Aldrin.............................................. 0.81C+0.04 0.16X-0.04 0.20X-0.01
[alpha]-BHC......................................... 0.84C+0.03 0.13X+0.04 0.23X-0.00
[beta]-BHC.......................................... 0.81C+0.07 0.22X-0.02 0.33X-0.05
[delta]-BHC......................................... 0.81C+0.07 0.18X+0.09 0.25X+0.03
[gamma]-BHC......................................... 0.82C-0.05 0.12X+0.06 0.22X+0.04
Chlordane........................................... 0.82C-0.04 0.13X+0.13 0.18X+0.18
4,4'-DDD............................................ 0.84C+0.30 0.20X-0.18 0.27X-0.14
4,4'-DDE............................................ 0.85C+0.14 0.13X+0.06 0.28X-0.09
4,4'-DDT............................................ 0.93C-0.13 0.17X+0.39 0.31X-0.21
Dieldrin............................................ 0.90C+0.02 0.12X+0.19 0.16X+0.16
Endosulfan I........................................ 0.97C+0.04 0.10X+0.07 0.18X+0.08
Endosulfan II....................................... 0.93C+0.34 0.41X--0.65 0.47X-0.20
Endosulfan Sulfate.................................. 0.89C-0.37 0.13X+0.33 0.24X+0.35
Endrin.............................................. 0.89C-0.04 0.20X+0.25 0.24X+0.25
Heptachlor.......................................... 0.69C+0.04 0.06X+0.13 0.16X+0.08
Heptachlor epoxide.................................. 0.89C+0.10 0.18X-0.11 0.25X-0.08
Toxaphene........................................... 0.80C+1.74 0.09X+3.20 0.20X+0.22
PCB-1016............................................ 0.81C+0.50 0.13X+0.15 0.15X+0.45
PCB-1221............................................ 0.96C+0.65 0.29X-0.76 0.35X-0.62
PCB-1232............................................ 0.91C+10.79 0.21X-1.93 0.31X+3.50
PCB-1242............................................ 0.93C+0.70 0.11X+1.40 0.21X+1.52
PCB-1248............................................ 0.97C+1.06 0.17X+0.41 0.25X-0.37
PCB-1254............................................ 0.76C+2.07 0.15X+1.66 0.17X+3.62
PCB-1260............................................ 0.66C+3.76 0.22X-2.37 0.39X-4.86
----------------------------------------------------------------------------------------------------------------
X'=Expected recovery for one or more measurements of a sample containing a concentration of C, in [micro]g/L.
sr'=Expected single analyst standard deviation of measurements at an average concentration found of X, in
[micro]g/L.
S'=Expected interlaboratory standard deviation of measurements at an average concentration found of X, in
[micro]g/L.
C=True value for the concentration, in [micro]g/L.
X=Average recovery found for measurements of samples containing a concentration of C, in [micro]g/L.
[[Page 132]]
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Method 609--Nitroaromatics and Isophorone
1. Scope and Application
1.1 This method covers the determination of certain nitroaromatics
and isophorone. The following parameters may be determined by this
method:
------------------------------------------------------------------------
Parameter STORET No. CAS No.
------------------------------------------------------------------------
2,4-Dinitrotoluene............................ 34611 121-14-2
2,6-Dinitrotoluene............................ 34626 606-20-2
Isophorone.................................... 34408 78-59-1
Nitrobenzene.................................. 34447 98-95-3
------------------------------------------------------------------------
1.2 This is a gas chromatographic (GC) method applicable to the
determination of
[[Page 142]]
the compounds listed above in municipal and industrial discharges as
provided under 40 CFR 136.1. When this method is used to analyze
unfamiliar samples for any or all of the compounds above, compound
identifications should be supported by at least one additional
qualitative technique. This method describes analytical conditions for a
second gas chromatographic column that can be used to confirm
measurements made with the primary column. Method 625 provides gas
chromatograph/mass spectrometer (GC/MS) conditions appropriate for the
qualitative and quantitative confirmation of results for all of the
parameters listed above, using the extract produced by this method.
1.3 The method detection limit (MDL, defined in Section 14.1)\1\ for
each parameter is listed in Table 1. The MDL for a specific wastewater
may differ from those listed, depending upon the nature of interferences
in the sample matrix.
1.4 The sample extraction and concentration steps in this method are
essentially the same as in Methods 606, 608, 611, and 612. Thus, a
single sample may be extracted to measure the parameters included in the
scope of each of these methods. When cleanup is required, the
concentration levels must be high enough to permit selecting aliquots,
as necessary, to apply appropriate cleanup procedures. The analyst is
allowed the latitude, under Section 12, to select chromatographic
conditions appropriate for the simultaneous measurement of combinations
of these parameters.
1.5 Any modification of this method, beyond those expressly
permitted, shall be considered as a major modification subject to
application and approval of alternate test procedures under 40 CFR 136.4
and 136.5.
1.6 This method is restricted to use by or under the supervision of
analysts experienced in the use of a gas chromatograph and in the
interpretation of gas chromatograms. Each analyst must demonstrate the
ability to generate acceptable results with this method using the
procedure described in Section 8.2.
2. Summary of Method
2.1 A measured volume of sample, approximately 1-L, is extracted
with methylene chloride using a separatory funnel. The methylene
chloride extract is dried and exchanged to hexane during concentration
to a volume of 10 mL or less. Isophorone and nitrobenzene are measured
by flame ionization detector gas chromatography (FIDGC). The
dinitrotoluenes are measured by electron capture detector gas
chromatography (ECDGC).\2\
2.2 The method provides a Florisil column cleanup procedure to aid
in the elimination of interferences that may be encountered.
3. Interferences
3.1 Method interferences may be caused by contaminants in solvents,
reagents, glassware, and other sample processing hardware that lead to
discrete artifacts and/or elevated baseliles in gas chromatograms. All
of these materials must be routinely demonstrated to be free from
interferences under the conditions of the analysis by running laboratory
reagent blanks as described in Section 8.1.3.
3.1.1 Glassware must be scrupulously cleaned.\3\ Clean all glassware
as soon as possible after use by rinsing with the last solvent used in
it. Solvent rinsing should be followed by detergent washing with hot
water, and rinses with tap water and distilled water. The glassware
should then be drained dry, and heated in a muffle furnace at 400 [deg]C
for 15 to 30 min. Some thermally stable materials, such as PCBs, may not
be eliminated by this treatment. Solvent rinses with acetone and
pesticide quality hexane may be substituted for the muffle furnace
heating. Thorough rinsing with such solvents usually eliminates PCB
interference. Volumetric ware should not be heated in a muffle furnace.
After drying and cooling, glassware should be sealed and stored in a
clean environment to prevent any accumulation of dust or other
contaminants. Store inverted or capped with aluminum foil.
3.1.2 The use of high purity reagents and solvents helps to minimize
interference problems. Purification of solvents by distillation in all-
glass systems may be required.
3.2 Matrix interferences may be caused by contaminants that are co-
extracted from the sample. The extent of matrix interferences will vary
considerably from source to source, depending upon the nature and
diversity of the industrial complex or municipality being sampled. The
cleanup procedure in Section 11 can be used to overcome many of these
interferences, but unique samples may require additional cleanup
approaches to achieve the MDL listed in Table 1.
4. Safety
4.1 The toxicity or carcinogenicity of each reagent used in this
method has not been precisely defined; however, each chemical compound
should be treated as a potential health hazard. From this viewpoint,
exposure to these chemicals must be reduced to the lowest possible level
by whatever means available. The laboratory is responsible for
maintaining a current awareness file of OSHA regulations regarding the
safe handling of the chemicals specified in this method. A reference
file of material data handling sheets should also be made available to
all personnel involved in the chemical analysis. Additional references
to laboratory safety are available and have been identified
4-6 for the information of the analyst.
[[Page 143]]
5. Apparatus and Materials
5.1 Sampling equipment, for discrete or composite sampling.
5.1.1 Grab sample bottle--1-L or 1-qt, amber glass, fitted with a
screw cap lined with Teflon. Foil may be substituted for Teflon if the
sample is not corrosive. If amber bottles are not available, protect
samples from light. The bottle and cap liner must be washed, rinsed with
acetone or methylene chloride, and dried before use to minimize
contamination.
5.1.2 Automatic sampler (optional)--The sampler must incorporate
glass sample containers for the collection of a minimum of 250 mL of
sample. Sample containers must be kept refrigerated at 4 [deg]C and
protected from light during compositing. If the sampler uses a
peristaltic pump, a minimum length of compressible silicone rubber
tubing may be used. Before use, however, the compressible tubing should
be thoroughly rinsed with methanol, followed by repeated rinsings with
distilled water to minimize the potential for contamination of the
sample. An integrating flow meter is required to collect flow
proportional composites.
5.2 Glassware (All specifications are suggested. Catalog numbers are
included for illustration only.):
5.2.1 Separatory funnel--2-L, with Teflon stopcock.
5.2.2 Drying column--Chromatographic column, approximately 400 mm
long x 19 mm ID, with coarse frit filter disc.
5.2.3 Chromatographic column--100 mm long x 10 mm ID, with Teflon
stopcock.
5.2.4 Concentrator tube, Kuderna-Danish--10-mL, graduated (Kontes K-
570050-1025 or equivalent). Calibration must be checked at the volumes
employed in the test. Ground glass stopper is used to prevent
evaporation of extracts.
5.2.5 Evaporative flask, Kuderna-Danish--500-mL (Kontes K-570001-
0500 or equivalent). Attach to concentrator tube with springs.
5.2.6 Snyder column, Kuderna-Danish--Three-ball macro (Kontes K-
503000-0121 or equivalent).
5.2.7 Snyder column, Kuderna-Danish--Two-ball micro (Kontes K-
569001-0219 or equivalent).
5.2.8 Vials--10 to 15-mL, amber glass, with Teflon-lined screw cap.
5.3 Boiling chips--Approximately 10/40 mesh. Heat to 400 [deg]C for
30 min or Soxhlet extract with methylene chloride.
5.4 Water bath--Heated, with concentric ring cover, capable of
temperature control (2 [deg]C). The bath should be
used in a hood.
5.5 Balance--Analytical, capable of accurately weighing 0.0001 g.
5.6 Gas chromatograph--An analytical system complete with gas
chromatograph suitable for on-column injection and all required
accessories including syringes, analytical columns, gases, detector, and
strip-chart recorder. A data system is recommended for measuring peak
areas.
5.6.1 Column 1--1.2 m long x 2 or 4 mm ID glass, packed with 1.95%
QF-1/1.5% OV-17 on Gas-Chrom Q (80/100 mesh) or equivalent. This column
was used to develop the method performance statements given in Section
14. Guidelines for the use of alternate column packings are provided in
Section 12.1.
5.6.2 Column 2--3.0 m long x 2 or 4 mm ID glass, packed with 3% OV-
101 on Gas-Chrom Q (80/100 mesh) or equivalent.
5.6.3 Detectors--Flame ionization and electron capture detectors.
The flame ionization detector (FID) is used when determining isophorone
and nitrobenzene. The electron capture detector (ECD) is used when
determining the dinitrotoluenes. Both detectors have proven effective in
the analysis of wastewaters and were used in develop the method
performance statements in Section 14. Guidelines for the use to
alternate detectors are provided in Section 12.1.
6. Reagents
6.1 Reagent water--Reagent water is defined as a water in which an
interferent is not observed at the MDL of the parameters of interest.
6.2 Sodium hydroxide solution (10 N)--Dissolve 40 g of NaOH (ACS) in
reagent water and dilute to 100 mL.
6.3 Sulfuric acid (1+1)--Slowly, add 50 mL of
H2SO4 (ACS, sp. gr. 1.84) to 50 mL of reagent
water.
6.4 Acetone, hexane, methanol, methylene chloride--Pesticide quality
or equivalent.
6.5 Sodium sulfate--(ACS) Granular, anhydrous. Purify by heating at
400 [deg]C for 4 h in a shallow tray.
6.6 Florisil--PR grade (60/100 mesh). Purchase activated at 1250
[deg]F and store in dark in glass containers with ground glass stoppers
or foil-lined screw caps. Before use, activate each batch at least 16 h
at 200 [deg]C in a foil-covered glass container and allow to cool.
6.7 Stock standard solutions (1.00 [micro]g/[micro]L)--Stock
standard solutions can be prepared from pure standard materials or
purchased as certified solutions.
6.7.1 Prepare stock standard solutions by accurately weighing about
0.0100 g of pure material. Dissolve the material in hexane and dilute to
volume in a 10-mL volumetric flask. Larger volumes can be used at the
convenience of the analyst. When compound purity is assayed to be 96% or
greater, the weight can be used without correction to calculate the
concentration of the stock standard. Commercially prepared stock
standards can be used at any concentration if they are certified by the
manufacturer or by an independent source.
6.7.2 Transfer the stock standard solutions into Teflon-sealed
screw-cap bottles.
[[Page 144]]
Store at 4 [deg]C and protect from light. Stock standard solutions
should be checked frequently for signs of degradation or evaporation,
especially just prior to preparing calibration standards from them.
6.7.3 Stock standard solutions must be replaced after six months, or
sooner if comparison with check standards indicates a problem.
6.8 Quality control check sample concentrate--See Section 8.2.1.
7. Calibration
7.1 Establish gas chromatographic operating conditions equivalent to
those given in Table 1. The gas chromatographic system can be calibrated
using the external standard technique (Section 7.2) or the internal
standard technique (Section 7.3).
7.2 External standard calibration procedure:
7.2.1 Prepare calibration standards at a minimum of three
concentration levels for each parameter of interest by adding volumes of
one or more stock standards to a volumetric flask and diluting to volume
with hexane. One of the external standards should be at a concentration
near, but above, the MDL (Table 1) and the other concentrations should
correspond to the expected range of concentrations found in real samples
or should define the working range of the detector.
7.2.2 Using injections of 2 to 5 [micro]L, analyze each calibration
standard according to Section 12 and tabulate peak height or area
responses against the mass injected. The results can be used to prepare
a calibration curve for each compound. Alternatively, if the ratio of
response to amount injected (calibration factor) is a constant over the
working range (<10% relative standard deviation, RSD) linearity through
the origin can be assumed and the average ratio or calibration factor
can be used in place of a calibration curve.
7.3 Internal standard calibration procedure--To use this approach,
the analyst must select one or more internal standards that are similar
in analytical behavior to the compounds of interest. The analyst must
further demonstrate that the measurement of the internal standard is not
affected by method or matrix interferences. Because of these
limitations, no internal standard can be suggested that is applicable to
all samples.
7.3.1 Prepare calibration standards at a minimum of three
concentration levels for each parameter of interest by adding volumes of
one or more stock standards to a volumetric flash. To each calibration
standard, add a known constant amount of one or more internal standards,
and dilute to volume with hexane. One of the standards should be at a
concentration near, but above, the MDL and the other concentrations
should correspond to the expected range of concentrations found in real
samples or should define the working range of the detector.
7.3.2 Using injections of 2 to 5 [micro]L, analyze each calibration
standard according to Section 12 and tabulate peak height or area
responses against concentration for each compound and internal standard.
Calculate response factors (RF) for each compound using Equation 1.
Equation 1.
[GRAPHIC] [TIFF OMITTED] TC15NO91.110
where:
As=Response for the parameter to be measured.
Ais=Response for the internal standard.
Cis=Concentration of the internal standard ([micro]g/L).
Cs=Concentration of the parameter to be measured ([micro]g/
L).
If the RF value over the working range is a constant (<10% RSD), the
RF can be assumed to be invariant and the average RF can be used for
calculations. Alternatively, the results can be used to plot a
calibration curve of response ratios, As/Ais, vs.
RF.
7.4 The working calibration curve, calibration factor, or RF must be
verified on each working day by the measurement of one or more
calibration standards. If the response for any parameter varies from the
predicted response by more than 15%, a new
calibration curve must be prepared for that compound.
7.5 Before using any cleanup procedure, the analyst must process a
series of calibration standards through the procedure to validate
elution patterns and the absence of interferences from the reagents.
8. Quality Control
8.1 Each laboratory that uses this method is required to operate a
formal quality control program. The minimum requirements of this program
consist of an initial demonstration of laboratory capability and an
ongoing analysis of spiked samples to evaluate and document data
quality. The laboratory must maintain records to document the quality of
data that is generated. Ongoing data quality checks are compared with
established performance criteria to determine if the results of analyses
meet the performance characteristics of the method. When results of
sample spikes indicate atypical method performance, a quality control
check standard must be analyzed to confirm that the measurements were
performed in an in-control mode of operation.
8.1.1 The analyst must make an initial, one-time, demonstration of
the ability to
[[Page 145]]
generate acceptable accuracy and precision with this method. This
ability is established as described in Section 8.2.
8.1.2 In recognition of advances that are occurring in
chromatography, the analyst is permitted certain options (detailed in
Sections 10.4, 11.1, and 12.1) to improve the separations or lower the
cost of measurements. Each time such a modification is made to the
method, the analyst is required to repeat the procedure in Section 8.2.
8.1.3 Before processing any samples, the analyst must analyze a
reagent water blank to demonstrate that interferences from the
analytical system and glassware are under control. Each time a set of
samples is extracted or reagents are changed, a reagent water blank must
be processed as a safeguard against laboratory contamination.
8.1.4 The laboratory must, on an ongoing basis, spike and analyze a
minimum of 10% of all samples to monitor and evaluate laboratory data
quality. This procedure is described in Section 8.3.
8.1,5 The laboratory must, on an ongoing basis, demonstrate through
the analyses of quality control check standards that the operation of
the measurement system is in control. This procedure is described in
Section 8.4. The frequency of the check standard analyses is equivalent
to 10% of all samples analyzed but may be reduced if spike recoveries
from samples (Section 8.3) meet all specified quality control criteria.
8.1.6 The laboratory must maintain performance records to document
the quality of data that is generated. This procedure is described in
Section 8.5.
8.2 To establish the ability to generate acceptable accuracy and
precision, the analyst must perform the following operations.
8.2.1 A quality control (QC) check sample concentrate is required
containing each parameter of interest in acetone at a concentration of
20 [micro]g/mL for each dinitrotoluene and 100 [micro]g/mL for
isophorone and nitrobenzene. The QC check sample concentrate must be
obtained from the U.S. Environmental Protection Agency, Environmental
Monitoring and Support Laboratory in Cincinnati, Ohio, if available. If
not available from that source, the QC check sample concentrate must be
obtained from another external source. If not available from either
source above, the QC check sample concentrate must be prepared by the
laboratory using stock standards prepared independently from those used
for calibration.
8.2.2 Using a pipet, prepare QC check samples at the test
concentrations shown in Table 2 by adding 1.00 mL of QC check sample
concentrate to each of four 1-L aliquots of reagent water.
8.2.3 Analyze the well-mixed QC check samples according to the
method beginning in Section 10.
8.2.4 Calculate the average recovery (X) in [micro]g/L, and the
standard deviation of the recovery (s) in [micro]g/L, for each parameter
using the four results.
8.2.5 For each parameter compare s and X with the corresponding
acceptance criteria for precision and accuracy, respectively, found in
Table 2. If s and X for all parameters of interest meet the acceptance
criteria, the system performance is acceptable and analysis of actual
samples can begin. If any individual s exceeds the precision limit or
any individual X falls outside the range for accuracy, the system
performance is unacceptable for that parameter. Locate and correct the
source of the problem and repeat the test for all parameters of interest
beginning with Section 8.2.2.
8.3 The laboratory must, on an ongoing basis, spike at least 10% of
the samples from each sample site being monitored to assess accuracy.
For laboratories analyzing one to ten samples per month, at least one
spiked sample per month is required.
8.3.1 The concentration of the spike in the sample should be
determined as follows:
8.3.1.1 If, as in compliance monitoring, the concentration of a
specific parameter in the sample is being checked against a regulatory
concentration limit, the spike should be at that limit or 1 to 5 times
higher than the background concentration determined in Section 8.3.2,
whichever concentration would be larger.
8.3.1.2 If the concentration of a specific parameter in the sample
is not being checked against a limit specific to that parameter, the
spike should be at the test concentration in Section 8.2.2 or 1 to 5
times higher than the background concentration determined in Section
8.3.2, whichever concentration would be larger.
8.3.1.3 If it is impractical to determile background levels before
spiking (e.g., maximum holding times will be exceeded), the spike
concentration should be (1) the regulatory concentration limit, if any;
or, if none (2) the larger of either 5 times higher than the expected
background concentration or the test concentration in Section 8.2.2.
8.3.2 Analyze one sample aliquot to determine the background
concentration (B) of each parameter. If necessary, prepare a new QC
check sample concentrate (Section 8.2.1) appropriate for the background
concentrations in the sample. Spike a second sample aliquot with 1.0 mL
of the QC check sample concentrate and analyze it to determine the
concentration after spiking (A) of each parameter. Calculate each
percent recovery (P) as 100 (A-B)%/T, where T is the known true value of
the spike.
8.3.3 Compare the percent recovery (P) for each parameter with the
corresponding QC acceptance criteria found in Table 2. These acceptance
criteria were calculated to include an allowance for error in
measurement
[[Page 146]]
of both the background and spike concentrations, assuming a spike to
background ratio of 5:1. This error will be accounted for to the extent
that the analyst's spike to background ratio approaches 5:1.\7\ If
spiking was performed at a concentration lower than the test
concentration in Section 8.2.2, the analyst must use either the QC
acceptance criteria in Table 2, or optional QC acceptance criteria
calculated for the specific spike concentration. To calculate optional
acceptance criteria for the recovery of a parameter: (1) Calculate
accuracy (X') using the equation in Table 3, substituting the spike
concentration (T) for C; (2) calculate overall precision (S') using the
equation in Table 3, substituting X' for X8; (3) calculate the range for
recovery at the spike concentration as (100 X'/T) 2.44 (100 S'/T)%.\7\
8.3.4 If any individual P falls outside the designated range for
recovery, that parameter has failed the acceptance criteria. A check
standard containing each parameter that failed the criteria must be
analyzed as described in Section 8.4.
8.4. If any parameter fails the acceptance criteria for recovery in
Section 8.3, a QC check standard containing each parameter that failed
must be prepared and analyzed.
Note: The frequency for the required analysis of a QC check standard
will depend upon the number of parameters being simultaneously tested,
the complexity of the sample matrix, and the performance of the
laboratory.
8.4.1 Prepare the QC check standard by adding 1.0 mL of QC check
sample concentrate (Section 8.2.1 or 8.3.2) to 1 L of reagent water. The
QC check standard needs only to contain the parameters that failed
criteria in the test in Section 8.3.
8.4.2 Analyze the QC check standard to determine the concentration
measured (A) of each parameter. Calculate each percent recovery
(Ps) as 100 (A/T)%, where T is the true value of the standard
concentration.
8.4.3 Compare the percent recovery (Ps) for each
parameter with the corresponding QC acceptance criteria found in Table
2. Only parameters that failed the test in Section 8.3 need to be
compared with these criteria. If the recovery of any such parameter
falls outside the designated range, the laboratory performance for that
parameter is judged to be out of control, and the problem must be
immediately identified and corrected. The analytical result for that
parameter in the unspiked sample is suspect and may not be reported for
regulatory compliance purposes.
8.5 As part of QC program for the laboratory, method accuracy for
wastewater samples must be assessed and records must be maintained.
After the analysis of five spiked wastewater samples as in Section 8.3,
calculate the average percent recovery (P) and the standard deviation of
the percent recovery (sp). Express the accuracy assessment as
a percent recovery interval from P-2sp to P+2sp.
If P=90% and sp = 10%, for example, the accuracy interval is
expressed as 70-110%. Update the accuracy assessment for each parameter
on a regular basis (e.g. after each five to ten new accuracy
measurements).
8.6 It is recommended that the laboratory adopt additional quality
assurance practices for use with this method. The specific practices
that are most productive depend upon the needs of the laboratory and the
nature of the samples. Field duplicates may be analyzed to assess the
precision of the environmental measurements. When doubt exists over the
identification of a peak on the chromatogram, confirmatory techniques
such as gas chromatography with a dissimilar column, specific element
detector, or mass spectrometer must be used. Whenever possible, the
laboratory should analyze standard reference materials and participate
in relevant performance evaluation studies.
9. Sample Collection, Preservation, and Handling
9.1 Grab samples must be collected in glass containers. Conventional
sampling practices \8\ should be followed, except that the bottle must
not be prerinsed with sample before collection. Composite samples should
be collected in refrigerated glass containers in accordance with the
requirements of the program. Automatic sampling equipment must be as
free as possible of Tygon tubing and other potential sources of
contamination.
9.2 All samples must be iced or refrigerated at 4 [deg]C from the
time of collection until extraction.
9.3 All samples must be extracted within 7 days of collection and
completely analyzed within 40 days of extraction.\2\
10. Sample Extraction
10.1 Mark the water meniscus on the side of the sample bottle for
later determination of sample volume. Pour the entire sample into a 2-L
separatory funnel. Check the pH of the sample with wide-range pH paper
and adjust to within the range of 5 to 9 with sodium hydroxide solution
or sulfuric acid.
10.2 Add 60 mL of methylene chloride to the sample bottle, seal, and
shake 30 s to rinse the inner surface. Transfer the solvent to the
separatory funnel and extract the sample by shaking the funnel for 2
min. with periodic venting to release excess pressure. Allow the organic
layer to separate from the water phase for a minimum of 10 min. If the
emulsion interface between layers is more than one-third the volume of
the solvent layer, the analyst must employ mechanical techniques to
complete the phase separation. The optimum technique depends upon the
sample, but may include stirring, filtration
[[Page 147]]
of the emulsion through glass wool, centrifugation, or other physical
methods. Collect the methylene chloride extract in a 250-mL Erlenmeyer
flask.
10.3 Add a second 60-mL volume of methylene chloride to the sample
bottle and repeat the extraction procedure a second time, combining the
extracts in the Erlenmeyer flask. Perform a third extraction in the same
manner.
10.4 Assemble a Kuderna-Danish (K-D) concentrator by attaching a 10-
mL concentrator tube to a 500-mL evaporative flask. Other concentration
devices or techniques may be used in place of the K-D concentrator if
the requirements of Section 8.2 are met.
10.5 Pour the combined extract through a solvent-rinsed drying
column containing about 10 cm of anhydrous sodium sulfate, and collect
the extract in the K-D concentrator. Rinse the Erlenmeyer flask and
column with 20 to 30 mL of methylene chloride to complete the
quantitative transfer.
10.6 Sections 10.7 and 10.8 describe a procedure for exchanging the
methylene chloride solvent to hexane while concentrating the extract
volume to 1.0 mL. When it is not necessary to achieve the MDL in Table
2, the solvent exchange may be made by the addition of 50 mL of hexane
and concentration to 10 mL as described in Method 606, Sections 10.7 and
10.8.
10.7 Add one or two clean boiling chips to the evaporative flask and
attach a three-ball Snyder column. Prewet the Snyder column by adding
about 1 mL of methylene chloride to the top. Place the K-D apparatus on
a hot water bath (60 to 65 [deg]C) so that the concentrator tube is
partially immersed in the hot water, and the entire lower rounded
surface of the flask is bathed with hot vapor. Adjust the vertical
position of the apparatus and the water temperature as required to
complete the concentration in 15 to 20 min. At the proper rate of
distillation the balls of the column will actively chatter but the
chambers will not flood with condensed solvent. When the apparent volume
of liquid reaches 1 mL, remove the K-D apparatus and allow it to drain
and cool for at least 10 min.
10.8 Remove the Snyder column and rinse the flask and its lower
joint into the concentrator tube with 1 to 2 mL of methylene chloride. A
5-mL syringe is recommended for this operation. Add 1 to 2 mL of hexane
and a clean boiling chip to the concentrator tube and attach a two-ball
micro-Snyder column. Prewet the column by adding about 0.5 mL of hexane
to the top. Place the micro-K-D apparatus on a hot water bath (60 to 65
[deg]C) so that the concentrator tube is partially immersed in the hot
water. Adjust the vertical position of the apparatus and the water
temperature as required to complete the concentration in 5 to 10 min. At
the proper rate of distillation the balls of the column will actively
chatter but the chambers will not flood. When the apparent volume of
liquid reaches 0.5 mL, remove the K-D apparatus and allow it to drain
and cool for at least 10 min.
10.9 Remove the micro-Snyder column and rinse its lower joint into
the concentrator tube with a minimum amount of hexane. Adjust the
extract volume to 1.0 mL. Stopper the concentrator tube and store
refrigerated if further processing will not be performed immediately. If
the extract will be stored longer than two days, it should be
transferred to a Teflon-sealed screw-cap vial. If the sample extract
requires no further cleanup, proceed with gas chromatographic analysis
(Section 12). If the sample requires further cleanup, proceed to Section
11.
10.10 Determine the original sample volume by refilling the sample
bottle to the mark and transferring the liquid to a 1000-mL graduated
cylinder. Record the sample volume to the nearest 5 mL.
11. Cleanup and Separation
11.1 Cleanup procedures may not be necessary for a relatively clean
sample matrix. If particular circumstances demand the use of a cleanup
procedure, the analyst may use the procedure below or any other
appropriate procedure. However, the analyst first must demonstrate that
the requirements of Section 8.2 can be met using the method as revised
to incorporate the cleanup procedure.
11.2 Florisil column cleanup:
11.2.1 Prepare a slurry of 10 g of acti vated Florisil in methylene
chloride/ hexane (1+9)(V/V) and place the Florisil into a
chromatographic column. Tap the column to settle the Florisil and add 1
cm of anhydrous sodium sulfate to the top. Adjust the elution rate to
about 2 mL/min.
11.2.2 Just prior to exposure of the sodium sulfate layer to the
air, quantitatively transfer the sample extract onto the column using an
additional 2 mL of hexane to complete the transfer. Just prior to
exposure of the sodium sulfate layer to the air, add 30 mL of methylene
chloride/hexane (1 + 9)(V/V) and continue the elution of the column.
Discard the eluate.
11.2.3 Next, elute the column with 30 mL of acetone/methylene
chloride (1 + 9)(V/V) into a 500-mL K-D flask equipped with a 10-mL
concentrator tube. Concentrate the collected fraction as in Sections
10.6, 10.7, 10.8, and 10.9 including the solvent exchange to 1 mL of
hexane. This fraction should contain the nitroaromatics and isophorone.
Analyze by gas chromatography (Section 12).
12. Gas Chromatography
12.1 Isophorone and nitrobenzene are analyzed by injection of a
portion of the extract into an FIDGC. The dinitrotoluenes are analyzed
by a separate injection into an ECDGC. Table 1 summarizes the
recommended operating conditions for the gas chromatograph.
[[Page 148]]
Included in this table are retention times and MDL that can be achieved
under these conditions. Examples of the separations achieved by Column 1
are shown in Figures 1 and 2. Other packed or capillary (open-tubular)
columns, chromatographic conditions, or detectors may be used if the
requirements of Section 8.2 are met.
12.2 Calibrate the system daily as described in Section 7.
12.3 If the internal standard calibration procedure is being used,
the internal standard must be added to the same extract and mixed
thoroughly immediately before injection into the gas chromatograph.
12.4 Inject 2 to 5 [micro]L of the sample extract or standard into
the gas chromatograph using the solvent-flush technique.\9\ Smaller (1.0
[micro]L) volumes may be injected if automatic devices are employed.
Record the volume injected to the nearest 0.05 [micro]L, the total
extract volume, and the resulting peak size in area or peak height
units.
12.5 Identify the parameters in the sample by comparing the
retention times of the peaks in the sample chromatogram with those of
the peaks in standard chromatograms. The width of the retention time
window used to make identifications should be based upon measurements of
actual retention time variations of standards over the course of a day.
Three times the standard deviation of a retention time for a compound
can be used to calculate a suggested window size; however, the
experience of the analyst should weigh heavily in the interpretation of
chromatograms.
12.6 If the response for a peak exceeds the working range of the
system, dilute the extract and reanalyze.
12.7 If the measurement of the peak response is prevented by the
presence of interferences, further cleanup is required.
13. Calculations
13.1 Determine the concentration of individual compounds in the
sample.
13.1.1 If the external standard calibration procedure is used,
calculate the amount of material injected from the peak response using
the calibration curve or calibration factor determined in Section 7.2.2.
The concentration in the sample can be calculated from Equation 2.
[GRAPHIC] [TIFF OMITTED] TC15NO91.111
Equation 2
where:
A=Amount of material injected (ng).
Vi=Volume of extract injected ([micro]L).
Vt=Volume of total extract ([micro]L).
Vs=Volume of water extracted (mL).
13.1.2 If the internal standard calibration procedure is used,
calculate the concentration in the sample using the response factor (RF)
determined in Section 7.3.2 and Equation 3.
[GRAPHIC] [TIFF OMITTED] TC15NO91.112
Equation 3
where:
As=Response for the parameter to be measured.
Ais=Response for the internal standard.
Is=Amount of internal standard added to each extract
([micro]g).
Vo=Volume of water extracted (L).
13.2 Report results in [micro]g/L without correction for recovery
data. All QC data obtained should be reported with the sample results.
14. Method Performance
14.1 The method detection limit (MDL) is defined as the minimum
concentration of a substance that can be measured and reported with 99%
confidence that the value is above zero.\1\ The MDL concentrations
listed in Table 1 were obtained using reagent water.\10\ Similar results
were achieved using representative wastewaters. The MDL actually
achieved in a given analysis will vary depending on instrument
sensitivity and matrix effects.
14.2 This method has been tested for linearity of spike recovery
from reagent water and has been demonstrated to be applicable over the
concentration range from 7xMDL to 1000xMDL.\10\
14.3 This method was tested by 18 laboratories using reagent water,
drinking water, surface water, and three industrial wastewaters spiked
at six concentrations over the range 1.0 to 515 [micro]g/L.\11\ Single
operator precision, overall precision, and method accuracy were found to
be directly related to the concentration of the parameter and
essentially independent of the sample matrix. Linear equations to
describe these relationships are presented in Table 3.
References
1. 40 CFR part 136, appendix B.
2. ``Determination of Nitroaromatic Compounds and Isophorone in
Industrial and Municipal Wastewaters,'' EPA 600/ 4-82-024, National
Technical Information Service, PB82-208398, Springfield, Virginia 22161,
May 1982.
3. ASTM Annual Book of Standards, Part 31, D3694-78. ``Standard
Practices for Preparation of Sample Containers and for Preservation of
Organic Constituents,'' American Society for Testing and Materials,
Philadelphia.
[[Page 149]]
4. ``Carcinogens--Working With Carcinogens,'' Department of Health,
Education, and Welfare, Public Health Service, Center for Disease
Control, National Institute for Occupational Safety and Health,
Publication No. 77-206, August 1977.
5. ``OSHA Safety and Health Standards, General Industry,'' (29 CFR
part 1910), Occupational Safety and Health Administration, OSHA 2206
(Revised, January 1976).
6. ``Safety in Academic Chemistry Laboratories,'' American Chemical
Society Publication, Committee on Chemical Safety, 3rd Edition, 1979.
7. Provost, L.P., and Elder, R.S. ``Interpretation of Percent
Recovery Data,'' American Laboratory, 15, 58-63 (1983). (The value 2.44
used in the equation in Section 8.3.3 is two times the value 1.22
derived in this report.)
8. ASTM Annual Book of Standards, Part 31, D3370-76. ``Standard
Practices for Sampling Water,'' American Society for Testing and
Materials, Philadelphia.
9. Burke, J.A. ``Gas Chromatography for Pesticide Residue Analysis;
Some Practical Aspects,'' Journal of the Association of Official
Analytical Chemists, 48, 1037 (1965).
10. ``Determination of Method Detection Limit and Analytical Curve
for EPA Method 609--Nitroaromatics and Isophorone,'' Special letter
report for EPA Contract 68-03-2624, U.S. Environmental Protection
Agency, Environmental Monitoring and Support Laboratory, Cincinnati,
Ohio 45268, June 1980.
11. ``EPA Method Study 19, Method 609 (Nitroaromatics and
Isophorone),'' EPA 600/4-84-018, National Technical Information Service,
PB84-176908, Springfield, Virginia 22161, March 1984.
Table 1--Chromatographic Conditions and Method Detection Limits
----------------------------------------------------------------------------------------------------------------
Retention time (min) Method detection limit
---------------------------- ([micro]g/L)
Parameter ---------------------------
Col. 1 Col. 2 ECDGC FIDGC
----------------------------------------------------------------------------------------------------------------
Nitrobenzene............................................ 3.31 4.31 13.7 3.6
2,6-Dinitrotoluene...................................... 3.52 4.75 0.01 -
Isophorone.............................................. 4.49 5.72 15.7 5.7
2,4-Dinitrotoluene...................................... 5.35 6.54 0.02 -
----------------------------------------------------------------------------------------------------------------
AAColumn 1 conditions: Gas-Chrom Q (80/100 mesh) coated with 1.95% QF-1/1.5% OV-17 packed in a 1.2 m long x 2
mm or 4 mm ID glass column. A 2 mm ID column and nitrogen carrier gas at 44 mL/min flow rate were used when
determining isophorone and nitrobenzene by FIDGC. The column temperature was held isothermal at 85 [deg]C. A 4
mm ID column and 10% methane/90% argon carrier gas at 44 mL/min flow rate were used when determining the
dinitrotol uenes by ECDGC. The column temperature was held iso thermal at 145 [deg]C.
AAColumn 2 conditions: Gas-Chrom Q (80/100 mesh) coated with 3% OV-101 packed in a 3.0 m long x 2 mm or 4 mm ID
glass column. A 2 mm ID column and nitrogen carrier gas at 44 mL/min flow rate were used when determining
isophorone and nitrobenzene by FIDGC. The column temperature was held isothermal at 100 [deg]C. A 4 mm ID
column and 10% methane/90% argon carrier gas at 44 mL/min flow rate were used when determining the
dinitrotoluenes by ECDGC. The column temperature was held isothermal at 150 [deg]C.
Table 2--QC Acceptance Criteria--Method 609
----------------------------------------------------------------------------------------------------------------
Test Conc. Range for X
Parameter ([micro]g/ Limit for s ([micro]g/L) Range for
L) ([micro]g/L) P, Ps (%)
----------------------------------------------------------------------------------------------------------------
2,4-Dinitrotoluene........................................ 20 5.1 3.6-22.8 6-125
2,6-Dinitrotoluene........................................ 20 4.8 3.8-23.0 8-126
Isophorone................................................ 100 32.3 8.0-100.0 D-117
Nitrobenzene.............................................. 100 33.3 25.7-100.0 6-118
----------------------------------------------------------------------------------------------------------------
s=Standard deviation of four recovery measurements, in [micro]g/L (Section 8.2.4).
X=Average recovery for four recovery measurements, in [micro]g/L (Section 8.2.4).
P, Ps=Percent recovery measured (Section 8.3.2, Section 8.4.2).
D=Detected; result must be greater than zero.
Note: These criteria are based directly upon the method performance data in Table 3. Where necessary, the limits
for recovery have been broadened to assure applicability of the limits to concentrations below those used to
develop Table 3.
Table 3--Method Accuracy and Precision as Functions of Concentration--Method 609
----------------------------------------------------------------------------------------------------------------
Accuracy, as Single analyst Overall
Parameter recovery, X' precision, sr' precision, S'
([micro]g/L) ([micro]g/L) ([micro]g/L)
----------------------------------------------------------------------------------------------------------------
2,4-Dinitro-
toluene............................................... 0.65C+0.22 0.20X+0.08 0.37X-0.07
2,6-Dinitro-
toluene............................................... 0.66C+0.20 0.19X+0.06 0.36X-0.00
Isophorone............................................. 0.49C+2.93 0.28X+2.77 0.46X+0.31
Nitrobenzene........................................... 0.60C+2.00 0.25X+2.53 0.37X-0.78
----------------------------------------------------------------------------------------------------------------
X'=Expected recovery for one or more measurements of a sample containing a concentration of C, in [micro]g/L.
sr'=Expected single analyst standard deviation of measurements at an average concentration found of X, in
[micro]g/L.
S'=Expected interlaboratory standard deviation of measurements at an average concentration found of X, in
[micro]g/L.
C=True value for the concentration, in [micro]g/L.
X=Average recovery found for measurements of samples containing a concentration of C, in [micro]g/L.
[[Page 150]]
[GRAPHIC] [TIFF OMITTED] TC02JY92.029
[[Page 151]]
[GRAPHIC] [TIFF OMITTED] TC02JY92.030
[[Page 152]]
Method 610--Polynuclear Aromatic Hydrocarbons
1. Scope and Application
1.1 This method covers the determination of certain polynuclear
aromatic hydrocarbons (PAH). The following parameters can be determined
by this method:
------------------------------------------------------------------------
Parameter STORET No. CAS No.
------------------------------------------------------------------------
Acenaphthene................................ 34205 83-32-9
Acenaphthylene.............................. 34200 208-96-8
Anthracene.................................. 34220 120-12-7
Benzo(a)anthracene.......................... 34526 56-55-3
Benzo(a)pyrene.............................. 34247 50-32-8
Benzo(b)fluoranthene........................ 34230 205-99-2
Benzo(ghi)perylene.......................... 34521 191-24-2
Benzo(k)fluoranthene........................ 34242 207-08-9
Chrysene.................................... 34320 218-01-9
Dibenzo(a,h)anthracene...................... 34556 53-70-3
Fluoranthene................................ 34376 206-44-0
Fluorene.................................... 34381 86-73-7
Indeno(1,2,3-cd)pyrene...................... 34403 193-39-5
Naphthalene................................. 34696 91-20-3
Phenanthrene................................ 34461 85-01-8
Pyrene...................................... 34469 129-00-0
------------------------------------------------------------------------
1.2 This is a chromatographic method applicable to the determination
of the compounds listed above in municipal and industrial discharges as
provided under 40 CFR 136.1. When this method is used to analyze
unfamiliar samples for any or all of the compounds above, compound
identifications should be supported by at least one additional
qualitative technique. Method 625 provides gas chromatograph/mass
spectrometer (GC/MS) conditions appropriate for the qualitative and
quantitative confirmation of results for many of the parameters listed
above, using the extract produced by this method.
1.3 This method provides for both high performance liquid
chromatographic (HPLC) and gas chromatographic (GC) approaches for the
determination of PAHs. The gas chromatographic procedure does not
adequately resolve the following four pairs of compounds: Anthracene and
phenanthrene; chrysene and benzo(a)anthracene; benzo(b)fluoranthene and
benzo(k)fluoranthene; and dibenzo(a,h) anthracene and indeno (1,2,3-
cd)pyrene. Unless the purpose for the analysis can be served by
reporting the sum of an unresolved pair, the liquid chromatographic
approach must be used for these compounds. The liquid chromatographic
method does resolve all 16 of the PAHs listed.
1.4 The method detection limit (MDL, defined in Section 15.1) \1\
for each parameter is listed in Table 1. The MDL for a specific
wastewater may differ from those listed, depending upon the nature of
interferences in the sample matrix.
1.5 The sample extraction and concentration steps in this method are
essentially the same as in Methods 606, 608, 609, 611, and 612. Thus, a
single sample may be extracted to measure the parameters included in the
scope of each of these methods. When cleanup is required, the
concentration levels must be high enough to permit selecting aliquots,
as necessary, to apply appropriate cleanup procedures. Selection of the
aliquots must be made prior to the solvent exchange steps of this
method. The analyst is allowed the latitude, under Sections 12 and 13,
to select chromatographic conditions appropriate for the simultaneous
measurement of combinations of these parameters.
1.6 Any modification of this method, beyond those expressly
permitted, shall be considered as a major modification subject to
application and approval of alternate test procedures under 40 CFR 136.4
and 136.5.
1.7 This method is restricted to use by or under the supervision of
analysts experienced in the use of HPLC and GC systems and in the
interpretation of liquid and gas chromatograms. Each analyst must
demonstrate the ability to generate acceptable results with this method
using the procedure described in Section 8.2.
2. Summary of Method
2.1 A measured volume of sample, approximately 1-L, is extracted
with methylene chloride using a separatory funnel. The methylene
chloride extract is dried and concentrated to a volume of 10 mL or less.
The extract is then separated by HPLC or GC. Ultraviolet (UV) and
fluorescence detectors are used with HPLC to identify and measure the
PAHs. A flame ionization detector is used with GC.\2\
2.2 The method provides a silica gel column cleanup procedure to aid
in the elimination of interferences that may be encountered.
3. Interferences
3.1 Method interferences may be caused by contaminants in solvents,
reagents, glassware, and other sample processing hardward that lead to
discrete artifacts and/or elevated baselines in the chromatograms. All
of these materials must be routinely demonstrated to be free from
interferences under the conditions of the analysis by running laboratory
reagent blanks as described in Section 8.1.3.
3.1.1 Glassware must be scrupulously cleaned.\3\ Clean all glassware
as soon as possible after use by rinsing with the last solvent used in
it. Solvent rinsing should be followed by detergent washing with hot
water, and rinses with tap water and distilled water. The glassware
should then be drained dry, and heated in a muffle furnace at 400 [deg]C
for 15 to 30 min. Some thermally stable materials, such as PCBs, may not
be eliminated by this treatment. Solvent rinses with acetone and
pesticide quality hexane may be
[[Page 153]]
substituted for the muffle furnace heating. Thorough rinsing with such
solvents usually eliminates PCB interference. Volumetric ware should not
be heated in a muffle furnace. After drying and cooling, glassware
should be sealed and stored in a clean environment to prevent any
accumulation of dust or other contaminants. Store inverted or capped
with aluminum foil.
3.1.2 The use of high purity reagents and solvents helps to minimize
interference problems. Purification of solvents by distillation in all-
glass systems may be required.
3.2 Matrix interferences may be caused by contaminants that are co-
extracted from the sample. The extent of matrix interferences will vary
considerably from source to source, depending upon the nature and
diversity of the industrial complex or municipality being sampled. The
cleanup procedure in Section 11 can be used to overcome many of these
interferences, but unique samples may require additional cleanup
approaches to achieve the MDL listed in Table 1.
3.3 The extent of interferences that may be encountered using liquid
chromatographic techniques has not been fully assessed. Although the
HPLC conditions described allow for a unique resolution of the specific
PAH compounds covered by this method, other PAH compounds may interfere.
4. Safety
4.1 The toxicity or carcinogenicity of each reagent used in this
method have not been precisely defined; however, each chemical compound
should be treated as a potential health hazard. From this viewpoint,
exposure to these chemicals must be reduced to the lowest possible level
by whatever means available. The laboratory is responsible for
maintaining a current awareness file of OSHA regulations regarding the
safe handling of the chemicals specified in this method. A reference
file of material data handling sheets should also be made available to
all personnel involved in the chemical analysis. Additional references
to laboratory safety are available and have been identified
4-6 for the information of the analyst.
4.2 The following parameters covered by this method have been
tentatively classified as known or suspected, human or mammalian
carcinogens: benzo(a)anthracene, benzo(a)pyrene, and dibenzo(a,h)-
anthracene. Primary standards of these toxic compounds should be
prepared in a hood. A NIOSH/MESA approved toxic gas respirator should be
worn when the analyst handles high concentrations of these toxic
compounds.
5. Apparatus and Materials
5.1 Sampling equipment, for discrete or composite sampling.
5.1.1 Grab sample bottle--1-L or 1-qt, amber glass, fitted with a
screw cap lined with Teflon. Foil may be substituted for Teflon if the
sample is not corrosive. If amber bottles are not available, protect
samples from light. The bottle and cap liner must be washed, rinsed with
acetone or methylene chloride, and dried before use to minimize
contamination.
5.1.2 Automatic sampler (optional)--The sampler must incorporate
glass sample containers for the collection of a minimum of 250 mL of
sample. Sample containers must be kept refrigerated at 4 [deg]C and
protected from light during compositing. If the sampler uses a
peristaltic pump, a minimum length of compressible silicone rubber
tubing may be used. Before use, however, the compressible tubing should
be thoroughly rinsed with methanol, followed by repeated rinsings with
distilled water to minimize the potential for contamination of the
sample. An integrating flow meter is required to collect flow
proportional composites.
5.2 Glassware (All specifications are suggested. Catalog numbers are
included for illustration only.):
5.2.1 Separatory funnel--2-L, with Teflon stopcock.
5.2.2 Drying column--Chromatographic column, approximately 400 mm
long x 19 mm ID, with coarse frit filter disc.
5.2.3 Concentrator tube, Kuderna-Danish--10-mL, graduated (Kontes K-
570050-1025 or equivalent). Calibration must be checked at the volumes
employed in the test. Ground glass stopper is used to prevent
evaporation of extracts.
5.2.4 Evaporative flask, Kuderna-Danish--500-mL (Kontes K-570001-
0500 or equivalent). Attach to concentrator tube with springs.
5.2.5 Snyder column, Kuderna-Danish--Three-ball macro (Kontes K-
503000-0121 or equivalent).
5.2.6 Snyder column, Kuderna-Danish--Two-ball micro (Kontes K-
569001-0219 or equivalent).
5.2.7 Vials--10 to 15-mL, amber glass, with Teflon-lined screw cap.
5.2.8 Chromatographic column--250 mm long x 10 mm ID, with coarse
frit filter disc at bottom and Teflon stopcock.
5.3 Boiling chips--Approximately 10/40 mesh. Heat to 400 [deg]C for
30 min or Soxhlet extract with methylene chloride.
5.4 Water bath--Heated, with concentric ring cover, capable of
temperature control (2 [deg]C). The bath should be
used in a hood.
5.5 Balance--Analytical, capable of accurately weighing 0.0001 g.
5.6 High performance liquid chromatograph (HPLC)--An analytical
system complete with column supplies, high pressure syringes, detectors,
and compatible strip-chart recorder. A data system is recommended for
measuring peak areas and retention times.
5.6.1 Gradient pumping system--Constant flow.
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5.6.2 Reverse phase column--HC-ODS Sil-X, 5 micron particle
diameter, in a 25 cm x 2.6 mm ID stainless steel column (Perkin Elmer
No. 089-0716 or equivalent). This column was used to develop the method
performance statements in Section 15. Guidelines for the use of
alternate column packings are provided in Section 12.2.
5.6.3 Detectors--Fluorescence and/or UV detectors. The fluorescence
detector is used for excitation at 280 nm and emission greater than 389
nm cutoff (Corning 3-75 or equivalent). Fluorometers should have
dispersive optics for excitation and can utilize either filter or
dispersive optics at the emission detector. The UV detector is used at
254 nm and should be coupled to the fluorescence detector. These
detectors were used to develop the method performance statements in
Section 15. Guidelines for the use of alternate detectors are provided
in Section 12.2.
5.7 Gas chromatograph--An analytical system complete with
temperature programmable gas chromatograph suitable for on-column or
splitless injection and all required accessories including syringes,
analytical columns, gases, detector, and strip-chart recorder. A data
system is recommended for measuring peak areas.
5.7.1 Column--1.8 m long x 2 mm ID glass, packed with 3% OV-17 on
Chromosorb W-AW-DCMS (100/120 mesh) or equivalent. This column was used
to develop the retention time data in Table 2. Guidelines for the use of
alternate column packings are provided in Section 13.3.
5.7.2 Detector--Flame ionization detector. This detector has proven
effective in the analysis of wastewaters for the parameters listed in
the scope (Section 1.1), excluding the four pairs of unresolved
compounds listed in Section 1.3. Guidelines for the use of alternate
detectors are provided in Section 13.3.
6. Reagents
6.1 Reagent water--Reagent water is defined as a water in which an
interferent is not observed at the MDL of the parameters of interest.
6.2 Sodium thiosulfate--(ACS) Granular.
6.3 Cyclohexane, methanol, acetone, methylene chloride, pentane--
Pesticide quality or equivalent.
6.4 Acetonitrile--HPLC quality, distilled in glass.
6.5 Sodium sulfate--(ACS) Granular, anhydrous. Purify by heating at
400 [deg]C for 4 h in a shallow tray.
6.6 Silica gel--100/200 mesh, desiccant, Davison, grade-923 or
equivalent. Before use, activate for at least 16 h at 130 [deg]C in a
shallow glass tray, loosely covered with foil.
6.7 Stock standard solutions (1.00 [micro]g/[micro]L)--Stock
standard solutions can be prepared from pure standard materials or
purchased as certified solutions.
6.7.1 Prepare stock standard solutions by accurately weighing about
0.0100 g of pure material. Dissolve the material in acetonitrile and
dilute to volume in a 10-mL volumetric flask. Larger volumes can be used
at the convenience of the analyst. When com pound purity is assayed to
be 96% or greater, the weight can be used without cor rection to
calculate the concentration of the stock standard. Commercially prepared
stock standards can be used at any concentration if they are certified
by the manufacturer or by an independent source.
6.7.2 Transfer the stock standard solutions into Teflon-sealed
screw-cap bottles. Store at 4 [deg]C and protect from light. Stock
standard solutions should be checked frequently for signs of degradation
or evaporation, especially just prior to preparing calibration standards
from them.
6.7.3 Stock standard solutions must be replaced after six months, or
sooner if comparison with check standards indicates a problem.
6.8 Quality control check sample concentrate--See Section 8.2.1.
7. Calibration
7.1 Establish liquid or gas chroma tog ra phic operating conditions
equivalent to those given in Table 1 or 2. The chromatographic system
can be calibrated using the external standard technique (Section 7.2) or
the internal standard technique (Section 7.3).
7.2 External standard calibration procedure:
7.2.1 Prepare calibration standards at a minimum of three
concentration levels for each parameter of interest by adding volumes of
one or more stock standards to a volumetric flask and diluting to volume
with acetonitrile. One of the external standards should be at a
concentration near, but above, the MDL (Table 1) and the other
concentrations should correspond to the expected range of concentrations
found in real samples or should define the working range of the
detector.
7.2.2 Using injections of 5 to 25 [micro]L for HPLC and 2 to 5
[micro]L for GC, analyze each calibration standard according to Section
12 or 13, as appropriate. Tabulate peak height or area responses against
the mass injected. The results can be used to prepare a calibration
curve for each compound. Alternatively, if the ratio of response to
amount injected (calibration factor) is a constant over the working
range (<10% relative standard deviation, RSD), linearity through the
origin can be assumed and the average ratio or calibration factor can be
used in place of a calibration curve.
7.3 Internal standard calibration procedure--To use this approach,
the analyst must select one or more internal standards that are similar
in analytical behavior to the
[[Page 155]]
compounds of interest. The analyst must further demonstrate that the
measurement of the internal standard is not affected by method or matrix
interferences. Because of these limitations, no internal standard can be
suggested that is applicable to all samples.
7.3.1 Prepare calibration standards at a minimum of three
concentration levels for each parameter of interest by adding volumes of
one or more stock standards to a volumetric flask. To each calibration
standard, add a known constant amount of one or more internal standards,
and dilute to volume with acetonitrile. One of the standards should be
at a concentration near, but above, the MDL and the other concentrations
should correspond to the expected range of concentrations found in real
samples or should define the working range of the detector.
7.3.2 Using injections of 5 to 25 [micro]L for HPLC and 2 to 5
[micro]L for GC, analyze each calibration standard according to Section
12 or 13, as appropriate. Tabulate peak height or area responses against
concentration for each compound and internal standard. Calculate
response factors (RF) for each compound using Equation 1.
[GRAPHIC] [TIFF OMITTED] TC15NO91.113
Equation 1
where:
As=Response for the parameter to be measured.
Ais=Response for the internal standard.
Cis=Concentration of the internal standard ([micro]g/L).
Cs=Concentration of the parameter to be measured ([micro]g/
L).
If the RF value over the working range is a constant (<10% RSD), the RF
can be assumed to be invariant and the average RF can be used for
calculations. Alternatively, the results can be used to plot a
calibration curve of response ratios, As/Ais, vs.
RF.
7.4 The working calibration curve, calibration factor, or RF must be
verified on each working day by the measurement of one or more
calibration standards. If the response for any parameter varies from the
predicted response by more than 15%, the test must
be repeated using a fresh calibration standard. Alternatively, a new
calibration curve must be prepared for that compound.
7.5 Before using any cleanup procedure, the analyst must process a
series of calibration standards through the procedure to validate
elution patterns and the absence of interferences from the reagents.
8. Quality Control
8.1 Each laboratory that uses this method is required to operate a
formal quality control program. The minimum requirements of this program
consist of an initial demonstration of laboratory capability and an
ongoing analysis of spiked samples to evaluate and document data
quality. The laboratory must maintain records to document the quality of
data that is generated. Ongoing data quality checks are compared with
established performance criteria to determine if the results of analyses
meet the performance characteristics of the method. When results of
sample spikes indicate atypical method performance, a quality control
check standard must be analyzed to confirm that the measurements were
performed in an in-control mode of operation.
8.1.1 The analyst must make an initial, one-time, demonstration of
the ability to generate acceptable accuracy and precision with this
method. This ability is established as described in Section 8.2.
8.1.2 In recognition of advances that are occurring in
chromatography, the analyst is permitted certain options (detailed in
Sections 10.4, 11.1, 12.2, and 13.3) to improve the separations or lower
the cost of measurements. Each time such a modification is made to the
method, the analyst is required to repeat the procedure in Section 8.2.
8.1.3 Before processing any samples the analyst must analyze a
reagent water blank to demonstrate that interferences from the
analytical system and glassware are under control. Each time a set of
samples is extracted or reagents are changed a reagent water blank must
be processed as a safeguard against laboratory contamination.
8.1.4 The laboratory must, on an ongoing basis, spike and analyze a
minimum of 10% of all samples to monitor and evaluate laboratory data
quality. This procedure is described in Section 8.3.
8.1.5 The laboratory must, on an ongoing basis, demonstrate through
the analyses of quality control check standards that the operation of
the measurement system is in control. This procedure is described in
Section 8.4. The frequency of the check standard analyses is equivalent
to 10% of all samples analyzed but may be reduced if spike recoveries
from samples (Section 8.3) meet all specified quality control criteria.
8.1.6 The laboratory must maintain performance records to document
the quality of data that is generated. This procedure is described in
Section 8.5.
8.2 To establish the ability to generate acceptable accuracy and
precision, the analyst must perform the following operations.
8.2.1 A quality control (QC) check sample concentrate is required
containing each parameter of interest at the following concentrations in
acetonitrile: 100 [micro]g/mL of any
[[Page 156]]
of the six early-eluting PAHs (naphthalene, acenaphthylene,
acenaphthene, fluorene, phenanthrene, and anthracene); 5 [micro]g/mL of
benzo(k)fluoranthene; and 10 [micro]g/mL of any of the other PAHs. The
QC check sample concentrate must be obtained from the U.S. Environmental
Protection Agency, Environmental Monitoring and Support Laboratory in
Cincinnati, Ohio, if available. If not available from that source, the
QC check sample concentrate must be obtained from another external
source. If not available from either source above, the QC check sample
concentrate must be prepared by the laboratory using stock standards
prepared independently from those used for calibration.
8.2.2 Using a pipet, prepare QC check samples at the test
concentrations shown in Table 3 by adding 1.00 mL of QC check sample
concentrate to each of four 1-L aliquots of reagent water.
8.2.3 Analyze the well-mixed QC check samples according to the
method beginning in Section 10.
8.2.4 Calculate the average recovery (X) in [micro]g/L, and the
standard deviation of the recovery (s) in [micro]g/L, for each parameter
using the four results.
8.2.5 For each parameter compare s and X with the corresponding
acceptance criteria for precision and accuracy, respectively, found in
Table 3. If s and X for all parameters of interest meet the acceptance
criteria, the system performance is acceptable and analysis of actual
samples can begin. If any individual s exceeds the precision limit or
any individual X falls outside the range for accuracy, the system
performance is unacceptable for that parameter.
Note: The large number of parameters in Table 3 present a
substantial probability that one or more will fail at least one of the
acceptance criteria when all parameters are analyzed.
8.2.6 When one or more of the parameters tested fail at least one of
the acceptance criteria, the analyst must proceed according to Section
8.2.6.1 or 8.2.6.2.
8.2.6.1 Locate and correct the source of the problem and repeat the
test for all parameters of interest beginning with Section 8.2.2.
8.2.6.2 Beginning with Section 8.2.2, repeat the test only for those
parameters that failed to meet criteria. Repeated failure, however, will
confirm a general problem with the measurement system. If this occurs,
locate and correct the source of the problem and repeat the test for all
compounds of interest beginning with Section 8.2.2.
8.3 The laboratory must, on an ongoing basis, spike at least 10% of
the samples from each sample site being monitored to assess accuracy.
For laboratories analyzing one to ten samples per month, at least one
spiked sample per month is required.
8.3.1 The concentration of the spike in the sample should be
determined as follows:
8.3.1.1 If, as in compliance monitoring, the concentration of a
specific parameter in the sample is being checked against a regulatory
concentration limit, the spike should be at that limit or 1 to 5 times
higher than the background concentration determined in Section 8.3.2,
whichever concentration would be larger.
8.3.1.2 If the concentration of a specific parameter in the sample
is not being checked against a limit specific to that parameter, the
spike should be at the test concentration in Section 8.2.2 or 1 to 5
times higher than the background concentration determined in Section
8.3.2, whichever concentration would be larger.
8.3.1.3 If it is impractical to determine background levels before
spiking (e.g., maximum holding times will be exceeded), the spike
concentration should be (1) the regulatory concentration limit, if any;
or, if none, (2) the larger of either 5 times higher than the expected
background concentration or the test concentration in Section 8.2.2.
8.3.2 Analyze one sample aliquot to determine the background
concentration (B) of each parameter. If necessary, prepare a new QC
check sample concentrate (Section 8.2.1) appropriate for the background
concentrations in the sample. Spike a second sample aliquot with 1.0 mL
of the QC check sample concentrate and analyze it to determine the
concentration after spiking (A) of each parameter. Calculate each
percent recovery (P) as 100 (A-B)%/T, where T is the known true value of
the spike.
8.3.3 Compare the percent recovery (P) for each parameter with the
corresponding QC acceptance criteria found in Table 3. These acceptance
criteria were calculated to include an allowance for error in
measurement of both the background and spike concentrations, assuming a
spike to background ratio of 5:1. This error will be accounted for to
the extent that the analyst's spike to background ratio approaches
5:1.\7\ If spiking was performed at a concentration lower than the test
concentration in Section 8.2.2, the analyst must use either the QC
acceptance criteria in Table 3, or optional QC acceptance criteria
calculated for the specific spike concentration. To calculate optional
acceptance criteria for the recovery of a parameter: (1) Calculate
accuracy (X') using the equation in Table 4, substituting the spike
concentration (T) for C; (2) calculate overall precision (S') using the
equation in Table 4, substituting X' for X; (3) calculate the range for
recovery at the spike concentration as (100 X'/T)2.44(100 S'/T)%.\7\
8.3.4 If any individual P falls outside the designated range for
recovery, that parameter has failed the acceptance criteria. A check
standard containing each parameter
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that failed the critiera must be analyzed as described in Section 8.4.
8.4 If any parameter fails the acceptance criteria for recovery in
Section 8.3, a QC check standard containing each parameter that failed
must be prepared and analyzed.
Note: The frequency for the required analysis of a QC check standard
will depend upon the number of parameters being simultaneously tested,
the complexity of the sample matrix, and the performance of the
laboratory. If the entire list of parameters in Table 3 must be measured
in the sample in Section 8.3, the probability that the analysis of a QC
check standard will be required is high. In this case the QC check
standard should be routinely analyzed with the spike sample.
8.4.1 Prepare the QC check standard by adding 1.0 mL of QC check
sample concentrate (Section 8.2.1 or 8.3.2) to 1 L of reagent water. The
QC check standard needs only to contain the parameters that failed
criteria in the test in Section 8.3.
8.4.2 Analyze the QC check standard to determine the concentration
measured (A) of each parameter. Calculate each percent recovery
(Ps) as 100 (A/T)%, where T is the true value of the standard
concentration.
8.4.3 Compare the percent recovery (Ps) for each
parameter with the corresponding QC acceptance criteria found in Table
3. Only parameters that failed the test in Section 8.3 need to be
compared with these criteria. If the recovery of any such parameter
falls outside the designated range, the laboratory performance for that
parameter is judged to be out of control, and the problem must be
immediately identified and corrected. The analytical result for that
parameter in the unspiked sample is suspect and may not be reported for
regulatory compliance purposes.
8.5 As part of the QC program for the laboratory, method accuracy
for wastewater samples must be assessed and records must be maintained.
After the analysis of five spiked wastewater samples as in Section 8.3,
calculate the average percent recovery (P) and the standard deviation of
the percent recovery (sp). Express the accuracy assessment as
a percent recovery interval from P-2sp to P+2sp.
If P=90% and sp=10%, for example, the accuracy interval is
expressed as 70-110%. Update the accuracy assessment for each parameter
on a regular basis (e.g. after each five to ten new accuracy
measurements).
8.6 It is recommended that the laboratory adopt additional quality
assurance practices for use with this method. The specific practices
that are most productive depend upon the needs of the laboratory and the
nature of the samples. Field duplicates may be analyzed to assess the
precision of the environmental measurements. When doubt exists over the
identification of a peak on the chromatogram, confirmatory techniques
such as gas chromatography with a dissimilar column, specific element
detector, or mass spectrometer must be used. Whenever possible, the
laboratory should analyze standard reference materials and participate
in relevant performance evaluation studies.
9. Sample Collection, Preservation, and Handling
9.1 Grab samples must be collected in glass containers. Conventional
sampling practices \8\ should be followed, except that the bottle must
not be prerinsed with sample before collection. Composite samples should
be collected in refrigerated glass containers in accordance with the
requirements of the program. Automatic sampling equipment must be as
free as possible of Tygon tubing and other potential sources of
contamination.
9.2 All samples must be iced or refrigerated at 4 [deg]C from the
time of collection until extraction. PAHs are known to be light
sensitive; therefore, samples, extracts, and standards should be stored
in amber or foil-wrapped bottles in order to minimize photolytic
decomposition. Fill the sample bottles and, if residual chlorine is
present, add 80 mg of sodium thiosulfate per liter of sample and mix
well. EPA Methods 330.4 and 330.5 may be used for measurement of
residual chlorine.\9\ Field test kits are available for this purpose.
9.3 All samples must be extracted within 7 days of collection and
completely analyzed within 40 days of extraction.\2\
10. Sample Extraction
10.1 Mark the water meniscus on the side of the sample bottle for
later determination of sample volume. Pour the entire sample into a 2-L
separatory funnel.
10.2 Add 60 mL of methylene chloride to the sample bottle, seal, and
shake 30 s to rinse the inner surface. Transfer the solvent to the
separatory funnel and extract the sample by shaking the funnel for 2
min. with periodic venting to release excess pressure. Allow the organic
layer to separate from the water phase for a minimum of 10 min. If the
emulsion interface between layers is more than one-third the volume of
the solvent layer, the analyst must employ mechanical techniques to
complete the phase separation. The optimum technique depends upon the
sample, but may include stirring, filtration of the emulsion through
glass wool, centrifugation, or other physical methods. Collect the
methylene chloride extract in a 250-mL Erlenmeyer flask.
10.3 Add a second 60-mL volume of methylene chloride to the sample
bottle and repeat the extraction procedure a second time, combining the
extracts in the Erlenmeyer flask. Perform a third extraction in the same
manner.
[[Page 158]]
10.4 Assemble a Kuderna-Danish (K-D) concentrator by attaching a 10-
mL concentrator tube to a 500-mL evaporative flask. Other concentration
devices or techniques may be used in place of the K-D concentrator if
the requirements of Section 8.2 are met.
10.5 Pour the combined extract through a solvent-rinsed drying
column containing about 10 cm of anhydrous sodium sulfate, and collect
the extract in the K-D concentrator. Rinse the Erlenmeyer flask and
column with 20 to 30 mL of methylene chloride to complete the
quantitative transfer.
10.6 Add one or two clean boiling chips to the evaporative flask and
attach a three-ball Snyder column. Prewet the Snyder column by adding
about 1 mL of methylene chloride to the top. Place the K-D apparatus on
a hot water bath (60 to 65 [deg]C) so that the concentrator tube is
partially immersed in the hot water, and the entire lower rounded
surface of the flask is bathed with hot vapor. Adjust the vertical
position of the apparatus and the water temperature as required to
complete the concentration in 15 to 20 min. At the proper rate of
distillation the balls of the column will actively chatter but the
chambers will not flood with condensed solvent. When the apparent volume
of liquid reaches 1 mL, remove the K-D apparatus and allow it to drain
and cool for at least 10 min.
10.7 Remove the Snyder column and rinse the flask and its lower
joint into the concentrator tube with 1 to 2 mL of methylene chloride. A
5-mL syringe is recommended for this operation. Stopper the concentrator
tube and store refrigerated if further processing will not be performed
immediately. If the extract will be stored longer than two days, it
should be transferred to a Teflon-sealed screw-cap vial and protected
from light. If the sample extract requires no further cleanup, proceed
with gas or liquid chromatographic analysis (Section 12 or 13). If the
sample requires further cleanup, proceed to Section 11.
10.8 Determine the original sample volume by refilling the sample
bottle to the mark and transferring the liquid to a 1000-mL graduated
cylinder. Record the sample volume to the nearest 5 mL.
11. Cleanup and Separation
11.1 Cleanup procedures may not be necessary for a relatively clean
sample matrix. If particular circumstances demand the use of a cleanup
procedure, the analyst may use the procedure below or any other
appropriate procedure. However, the analyst first must demonstrate that
the requirements of Section 8.2 can be met using the methods as revised
to incorporate the cleanup procedure.
11.2 Before the silica gel cleanup technique can be utilized, the
extract solvent must be exchanged to cyclohexane. Add 1 to 10 mL of the
sample extract (in methylene chloride) and a boiling chip to a clean K-D
concentrator tube. Add 4 mL of cyclohexane and attach a two-ball micro-
Snyder column. Prewet the column by adding 0.5 mL of methylene chloride
to the top. Place the micro-K-D apparatus on a boiling (100 [deg]C)
water bath so that the concentrator tube is partially immersed in the
hot water. Adjust the vertical position of the apparatus and the water
temperature as required to complete concentration in 5 to 10 min. At the
proper rate of distillation the balls of the column will actively
chatter but the chambers will not flood. When the apparent volume of the
liquid reaches 0.5 mL, remove the K-D apparatus and allow it to drain
and cool for at least 10 min. Remove the micro-Snyder column and rinse
its lower joint into the concentrator tube with a minimum amount of
cyclohexane. Adjust the extract volume to about 2 mL.
11.3 Silica gel column cleanup for PAHs:
11.3.1 Prepare a slurry of 10 g of activiated silica gel in
methylene chloride and place this into a 10-mm ID chromatographic
column. Tap the column to settle the silica gel and elute the methylene
chloride. Add 1 to 2 cm of anhydrous sodium sulfate to the top of the
silica gel.
11.3.2 Preelute the column with 40 mL of pentane. The rate for all
elutions should be about 2 mL/min. Discard the eluate and just prior to
exposure of the sodium sulfate layer to the air, transfer the 2-mL
cyclohexane sample extract onto the column using an additional 2 mL
cyclohexane to complete the transfer. Just prior to exposure of the
sodium sulfate layer to the air, add 25 mL of pentane and continue the
elution of the column. Discard this pentane eluate.
11.3.3 Next, elute the column with 25 mL of methylene chloride/
pentane (4+6)(V/V) into a 500-mL K-D flask equipped with a 10-mL
concentrator tube. Concentrate the collected fraction to less than 10 mL
as in Section 10.6. When the apparatus is cool, remove the Snyder column
and rinse the flask and its lower joint with pentane. Proceed with HPLC
or GC analysis.
12. High Performance Liquid Chromatography
12.1 To the extract in the concentrator tube, add 4 mL of
acetonitrile and a new boiling chip, then attach a two-ball micro-Snyder
column. Concentrate the solvent as in Section 10.6, except set the water
bath at 95 to 100 [deg]C. When the apparatus is cool, remove the micro-
Snyder column and rinse its lower joint into the concentrator tube with
about 0.2 mL of acetonitrile. Adjust the extract volume to 1.0 mL.
12.2 Table 1 summarizes the recommended operating conditions for the
HPLC. Included in this table are retention times, capacity factors, and
MDL that can be achieved under these conditions. The UV detector is
recommended for the determination of naphthalene, acenaphthylene,
acenapthene, and
[[Page 159]]
fluorene and the fluorescence detector is recommended for the remaining
PAHs. Examples of the separations achieved by this HPLC column are shown
in Figures 1 and 2. Other HPLC columns, chromatographic conditions, or
detectors may be used if the requirements of Section 8.2 are met.
12.3 Calibrate the system daily as described in Section 7.
12.4 If the internal standard calibration procedure is being used,
the internal standard must be added to the sample extract and mixed
thoroughly immediately before injection into the instrument.
12.5 Inject 5 to 25 [micro]L of the sample extract or standard into
the HPLC using a high pressure syringe or a constant volume sample
injection loop. Record the volume injected to the nearest 0.1 [micro]L,
and the resulting peak size in area or peak height units. Re-equilibrate
the HPLC column at the initial gradient conditions for at least 10 min
between injections.
12.6 Identify the parameters in the sam ple by comparing the
retention time of the peaks in the sample chromatogram with those of the
peaks in standard chromatograms. The width of the retention time window
used to make identifications should be based upon measurements of actual
retention time variations of standards over the course of a day. Three
times the standard deviation of a retention time for a compound can be
used to calculate a suggested window size; however, the experience of
the analyst should weigh heavily in the interpretation of chromatograms.
12.7 If the response for a peak exceeds the working range of the
system, dilute the extract with acetonitrile and reanalyze.
12.8 If the measurement of the peak response is prevented by the
presence of interferences, further cleanup is required.
13. Gas Chromatography
13.1 The packed column GC procedure will not resolve certain
isomeric pairs as indicated in Section 1.3 and Table 2. The liquid
chromatographic procedure (Section 12) must be used for these
parameters.
13.2 To achieve maximum sensitivity with this method, the extract
must be concentrated to 1.0 mL. Add a clean boiling chip to the
methylene chloride extract in the concentrator tube. Attach a two-ball
micro-Snyder column. Prewet the micro-Snyder column by adding about 0.5
mL of methylene chloride to the top. Place the micro-K-D apparatus on a
hot water bath (60 to 65 [deg]C) so that the concentrator tube is
partially immersed in the hot water. Adjust the vertical position of the
apparatus and the water temperature as required to complete the
concentration in 5 to 10 min. At the proper rate of distillation the
balls will actively chatter but the chambers will not flood. When the
apparent volume of liquid reaches 0.5 mL, remove the K-D apparatus and
allow it to drain and cool for at least 10 min. Remove the micro-Snyder
column and rinse its lower joint into the concentrator tube with a
minimum amount of methylene chloride. Adjust the final volume to 1.0 mL
and stopper the concentrator tube.
13.3 Table 2 summarizes the recommended operating conditions for the
gas chromatograph. Included in this table are retention times that were
obtained under these conditions. An example of the separations achieved
by this column is shown in Figure 3. Other packed or capillary (open-
tubular) columns, chromatographic conditions, or detectors may be used
if the requirements of Section 8.2 are met.
13.4 Calibrate the gas chromatographic system daily as described in
Section 7.
13.5 If the internal standard calibration procedure is being used,
the internal standard must be added to the sample extract and mixed
thoroughly immediately before injection into the gas chromatograph.
13.6 Inject 2 to 5 [micro]L of the sample extract or standard into
the gas chromatograph using the solvent-flush technique.\10\ Smaller
(1.0 [micro]L) volumes may be injected if automatic devices are
employed. Record the volume injected to the nearest 0.05 [micro]L, and
the resulting peak size in area or peak height units.
13.7 Identify the parameters in the sample by comparing the
retention times of the peaks in the sample chromatogram with those of
the peaks in standard chromatograms. The width of the retention time
window used to make identifications should be based upon measurements of
actual retention time variations of standards over the course of a day.
Three times the standard deviation of a retention time for a compound
can be used to calculate a suggested window size; however, the
experience of the analyst should weigh heavily in the interpretation of
chromatograms.
13.8 If the response for a peak exceeds the working range of the
system, dilute the extract and reanalyze.
13.9 If the measurement of the peak response is prevented by the
presence of interferences, further cleanup is required.
14. Calculations
14.1 Determine the concentration of individual compounds in the
sample.
14.1.1 If the external standard calibration procedure is used,
calculate the amount of material injected from the peak response using
the calibration curve or calibration factor determined in Section 7.2.2.
The concentration in the sample can be calculated from Equation 2.
[[Page 160]]
[GRAPHIC] [TIFF OMITTED] TC15NO91.114
Equation 2
where:
A=Amount of material injected (ng).
Vi=Volume of extract injected ([micro]L).
Vt=Volume of total extract ([micro]L).
Vs=Volume of water extracted (mL).
13.1.2 If the internal standard calibration procedure is used,
calculate the concentration in the sample using the response factor (RF)
determined in Section 7.3.2 and Equation 3.
[GRAPHIC] [TIFF OMITTED] TC15NO91.115
Equation 3
where:
As=Response for the parameter to be measured.
Ais=Response for the internal standard.
Is=Amount of internal standard added to each extract
([micro]g).
Vo=Volume of water extracted (L).
14.2 Report results in [micro]g/L without correction for recovery
data. All QC data obtained should be reported with the sample results.
15. Method Performance
15.1 The method detection limit (MDL) is defined as the minimum
concentration of a substance that can be measured and reported with 99%
confidence that the value is above zero.\1\ The MDL concentrations
listed in Table 1 were obtained using reagent water.\11\ Similar results
were achieved using representative wastewaters. MDL for the GC approach
were not determined. The MDL actually achieved in a given analysis will
vary depending on instrument sensitivity and matrix effects.
15.2 This method has been tested for linearity of spike recovery
from reagent water and has been demonstrated to be applicable over the
concentration range from 8 x MDL to 800 x MDL\11\ with the following
exception: benzo(ghi)perylene recovery at 80 x and 800 x MDL were low
(35% and 45%, respectively).
15.3 This method was tested by 16 laboratories using reagent water,
drinking water, surface water, and three industrial wastewaters spiked
at six concentrations over the range 0.1 to 425 [micro]g/L.\12\ Single
operator precision, overall precision, and method accuracy were found to
be directly related to the concentration of the parameter and
essentially independent of the sample matrix. Linear equations to
describe these relationships are presented in Table 4.
References
1. 40 CFR part 136, appendix B.
2. ``Determination of Polynuclear Aromatic Hydrocarbons in
Industrial and Municipal Wastewaters,'' EPA 600/4-82-025, National
Technical Information Service, PB82-258799, Springfield, Virginia 22161,
June 1982.
3. ASTM Annual Book of Standards, Part 31, D3694-78. ``Standard
Practices for Preparation of Sample Containers and for Preservation of
Organic Constituents,'' American Society for Testing and Materials,
Philadelphia.
4. ``Carcinogens--Working With Carcinogens,'' Department of Health,
Education, and Welfare, Public Health Service, Center for Disease
Control, National Institute for Occupational Safety and Health,
Publication No. 77-206, August 1977.
5. ``OSHA Safety and Health Standards, General Industry,'' (29 CFR
part 1910), Occupational Safety and Health Administration, OSHA 2206
(Revised, January 1976).
6. ``Safety in Academic Chemistry Laboratories,'' American Chemical
Society Publication, Committee on Chemical Safety, 3rd Edition, 1979.
7. Provost, L.P., and Elder, R.S. ``Interpretation of Percent
Recovery Data,'' American Laboratory, 15, 58-63 (1983). (The value 2.44
used in the equation in Section 8.3.3 is two times the value 1.22
derived in this report.)
8. ASTM Annual Book of Standards, Part 31, D3370-76. ``Standard
Practices for Sampling Water,'' American Society for Testing and
Materials, Philadelphia.
9. ``Methods 330.4 (Titrimetric, DPD-FAS) and 330.5
(Spectrophotometric, DPD) for Chlorine, Total Residual,'' Methods for
Chemical Analysis of Water and Wastes, EPA-600/4-79-020, U.S.
Environmental Protection Agency, Environmental Monitoring and Support
Laboratory, Cincinnati, Ohio 45268, March 1979.
10. Burke, J.A. ``Gas Chromatography for Pesticide Residue Analysis;
Some Practical Aspects,'' Journal of the Association of Official
Analytical Chemists, 48, 1037 (1965).
11. Cole, T., Riggin, R., and Glaser, J. ``Evaluation of Method
Detection Limits and Analytical Curve for EPA Method 610--PNAs,''
International Symposium on Polynuclear Aromatic Hydrocarbons, 5th,
Battelle's Columbus Laboratories, Columbus, Ohio (1980).
12. ``EPA Method Study 20, Method 610 (PNA's),'' EPA 600/4-84-063,
National Technical Information Service, PB84-211614, Springfield,
Virginia 22161, June 1984.
[[Page 161]]
Table 1--High Performance Liquid Chromatography Conditions and Method
Detection Limits
------------------------------------------------------------------------
Method
Retention Column detection
Parameter time capacity limit
(min) factor ([micro]g/
(k') L) a
------------------------------------------------------------------------
Naphthalene........................... 16.6 12.2 1.8
Acenaphthylene........................ 18.5 13.7 2.3
Acenaphthene.......................... 20.5 15.2 1.8
Fluorene.............................. 21.2 15.8 0.21
Phenanthrene.......................... 22.1 16.6 0.64
Anthracene............................ 23.4 17.6 0.66
Fluoranthene.......................... 24.5 18.5 0.21
Pyrene................................ 25.4 19.1 0.27
Benzo(a)anthracene.................... 28.5 21.6 0.013
Chrysene.............................. 29.3 22.2 0.15
Benzo(b)fluoranthene.................. 31.6 24.0 0.018
Benzo(k)fluoranthene.................. 32.9 25.1 0.017
Benzo(a)pyrene........................ 33.9 25.9 0.023
Dibenzo(a,h)anthracene................ 35.7 27.4 0.030
Benzo(ghi)perylene.................... 36.3 27.8 0.076
Indeno(1,2,3-cd)pyrene................ 37.4 28.7 0.043
------------------------------------------------------------------------
AAAHPLC column conditions: Reverse phase HC-ODS Sil-X, 5 micron
particle size, in a 25 cm x 2.6 mm ID stainless steel column.
Isocratic elution for 5 min. using acetonitrile/water (4+6), then
linear gradient elution to 100% acetonitrile over 25 min. at 0.5 mL/
min flow rate. If columns having other internal diameters are used,
the flow rate should be adjusted to maintain a linear velocity of 2 mm/
sec.
a The MDL for naphthalene, acenaphthylene, acenaphthene, and fluorene
were determined using a UV detector. All others were determined using
a fluorescence detector.
Table 2--Gas Chromatographic Conditions and Retention Times
------------------------------------------------------------------------
Retention
Parameter time (min)
------------------------------------------------------------------------
Naphthalene................................................. 4.5
Acenaphthylene.............................................. 10.4
Acenaphthene................................................ 10.8
Fluorene.................................................... 12.6
Phenanthrene................................................ 15.9
Anthracene.................................................. 15.9
Fluoranthene................................................ 19.8
Pyrene...................................................... 20.6
Benzo(a)anthracene.......................................... 24.7
Chrysene.................................................... 24.7
Benzo(b)fluoranthene........................................ 28.0
Benzo(k)fluoranthene........................................ 28.0
Benzo(a)pyrene.............................................. 29.4
Dibenzo(a,h)anthracene...................................... 36.2
Indeno(1,2,3-cd)pyrene...................................... 36.2
Benzo(ghi)perylene.......................................... 38.6
------------------------------------------------------------------------
GC Column conditions: Chromosorb W-AW-DCMS (100/120 mesh) coated with 3%
OV-17 packed in a 1.8 x 2 mm ID glass column with nitrogen carrier gas
at 40 mL/min. flow rate. Column temperature was held at 100 [deg]C for
4 min., then programmed at 8 [deg]C/min. to a final hold at 280
[deg]C.
Table 3--QC Acceptance Criteria--Method 610
----------------------------------------------------------------------------------------------------------------
Range for X
Test conc. Limit for s ([micro]g/ Range for
Parameter ([micro]g/ ([micro]g/ L) P, Ps (%)
L) L)
----------------------------------------------------------------------------------------------------------------
Acenaphthene................................................ 100 40.3 D-105.7 D-124
Acenaphthylene.............................................. 100 45.1 22.1-112.1 D-139
Anthracene.................................................. 100 28.7 11.2-112.3 D-126
Benzo(a)anthracene.......................................... 10 4.0 3.1-11.6 12-135
Benzo(a)pyrene.............................................. 10 4.0 0.2-11.0 D-128
Benzo(b)fluor-anthene....................................... 10 3.1 1.8-13.8 6-150
Benzo(ghi)perylene.......................................... 10 2.3 D-10.7 D-116
Benzo(k)fluo-ranthene....................................... 5 2.5 D-7.0 D-159
Chrysene.................................................... 10 4.2 D-17.5 D-199
Dibenzo(a,h)an-thracene..................................... 10 2.0 0.3-10.0 D-110
Fluoranthene................................................ 10 3.0 2.7-11.1 14-123
Fluorene.................................................... 100 43.0 D-119 D-142
Indeno(1,2,3-cd)pyrene...................................... 10 3.0 1.2-10.0 D-116
Naphthalene................................................. 100 40.7 21.5-100.0 D-122
Phenanthrene................................................ 100 37.7 8.4-133.7 D-155
Pyrene...................................................... 10 3.4 1.4-12.1 D-140
----------------------------------------------------------------------------------------------------------------
s=Standard deviation of four recovery measurements, in [micro]g/L (Section 8.2.4).
X=Average recovery for four recovery measurements, in [micro]g/L (Section 8.2.4).
P, Ps=Percent recovery measured (Section 8.3.2, Section 8.4.2).
D=Detected; result must be greater than zero.
Note: These criteria are based directly upon the method performance data in Table 4. Where necessary, the limits
for recovery have been broadened to assure applicability of the limits to concentrations below those used to
develop Table 4.
[[Page 162]]
Table 4--Method Accuracy and Precision as Functions of Concentration--Method 610
----------------------------------------------------------------------------------------------------------------
Accuracy, as Single analyst Overall
Parameter recovery, X' precision, sr' precision, S'
([micro]g/L) ([micro]g/L) ([micro]g/L)
----------------------------------------------------------------------------------------------------------------
Acenaphthene.................................................... 0.52C + 0.54 0.39X + 0.76 0.53X + 1.32
Acenaphthylene.................................................. 0.69C - 1.89 0.36X + 0.29 0.42X + 0.52
Anthracene...................................................... 0.63C - 1.26 0.23X + 1.16 0.41X + 0.45
Benzo(a)anthra cene............................................. 0.73C + 0.05 0.28X + 0.04 0.34X + 0.02
Benzo(a)pyrene.................................................. 0.56C + 0.01 0.38X - 0.01 0.53X - 0.01
Benzo(b)fluoran thene........................................... 0.78C + 0.01 0.21X + 0.01 0.38X - 0.00
Benzo(ghi)peryl ene............................................. 0.44C + 0.30 0.25X + 0.04 0.58X + 0.10
Benzo(k)fluoran thene........................................... 0.59C + 0.00 0.44X - 0.00 0.69X + 0.01
Chrysene........................................................ 0.77C - 0.18 0.32X - 0.18 0.66X - 0.22
Dibenzo(a,h)an thracene......................................... 0.41C + 0.11 0.24X + 0.02 0.45X + 0.03
Fluoranthene.................................................... 0.68C + 0.07 0.22X + 0.06 0.32X + 0.03
Fluorene........................................................ 0.56C - 0.52 0.44X - 1.12 0.63X - 0.65
Indeno(1,2,3-cd)pyrene.......................................... 0.54C + 0.06 0.29X + 0.02 0.42X + 0.01
Naphthalene..................................................... 0.57C - 0.70 0.39X - 0.18 0.41X + 0.74
Phenanthrene.................................................... 0.72C - 0.95 0.29X + 0.05 0.47X - 0.25
Pyrene.......................................................... 0.69C - 0.12 0.25X + 0.14 0.42X - 0.00
----------------------------------------------------------------------------------------------------------------
X'=Expected recovery for one or more measurements of a sample containing a concentration of C, in [micro]g/L.
sr'=Expected single analyst standard deviation of measurements at an average concentration found of X, in
[micro]g/L.
S'=Expected interlaboratory standard deviation of measurements at an average concentration found of X, in
[micro]g/L.
C=True value for the concentration, in [micro]g/L.
X=Average recovery found for measurements of samples containing a concentration of C, in [micro]g/L.
[GRAPHIC] [TIFF OMITTED] TC02JY92.031
[[Page 163]]
[GRAPHIC] [TIFF OMITTED] TC02JY92.032
[[Page 164]]
[GRAPHIC] [TIFF OMITTED] TC02JY92.033
Method 611--Haloethers
1. Scope and Application
1.1 This method covers the determination of certain haloethers. The
following parameters can be determined by this method:
------------------------------------------------------------------------
Parameter STORET No. CAS No.
------------------------------------------------------------------------
Bis(2-chloroethyl) ether...................... 34273 111-44-4
Bis(2-chloroethoxy) methane................... 34278 111-91-1
Bis(2-chloroisopropyl) ether.................. 34283 108-60-1
4-Bromophenyl phenyl ether.................... 34636 101-55-3
4-Chlorophenyl phenyl either.................. 34641 7005-72-3
------------------------------------------------------------------------
1.2 This is a gas chromatographic (GC) method applicable to the
determination of the compounds listed above in municipal and industrial
discharges as provided under 40 CFR 136.1. When this method is used to
analyze unfamiliar samples for any or all of the compounds above,
compound identifications should be supported by at least one additional
qualitative technique. This method describes analytical conditions for a
second gas chromatographic column that can be used to confirm
measurements made with the primary column. Method 625 provides gas
chromatograph/mass spectrometer (GC/MS) conditions appropriate for the
qualitative and quantitative confirmation of results for all of the
parameters listed above, using the extract produced by this method.
1.3 The method detection limit (MDL, defined in Section
14.1)1 for each parameter is listed in Table 1. The MDL for a
specific wastewater may differ from those listed, depending upon the
nature of interferences in the sample matrix.
1.4 The sample extraction and concentration steps in this method are
essentially the same as in Methods 606, 608, 609, and 612. Thus, a
single sample may be extracted to measure the parameters included in the
scope of each of these methods. When cleanup is required, the
concentration levels must be high enough to permit selecting aliquots,
as necessary, to apply appropriate cleanup procedures. The analyst is
allowed the latitude, under Section 12, to select
[[Page 165]]
chromatographic conditions appropriate for the simultaneous measurement
of combinations of these parameters.
1.5 Any modification of this method, beyond those expressly
permitted, shall be considered as a major modification subject to
application and approval of alternate test procedures under 40 CFR 136.4
and 136.5.
1.6 This method is restricted to use by or under the supervision of
analysts experienced in the use of a gas chromatograph and in the
interpretation of gas chromatograms. Each analyst must demonstrate the
ability to generate acceptable results with this method using the
procedure described in Section 8.2.
2. Summary of Method
2.1 A measured volume of sample, approximately 1-L, is extracted
with methylene chloride using a separatory funnel. The methylene
chloride extract is dried and exchanged to hexane during concentration
to a volume of 10 mL or less. The extract is separated by gas
chromatography and the parameters are then measured with a halide
specific detector.2
2.2 The method provides a Florisil column cleanup procedure to aid
in the elimination of interferences that may be encountered.
3. Interferences
3.1 Method interferences may be caused by contaminants in solvents,
reagents, glassware, and other sample processing hardware that lead to
discrete artifacts and/or elevated baselines in gas chromatograms. All
of these materials must be routinely demonstrated to be free from
interferences under the conditions of the analysis by running laboratory
reagent blanks as described in Section 8.1.3.
3.1.1 Glassware must be scrupulously cleaned.3 Clean all
glassware as soon as possible after use by rinsing with the last solvent
used in it. Solvent rinsing should be followed be detergent washing with
hot water, and rinses with tap water and distilled water. The glassware
should then be drained dry, and heated in a muffle furnace at 400 [deg]C
for 15 to 30 min. Some thermally stable materials, such a PCBs, may not
be eliminated by this treatment. Solvent rinses with acetone and
pesticide quality hexane may be substituted for the muffle furnace
heating. Thorough rinsing with such solvents usually eliminates PCB
interference. Volumetric ware should not be heated in a muffle furnace.
After drying and cooling, glassware should be sealed and stored in a
clean environment to prevent any accumulation of dust or other
contaminants. Store inverted or capped with aluminum foil.
3.1.2 The use of high purity reagents and solvents helps to minimize
interference problems. Purification of solvents by distillation in all-
glass systems may be required.
3.2 Matrix interferences may be caused by contaminants that are co-
extracted from the sample. The extent of matrix interferences will vary
considerably from source to source, depending upon the nature and
diversity of the industrial complex or municipality being sampled. The
cleanup procedure in Section 11 can be used to overcome many of these
interferences, but unique samples may require additional cleanup
approaches to achieve the MDL listed in Table 1.
3.3 Dichlorobenzenes are known to coelute with haloethers under some
gas chromatographic conditions. If these materials are present together
in a sample, it may be necessary to analyze the extract with two
different column packings to completely resolve all of the compounds.
4. Safety
4.1 The toxicity or carcinogenicity of each reagent used in this
method has not been precisely defined; however, each chemical compound
should be treated as a potential health hazard. From this viewpoint,
exposure to these chemicals must be reduced to the lowest possible level
by whatever means available. The laboratory is responsible for
maintaining a current awareness file of OSHA regulations regarding the
safe handling of the chemicals specified in this method. A reference
file of material data handling sheets should also be made available to
all personnel involved in the chemical analysis. Additional references
to laboratory safety are available and have been identified
4-6 for the information of the analyst.
5. Apparatus and Materials
5.1 Sampling equipment, for discrete or composite sampling.
5.1.1 Grab sample bottle--1-L or 1-qt, amber glass, fitted with a
screw cap lined with Teflon. Foil may be substituted for Teflon if the
sample is not corrosive. If amber bottles are not available, protect
samples from light. The bottle and cap liner must be washed, rinsed with
acetone or methylene chloride, and dried before use to minimize
contamination.
5.1.2 Automatic sampler (optional)--The sampler must incorporate
glass sample containers for the collection of a minimum of 250 mL of
sample. Sample containers must be kept refrigerated at 4 [deg]C and
protected from light during compositing. If the sampler uses a
peristaltic pump, a minimum length of compressible silicone rubber
tubing may be used. Before use, however, the compressible tubing should
be thoroughly rinsed with methanol, followed by repeated rinsings with
distilled water to minimize the potential for contamination of the
sample. An integrating
[[Page 166]]
flow meter is required to collect flow proportional composites.
5.2 Glassware (All specifications are suggested. Catalog numbers are
included for illustration only.):
5.2.1 Separatory funnel--2-L, with Teflon stopcock.
5.2.2 Drying column--Chromatographic col umn, approximately 400 mm
long x 19 mm ID, with coarse frit filter disc.
5.2.3 Chromatographic column--400 mm long x 19 mm ID, with Teflon
stopcock and coarse frit filter disc at bottom (Kontes K-420540-0224 or
equivalent).
5.2.4 Concentrator tube, Kuderna-Danish-- 10-mL, graduated (Kontes
K-570050-1025 or equival ent). Calibration must be checked at the
volumes em ployed in the test. Ground glass stopper is used to prevent
evaporation of extracts.
5.2.5 Evaporative flask, Kuderna-Danish--500-mL (Kontes K-570001-
0500 or equivalent). Attach to concentrator tube with springs.
5.2.6 Snyder column, Kuderna-Danish--Three-ball macro (Kontes K-
503000-0121 or equivalent).
5.2.7 Vials--10 to 15-mL, amber glass, with Teflon-lined screw cap.
5.3 Boiling chips--Approximately 10/40 mesh. Heat to 400 [deg]C for
30 min or Soxhlet extract with methylene chloride.
5.4 Water bath--Heated, with concentric ring cover, capable of
temperature control (2[deg]C). The bath should be
used in a hood.
5.5 Balance--Analytical, capable of accurately weighing 0.0001 g.
5.6 Gas chromatograph--An analytical system complete with
temperature programmable gas chromatograph suitable for on-column
injection and all required accessories including syringes, analytical
columns, gases, detector, and strip-chart recorder. A data system is
recommended for measuring peak areas.
5.6.1 Column 1--1.8 m long x 2 mm ID glass, packed with 3% SP-1000
on Supel co port (100/120 mesh) or equivalent. This column was used to
develop the method performance statements in Section 14. Guidelines for
the use of alternate column packings are provided in Section 12.1.
5.6.2 Column 2--1.8 m long x 2 mm ID glass, packed with 2,6-
diphenylene oxide polymer (60/80 mesh), Tenax, or equivalent.
5.6.3 Detector--Halide specific detector: electrolytic conductivity
or microcoulo metric. These detectors have proven effec tive in the
analysis of wastewaters for the parameters listed in the scope (Section
1.1). The Hall conductivity detector was used to develop the method
performance statements in Section 14. Guidelines for the use of
alternate detectors are provided in Section 12.1. Although less
selective, an electron capture detector is an acceptable alternative.
6. Reagents
6.1 Reagent water--Reagent water is defined as a water in which an
interferent is not observed at the MDL of the parameters of interest.
6.2 Sodium thiosulfate--(ACS) Granular.
6.3 Acetone, hexane, methanol, methylene chloride, petroleum ether
(boiling range 30-60 [deg]C)--Pesticide quality or equivalent.
6.4 Sodium sulfate--(ACS) Granular, anhydrous. Purify by heating at
400 [deg]C for 4 h in a shallow tray.
6.5 Florisil--PR Grade (60/100 mesh). Purchase activated at 1250
[deg]F and store in the dark in glass containers with ground glass
stoppers or foil-lined screw caps. Before use, activate each batch at
least 16 h at 130 [deg]C in a foil-covered glass container and allow to
cool.
6.6 Ethyl ether--Nanograde, redistilled in glass if necessary.
6.6.1 Ethyl ether must be shown to be free of peroxides before it is
used as indicated by EM Laboratories Quant test strips. (Available from
Scientific Products Co., Cat. No. P1126-8, and other suppliers.)
6.6.2 Procedures recommended for removal of peroxides are provided
with the test strips. After cleanup, 20 mL of ethyl alcohol preservative
must be added to each liter of ether.
6.7 Stock standard solutions (1.00 [micro]g/[micro]L)--Stock
standard solutions can be prepared from pure standard materials or
purchased as certified solutions.
6.7.1 Prepare stock standard solutions by accurately weighing about
0.0100 g of pure material. Dissolve the material in acetone and dilute
to volume in a 10-mL volumetric flask. Larger volumes can be used at the
convenience of the analyst. When compound purity is assayed to be 96% or
greater, the weight can be used without correction to calculate the
concentration of the stock standard. Commercially prepared stock
standards can be used at any concentration if they are certified by the
manufacturer or by an independent source.
6.7.2 Transfer the stock standard solutions into Teflon-sealed
screw-cap bottles. Store at 4 [deg]C and protect from light. Stock
standard solutions should be checked frequently for signs of degradation
or evaporation, especially just prior to preparing calibration standards
from them.
6.7.3 Stock standard solutions must be replaced after six months, or
sooner if comparison with check standards indicates a problem.
6.8 Quality control check sample concentrate--See Section 8.2.1.
7. Calibration
7.1 Establish gas chromatographic operating conditions equivalent to
those given in Table 1. The gas chromatographic system
[[Page 167]]
can be calibrated using the external standard technique (Section 7.2) or
the internal standard technique (Section 7.3).
7.2 External standard calibration procedure:
7.2.1 Prepare calibration standards at a minimum of three
concentration levels for each parameter of interest by adding volumes of
one or more stock standards to a volumetric flask and diluting to volume
with hexane. One of the external standards should be at a concentration
near, but above, the MDL (Table 1) and the other concentrations should
correspond to the expected range of concentrations found in real samples
or should define the working range of the detector.
7.2.2 Using injections of 2 to 5 [micro]L, analyze each calibration
standard according to Section 12 and tabulate peak height or area
responses against the mass injected. The results can be used to prepare
a calibration curve for each compound. Alternatively, if the ratio of
response to amount injected (calibration factor) is a constant over the
working range (<10% relative standard deviation, RSD), linearity through
the origin can be assumed and the average ratio or calibration factor
can be used in place of a calibration curve.
7.3 Internal standard calibration procedure--To use this approach,
the analyst must select one or more internal standards that are similar
in analytical behavior to the compounds of interest. The analyst must
further demonstrate that the measurement of the internal standard is not
affected by method or matrix interferences. Because of these
limitations, no internal standard can be suggested that is applicable to
all samples.
7.3.1 Prepare calibration standards at a minimum of three
concentration levels for each parameter of interest by adding volumes of
one or more stock standards to a volumetric flask. To each calibration
standard, add a known constant amount of one or more internal standards,
and dilute to volume with hexane. One of the standards should be at a
concentration near, but above, the MDL and the other concentrations
should correspond to the expected range of concentrations found in real
samples or should define the working range of the detector.
7.3.2 Using injections of 2 to 5 [micro]L, analyze each calibration
standard according to Section 12 and tabulate peak height or area
responses against concentration for each compound and internal standard.
Calculate response factors (RF) for each compound using Equation 1.
[GRAPHIC] [TIFF OMITTED] TC15NO91.116
Equation 1
where:
As=Response for the parameter to be measured.
Ais=Response for the internal standard.
Cis=Concentration of the internal standard ([micro]g/L).
Cs=Concentration of the parameter to be measured ([micro]g/
L).
If the RF value over the working range is a constant (<10% RSD), the RF
can be assumed to be invariant and the average RF can be used for
calculations. Alternatively, the results can be used to plot a
calibration curve of response ratios, As/Ais, vs.
RF.
7.4 The working calibration curve, calibration factor, or RF must be
verified on each working day by the measurement of one or more
calibration standards. If the response for any parameter varies from the
predicted response by more than 15%, a new
calibration curve must be prepared for that compound.
7.5 The cleanup procedure in Section 11 utilizes Florisil column
chromatography. Florisil from different batches or sources may vary in
adsorptive capacity. To standardize the amount of Florisil which is
used, the use of lauric acid value \7\ is suggested. The referenced
procedure determines the adsorption from hexane solution of lauric acid
(mg) per g of Florisil. The amount of Florisil to be used for each
column is calculated by dividing 110 by this ratio and multiplying by 20
g.
7.6 Before using any cleanup procedure, the analyst must process a
series of calibration standards through the procedure to validate
elution patterns and the absence of interferences from the reagents.
8. Quality Control
8.1 Each laboratory that uses this method is required to operate a
formal quality control program. The minimum requirements of this program
consist of an initial demonstration of laboratory capability and an
ongoing analysis of spiked samples to evaluate and document data
quality. The laboratory must maintain records to document the quality of
data that is generated. Ongoing data quality checks are compared with
established performance criteria to determine if the results of analyses
meet the performance characteristics of the method. When results of
sample spikes indicate atypical method performance, a quality control
check standard must be analyzed to confirm that the measurements were
performed in an in-control mode of operation.
8.1.1 The analyst must make an initial, one-time, demonstration of
the ability to generate acceptable accuracy and precision with this
method. This ability is established as described in Section 8.2.
[[Page 168]]
8.1.2 In recognition of advances that are occurring in
chromatography, the analyst is permitted certain options (detailed in
Sections 10.4, 11.1, and 12.1) to improve the separations or lower the
cost of measurements. Each time such a modification is made to the
method, the analyst is required to repeat the procedure in Section 8.2.
8.1.3 Before processing any samples, the analyst must analyze a
reagent water blank to demonstrate that interferences from the
analytical system and glassware are under control. Each time a set of
samples is extracted or reagents are changed, a reagent water blank must
be processed as a safeguard against laboratory contamination.
8.1.4 The laboratory must, on an ongoing basis, spike and analyze a
minimum of 10% of all samples to monitor and evaluate laboratory data
quality. This procedure is described in Section 8.3.
8.1.5 The laboratory must, on an ongoing basis, demonstrate through
the analyses of quality control check standards that the operation of
the measurement system is in control. This procedure is described in
Section 8.4. The frequency of the check standard analyses is equivalent
to 10% of all samples analyzed but may be reduced if spike recoveries
from samples (Section 8.3) meet all specified quality control criteria.
8.1.6 The laboratory must maintain performance records to document
the quality of data that is generated. This procedure is described in
Section 8.5.
8.2 To establish the ability to generate ac cepta ble accuracy and
precision, the analyst must perform the following operations.
8.2.1 A quality control (QC) check sample concentrate is required
containing each parameter of interest at a concentration of 100
[micro]g/mL in acetone. The QC check sample concentrate must be obtained
from the U.S. Environmental Protection Agency, Environmental Monitoring
and Support Laboratory in Cincinnati, Ohio, if available. If not
available from that source, the QC check sample concentrate must be
obtained from another external source. If not available from either
source above, the QC check sample concentrate must be prepared by the
laboratory using stock standards prepared independently from those used
for calibration.
8.2.2 Using a pipet, prepare QC check samples at a concentration of
100 [micro]g/L by adding 1.00 mL of QC check sample concentrate to each
of four 1-L aliquots of reagent water.
8.2.3 Analyze the well-mixed QC check sam ples according to the
method beginning in Section 10.
8.2.4 Calculate the average recovery (X) in [micro]g/L, and the
standard deviation of the recovery (s) in [micro]g/L, for each parameter
using the four results.
8.2.5 For each parameter compare s and X with the corresponding
acceptance criteria for precision and accuracy, respectively, found in
Table 2. If s and X for all parameters of interest meet the acceptance
criteria, the system performance is acceptable and analysis of actual
samples can begin. If any individual s exceeds the precision limit or
any individual X falls outside the range for accuracy, the system
performance is unacceptable for that parameter. Locate and correct the
source of the problem and repeat the test for all parameters of interest
beginning with Section 8.2.2.
8.3 The laboratory must, on an ongoing basis, spike at least 10% of
the samples from each sample site being monitored to assess accuracy.
For laboratories analyzing one to ten samples per month, at least one
spiked sample per month is required.
8.3.1. The concentration of the spike in the sample should be
determined as follows:
8.3.1.1 If, as in compliance monitoring, the concentration of a
specific parameter in the sample is being checked against a regulatory
concentration limit, the spike should be at that limit or 1 to 5 times
higher than the background concentration determined in Section 8.3.2,
whichever concentration would be larger.
8.3.1.2 If the concentration of a specific parameter in the sample
is not being checked against a limit specific to that parameter, the
spike should be at 100 [micro]g/L or 1 to 5 times higher than the
background concentration determined in Section 8.3.2, whichever
concentration would be larger.
8.3.1.3 If it is impractical to determine background levels before
spiking (e.g., maximum holding times will be exceeded), the spike
concentration should be (1) the regulatory concentration limit, if any;
or, if none (2) the larger of either 5 times higher than the expected
background concentration or 100 [micro]g/L.
8.3.2 Analyze one sample aliquot to determine the background
concentration (B) of each parameter. If necessary, prepare a new QC
check sample concentrate (Section 8.2.1) appropriate for the background
concentrations in the sample. Spike a second sample aliquot with 1.0 mL
of the QC check sample concentrate and analyze it to determine the
concentration after spiking (A) of each parameter. Calculate each
percent recovery (P) as 100(A-B)%/T, where T is the known true value of
the spike.
8.3.3 Compare the percent recovery (P) for each parameter with the
corresponding QC acceptance criteria found in Table 2. These acceptance
criteria were calculated to include an allowance for error in
measurement of both the background and spike concentrations, assuming a
spike to background ratio of 5:1. This error will be accounted for to
the extent that the analyst's spike to background ratio approaches
5:1.\8\ If spiking was performed at a concentration lower than 100
[micro]g/L, the analyst must use either the QC acceptance criteria in
Table 2, or optional QC
[[Page 169]]
acceptance criteria calculated for the specific spike concentration. To
calculate optional acceptance criteria for the recovery of a parameter:
(1) Calculate accuracy (X') using the equation in Table 3, substituting
the spike concentration (T) for C; (2) calculate overall precision (S')
using the equation in Table 3, substituting X' for X; (3) calculate the
range for recovery at the spike concentration as (100 X'/T)2.44(100 S'/T)%.\8\
8.3.4 If any individual P falls outside the designated range for
recovery, that parameter has failed the acceptance criteria. A check
standard containing each parameter that failed the criteria must be
analyzed as described in Section 8.4.
8.4 If any parameter fails the acceptance criteria for recovery in
Section 8.3, a QC check standard containing each parameter that failed
must be prepared and analyzed.
Note: The frequency for the required analysis of a QC check standard
will depend upon the number of parameters being simultaneously tested,
the complexity of the sample matrix, and the performance of the
laboratory.
8.4.1 Prepare the QC check standard by adding 1.0 m/L of QC check
sample concentrate (Section 8.2.1 or 8.3.2) to 1 L of reagent water. The
QC check standard needs only to contain the parameters that failed
criteria in the test in Section 8.3.
8.4.2 Analyze the QC check standard to determine the concentration
measured (A) of each parameter. Calculate each percent recovery
(Ps) as 100 (A/T)%, where T is the true value of the standard
concentration.
8.4.3 Compare the percent recovery (Ps) for each
parameter with the corresponding QC acceptance criteria found in Table
2. Only parameters that failed the test in Section 8.3 need to be
compared with these criteria. If the recovery of any such parameter
falls outside the designated range, the laboratory performance for that
parameter is judged to be out of control, and the problem must be
immediately identified and corrected. The analytical result for that
parameter in the unspiked sample is suspect and may not be reported for
regulatory compliance purposes.
8.5 As part of the QC program for the laboratory, method accuracy
for wastewater samples must be assessed and records must be maintained.
After the analysis of five spiked wastewater samples as in Section 8.3,
calculate the average percent recovery (P) and the standard deviation of
the percent recovery (sp). Express the accuracy assessment as
a percent recovery interval from P-2sp to P+2sp.
If P=90% and sp=10%, for example, the accuracy interval is
expressed as 70-110%. Update the accuracy assessment for each parameter
on a regular basis (e.g. after each five to ten new accuracy
measurements).
8.6 It is recommended that the laboratory adopt additional quality
assurance practices for use with this method. The specific practices
that are most productive depend upon the needs of the laboratory and the
nature of the samples. Field duplicates may be analyzed to assess the
precision of the environmental measurements. When doubt exists over the
identification of a peak on the chromatogram, confirmatory techniques
such as gas chromatography with a dissimilar column, specific element
detector, or mass spectrometer must be used. Whenever possible, the
laboratory should analyze standard reference materials and participate
in relevant performance evaluation studies.
9. Sample Collection, Preservation, and Handling
9.1 Grab samples must be collected in glass containers. Conventional
sampling prac tices9 should be followed, except that the
bottle must not be prerinsed with sample before collection. Composite
samples should be collected in refrigerated glass containers in
accordance with the requirements of the program. Automatic sampling
equipment must be as free as possible of Tygon tubing and other
potential sources of contamination.
9.2 All samples must be iced or refrigerated at 4 [deg]C from the
time of collection until extraction. Fill the sample bottles and, if
residual chlorine is present, add 80 mg of sodium thiosulfate per liter
of sample and mix well. EPA Methods 330.4 and 330.5 may be used for
measurement of residual chlorine.10 Field test kits are
available for this purpose.
9.3 All samples must be extracted within 7 days of collection and
completely analyzed within 40 days of extraction.2
10. Sample Extraction
10.1 Mark the water meniscus on the side of the sample bottle for
later determination of sample volume. Pour the entire sample into a 2-L
separatory funnel.
10.2 Add 60 mL methylene chloride to the sample bottle, seal, and
shake 30 s to rinse the inner surface. Transfer the solvent to the
separatory funnel and extract the sample by shaking the funnel for 2 min
with periodic venting to release excess pressure. Allow the organic
layer to separate from the water phase for a minimum of 10 min. If the
emulsion interface between layers is more than one-third the volume of
the solvent layer, the analyst must employ mechanical techniques to
complete the phase separation. The optimum technique depends upon the
sample, but may include stirring, filtration of the emulsion through
glass wool, centrifugation, or other physical methods. Collect the
methylene chloride extract in a 250-mL Erlenmeyer flask.
10.3 Add a second 60-mL volume of methylene chloride to the sample
bottle and repeat the extraction procedure a second time, combining the
extracts in the Erlenmeyer
[[Page 170]]
flask. Perform a third extraction in the same manner.
10.4 Assemble a Kuderna-Danish (K-D) concentrator by attaching a 10-
mL concentrator tube to a 500-mL evaporative flask. Other concentration
devices or techniques may be used in place of the K-D concentrator if
the requirements of Section 8.2 are met.
10.5 Pour the combined extract through a solvent-rinsed drying
column containing about 10 cm of anhydrous sodium sulfate, and collect
the extract in the K-D concentrator. Rinse the Erlenmeyer flask and
column with 20 to 30 mL of methylene chloride to complete the
quantitative transfer.
10.6 Add one or two clean boiling chips to the evaporative flask and
attach a three-ball Snyder column. Prewet the Snyder column by adding
about 1 mL of methylene chloride to the top. Place the K-D apparatus on
a hot water bath (60 to 65 [deg]C) so that the concentrator tube is
partially immersed in the hot water, and the entire lower rounded
surface of the flask is bathed with hot vapor. Adjust the vertical
position of the apparatus and the water temperature as required to
complete the concentration in 15 to 20 min. At the proper rate of
distillation the balls of the column will actively chatter but the
chambers will not flood with condensed solvent. When the apparent volume
of liquid reaches 1 mL, remove the K-D apparatus and allow it to drain
and cool for at least 10 min.
Note: Some of the haloethers are very volatile and significant
losses will occur in concentration steps if care is not exercised. It is
important to maintain a constant gentle evaporation rate and not to
allow the liquid volume to fall below 1 to 2 mL before removing the K-D
apparatus from the hot water bath.
10.7 Momentarily remove the Snyder column, add 50 mL of hexane and a
new boiling chip, and reattach the Snyder column. Raise the temperature
of the water bath to 85 to 90 [deg]C. Concentrate the extract as in
Section 10.6, except use hexane to prewet the column. The elapsed time
of concentration should be 5 to 10 min.
10.8 Remove the Snyder column and rinse the flask and its lower
joint into the concentrator tube with 1 to 2 mL of hexane. A 5-mL
syringe is recommended for this operation. Stopper the concentrator tube
and store refrigerated if further processing will not be performed
immediately. If the extract will be stored longer than two days, it
should be transferred to a Teflon-sealed screw- cap vial. If the sample
extract requires no further cleanup, proceed with gas chromatographic
analysis (Section 12). If the sam ple requires further cleanup, proceed
to Section 11.
10.9 Determine the original sample volume by refilling the sample
bottle to the mark and transferring the liquid to a 1000-mL graduated
cylinder. Record the sample volume to the nearest 5 mL.
11. Cleanup and Separation
11.1 Cleanup procedures may not be necessary for a relatively clean
sample matrix. If particular circumstances demand the use of a cleanup
procedure, the analyst may use the procedure below or any other
appropriate procedure. However, the analyst first must demonstrate that
the requirements of Section 8.2 can be met using the method as revised
to incorporate the cleanup procedure.
11.2 Florisil column cleanup for haloethers:
11.2.1 Adjust the sample extract volume to 10 mL.
11.2.2 Place a weight of Florisil (nominally 20 g) predetermined by
calibration (Section 7.5), into a chromatographic column. Tap the column
to settle the Florisil and add 1 to 2 cm of anhydrous sodium sulfate to
the top.
11.2.3 Preelute the column with 50 to 60 mL of petroleum ether.
Discard the eluate and just prior to exposure of the sodium sulfate
layer to the air, quantitatively transfer the sample extract onto the
column by decantation and subsequent petroleum ether washings. Discard
the eluate. Just prior to exposure of the sodium sulfate layer to the
air, begin eluting the column with 300 mL of ethyl ether/petroleum ether
(6+94) (V/V). Adjust the elution rate to approximately 5 mL/min and
collect the eluate in a 500-mL K-D flask equipped with a 10-mL
concentrator tube. This fraction should contain all of the haloethers.
11.2.4 Concentrate the fraction as in Section 10.6, except use
hexane to prewet the column. When the apparatus is cool, remove the
Snyder column and rinse the flask and its lower joint into the
concentrator tube with hexane. Adjust the volume of the cleaned up
extract to 10 mL with hexane and analyze by gas chromatography (Section
12).
12. Gas Chromatography
12.1 Table 1 summarizes the recommended operating conditions for the
gas chromatograph. Included in this table are retention times and MDL
that can be achieved under these conditions. Examples of the separations
achieved by Columns 1 and 2 are shown in Figures 1 and 2, respectively.
Other packed or capillary (open-tubular) columns, chromatographic
conditions, or detectors may be used if the requirements of Section 8.2
are met.
12.2 Calibrate the system daily as described in Section 7.
12.3 If the internal standard calibration procedure is being used,
the internal standard must be added to the sample extract and mixed
thoroughly immediately before injection into the gas chromatrograph.
12.4 Inject 2 to 5 [micro]L of the sample extract or standard into
the gas chromatograph using the solvent-flush technique.11
Smaller
[[Page 171]]
(1.0 [micro]L) volumes may be injected if automatic devices are
employed. Record the volume injected to the nearest 0.05 [micro]L, the
total extract volume, and the resulting peak size in area or peak height
units.
12.5 Identify the parameters in the sample by comparing the
retention times of the peaks in the sample chromatogram with those of
the peaks in standard chromatograms. The width of the retention time
window used to make identifications should be based upon measurements of
actual retention time variations of standards over the course of a day.
Three times the standard deviation of a retention time for a compound
can be used to calculate a suggested window size; however, the
experience of the analyst should weight heavily in the interpretation of
chromatograms.
12.6 If the response for a peak exceeds the working range of the
system, dilute the extract and reanalyze.
12.7 If the measurement of the peak response is prevented by the
presence of interferences, further cleanup is required.
13. Calculations
13.1 Determine the concentration of individual compounds in the
sample.
13.1.1 If the external standard calibration procedure is used,
calculate the amount of material injected from the peak response using
the calibration curve or calibration factor determined in Section 7.2.2.
The concentration in the sample can be calculated from Equation 2.
[GRAPHIC] [TIFF OMITTED] TC15NO91.117
Equation 2
where:
A=Amount of material injected (ng).
Vi=Volume of extract injected ([micro]L).
Vt=Volume of total extract ([micro]L).
Vs=Volume of water extracted (mL).
13.1.2 If the internal standard calibration procedure is used,
calculate the concentration in the sample using the response factor (RF)
determined in Section 7.3.2 and Equation 3.
[GRAPHIC] [TIFF OMITTED] TC15NO91.118
Equation 3
where:
As=Response for the parameter to be measured.
Ais=Response for the internal standard.
Is=Amount of internal standard added to each extract
([micro]g).
Vo=Volume of water extracted (L).
13.2 Report results in [micro]g/L without correction for recovery
data. All QC data obtained should be reported with the sample results.
14. Method Performance
14.1 The method detection limit (MDL) is defined as the minimum
concentration of a substance that can be measured and reported with 99%
confidence that the value is above zero.1 The MDL
concentrations listed in Table 1 were obtained using reagent
water.12 Similar results were achieved using representative
wastewaters. The MDL actually achieved in a given analysis will vary
depending on instrument sensitivity and matrix effects.
14.2 This method has been tested for linearity of spike recovery
from reagent water and has been demonstrated to be applicable over the
concentration range from 4 x MDL to 1000 x MDL.12
14.3 This method was tested by 20 laboratories using reagent water,
drinking water, surface water, and three industrial wastewaters spiked
at six concentrations over the range 1.0 to 626 [micro]/L.12
Single operator precision, overall precision, and method accuracy were
found to be directly related to the concentration of the parameter and
essentially independent of the sample matrix. Linear equations to
describe these relationships are presented in Table 3.
References
1. 40 CFR part 136, appendix B.
2. ``Determination of Haloethers in Industrial and Municipal
Wastewaters,'' EPA 600/4-81-062, National Technical Information Service,
PB81-232290, Springfield, Virginia 22161, July 1981.
3. ASTM Annual Book of Standards, Part 31, D3694-78. ``Standard
Practices for Preparation of Sample Containers and for Preservation of
Organic Constitutents,'' American Society for Testing and Materials,
Philadelphia.
4. ``Carcinogens--Working Carcinogens, '' Department of Health,
Education, and Welfare, Public Health Services, Center for Disease
Control, National Institute for Occupational Safety and Health,
Publication No. 77-206, August 1977.
5. ``OSHA Safety and Health Standards, General Industry,'' (29 CFR
part 1910), Occupational Safety and Health Administration, OSHA 2206
(Revised, January 1976).
6. ``Safety in Academic Chemistry Laboratories,'' American Chemical
Society Publication, Committee on Chemical Safety, 3rd Edition, 1979.
7. Mills., P.A. ``Variation of Florisil Activity: Simple Method for
Measuring Absorbent Capacity and Its Use in Standardizing Florisil
Columns,'' Journal of the Association of Official Analytical Chemists,
51, 29 (1968).
[[Page 172]]
8. Provost, L.P., and Elder, R.S. ``Interpretation of Percent
Recovery Data,'' American Laboratory, 15, 58-63 (1983). (The value 2.44
used in the equation in Section 8.3.3 is two times the value 1.22
derived in this report.)
9. ASTM Annual Book of Standards, Part 31, D3370-76. ``Standard
Practices for Sampling Water,'' American Society for Testing and
Materials, Philadelphia.
10. ``Methods 330.4 (Titrimetric, DPD-FAS) and 330.5
(Spectrophotometric, DPD) for Chlorine, Total Residual,'' Methods for
Chemical Analysis of Water and Wastes, EPA-600/4-79-020, U.S.
Environmental Protection Agency, Environmental Monitoring and Support
Laboratory, Cincinnati, Ohio 45268, March 1979.
11. Burke, J.A. ``Gas Chromatography for Pesticide Residue Analysis;
Some Practical Aspects,'' Journal of the Association of Official
Analytical Chemists, 48, 1037 (1965).
12. ``EPA Method Study 21, Method 611, Haloethers,'' EPA 600/4-84-
052, National Technical Information Service, PB84-205939, Springfield,
Virginia 22161, June 1984.
Table 1--Chromatographic Conditions and Methods Detection Limits
------------------------------------------------------------------------
Retention time (min) Method
---------------------- detection
Parameters limit
Column 1 Column 2 ([micro]/
L)
------------------------------------------------------------------------
Bis(2-chloroisopropyl) ether........... 8.4 9.7 0.8
Bis(2-chloroethyl) ether............... 9.3 9.1 0.3
Bis(2-chloroethoxy) methane............ 13.1 10.0 0.5
4-Chlorophenyl ether................... 19.4 15.0 3.9
4-Bromophenyl phenyl ether............. 21.2 16.2 2.3
------------------------------------------------------------------------
AColumn 1 conditions: Supelcoport (100/120 mesh) coated with 3% SP-1000
packed in a 1.8 m long x 2 mm ID glass column with helium carrier gas
at 40 mL/min. flow rate. Column temperature held at 60 [deg]C for 2
min. after injection then programmed at 8 [deg]C/min. to 230 [deg]C
and held for 4 min. Under these conditions the retention time for
Aldrin is 22.6 min.
AColumn 2 conditions: Tenax-GC (60/80 mesh) packed in a 1.8 m long x
2mm ID glass column with helium carrier gas at 40 mL/min. flow rate.
Column temperature held at 150 [deg]C for 4 min. after injection then
programmed at 16 [deg]C/min. to 310 [deg]C. Under these conditions the
retention time for Aldrin is 18.4 min.
Table 2--QC Acceptance Criteria--Method 611
----------------------------------------------------------------------------------------------------------------
Range for X
Test conc. Limit for s ([micro]g/ Range for
Parameter ([micro]g/ ([micro]g/L) L) P, Ps
L) percent
----------------------------------------------------------------------------------------------------------------
Bis (2-chloroethyl)ether................................... 100 26.3 26.3-136.8 11-152
Bis (2-chloroethoxy)methane................................ 100 25.7 27.3-115.0 12-128
Bis (2-chloroisopropyl)ether............................... 100 32.7 26.4-147.0 9-165
4-Bromophenyl phenyl ether................................. 100 39.3 7.6 -167.5 D-189
4-Chlorophenyl phenyl ether................................ 100 30.7 15.4-152.5 D-170
----------------------------------------------------------------------------------------------------------------
s=Standard deviation of four recovery measurements, in [micro]g/L (Section 8.2.4).
X=Average recovery for four recovery measurements, in [micro]g/L (Section 8.2.4).
P, Ps=Percent recovery measured (Section 8.3.2, Section 8.4.2).
D=Detected; result must be greater than zero.
Note: These criteria are based directly upon the method performance data in Table 3. Where necessary, the limits
for recovery have been broadened to assure applicability of the limits to concentrations below those used to
develop Table 3.
Table 3--Method Accuracy and Precision as Functions of Concentration--Method 611
----------------------------------------------------------------------------------------------------------------
Accuracy, as Single analyst Overall
Parameter recovery, X' precision, sr' precision, S'
([micro]g/L) ([micro]g/L) ([micro]g/L)
----------------------------------------------------------------------------------------------------------------
Bis(2-chloroethyl) ether........................................ 0.81C+0.54 0.19X+0.28 0.35X+0,36
Bis(2-chloroethoxy) methane..................................... 0.71C+0.13 0.20X+0.15 0.33X+0.11
Bis(2-chloroisopropyl) ether.................................... 0.85C+1.67 0.20X+1.05 0.36X+0.79
4-Bromophenyl phenyl ether...................................... 0.85C+2.55 0.25X+0.21 0.47X+0.37
4-Chlorophenyl phenyl ether..................................... 0.82C+1.97 0.18X+2.13 0.41X+0.55
----------------------------------------------------------------------------------------------------------------
X' = Expected recovery for one or more measuremelts of a sample containing a concentration of C, in [micro]g/L.
sr' = Expected single analyst standard deviation of measurements at an average concentration found of X, in
[micro]g/L.
S' = Expected interlaboratory standard deviation of measurements at an average concentration found of X, in
[micro]g/L.
C =True value for the concentration, in [micro]g/L.
X = Average recovery found for measurements of samples containing a concentration of C, in [micro]g/L.
[[Page 173]]
[GRAPHIC] [TIFF OMITTED] TC02JY92.034
[[Page 174]]
[GRAPHIC] [TIFF OMITTED] TC02JY92.035
Method 612--Chlorinated Hydrocarbons
1. Scope and Application
1.1 This method covers the determination of certain chlorinated
hydrocarbons. The following parameters can be determined by this method:
------------------------------------------------------------------------
STORET
Parameter No. CAS No.
------------------------------------------------------------------------
2-Chloronaphthalene.............................. 34581 91-58-7
1,2-Dichlorobenzene.............................. 34536 95-50-1
1,3-Dichlorobenzene.............................. 34566 541-73-1
1,4-Dichlorobenzene.............................. 34571 106-46-7
Hexachlorobenzene................................ 39700 118-74-1
Hexachlorobutadiene.............................. 34391 87-68-3
Hexachlorocyclopentadiene........................ 34386 77-47-4
Hexachloroethane................................. 34396 67-72-1
[[Page 175]]
1,2,4-Trichlorobenzene........................... 34551 120-82-1
------------------------------------------------------------------------
1.2 This is a gas chromatographic (GC) method applicable to the
determination of the compounds listed above in municipal and industrial
discharges as provided under 40 CFR 136.1. When this method is used to
analyze unfamiliar samples for any or all of the compounds above,
compound identifications should be supported by at least one additional
qualitative technique. This method describes a second gas
chromatographic column that can be used to confirm measurements made
with the primary column. Method 625 provides gas chromatograph/mass
spectrometer (GC/MS) conditions appropriate for the qualitative and
quantitative confirmation of results for all of the parameters listed
above, using the extract produced by this method.
1.3 The method detection limit (MDL, defined in Section 14.1)\1\ for
each parameter is listed in Table 1. The MDL for a specific wastewater
may differ from those listed, depending upon the nature of interferences
in the sample matrix.
1.4 The sample extraction and concentration steps in this method are
essentially the same as in Methods 606, 608, 609, and 611. Thus, a
single sample may be extracted to measure the parameters included in the
scope of each of these methods. When cleanup is required, the
concentration levels must be high enough to permit selecting aliquots,
as necessary, to apply appropriate cleanup procedures. The analyst is
allowed the latitude, under Section 12, to select chromatographic
conditions appropriate for the simultaneous measurement of combinations
of these parameters.
1.5 Any modification of this method, beyond those expressly
permitted, shall be considered as a major modification subject to
application and approval of alternate test procedures under 40 CFR 136.4
and 136.5.
1.6 This method is restricted to use by or under the supervision of
analysts experienced in the use of a gas chromatograph and in the
interpretation of gas chromatograms. Each analyst must demonstrate the
ability to generate acceptable results with this method using the
procedure described in Section 8.2.
2. Summary of Method
2.1 A measured volume of sample, approximately 1-L, is extracted
with methylene chloride using a separatory funnel. The methylene
chloride extract is dried and exchanged to hexane during concentration
to a volume of 10 mL or less. The extract is separated by gas
chromatography and the parameters are then measured with an electron
capture detector. \2\
2.2 The method provides a Florisil column cleanup procedure to aid
in the elimination of interferences that may be encountered.
3. Interferences
3.1 Method interferences may be caused by contaminants in solvents,
reagents, glassware, and other sample processing hardware that lead to
discrete artifacts and/or elevated baselines in gas chromatograms. All
of these materials must be routinely demonstrated to be free from
interferences under the conditions of the analysis by running laboratory
reagent blanks as described in Section 8.1.3.
3.1.1 Glassware must be scrupulously cleaned. \3\ Clean all
glassware as soon as possible after use by rinsing with the last solvent
used in it. Solvent rinsing should be followed by detergent washing with
hot water, and rinses with tap water and distilled water. The glassware
should then be drained dry, and heated in a muffle furnace at 400 [deg]C
for 15 to 30 min. Some thermally stable materials, such as PCBs, may not
be eliminated by this treatment. Solvent rinses with acetone and
pesticide quality hexane may be substituted for the muffle furnace
heating. Thorough rinsing with such solvents usually eliminates PCB
interference. Volumetric ware should not be heated in a muffle furnace.
After drying and cooling, glassware should be sealed and stored in a
clean environment to prevent any accumulation of dust or other
contaminants. Store inverted or capped with aluminum foil.
3.1.2 The use of high purity reagents and solvents helps to minimize
interference problems. Purification of solvents by distillation in all-
glass systems may be required.
3.2 Matrix interferences may be caused by contaminants that are co-
extracted from the sample. The extent of matrix interferences will vary
considerably from source to source, depending upon the nature and
diversity of the industrial complex or municipality being sampled. The
cleanup procedure in Section 11 can be used to overcome many of these
interferences, but unique samples may require additional cleanup
approaches to achieve the MDL listed in Table 1.
4. Safety
4.1 The toxicity or carcinogenicity of each reagent used in this
method has not been precisely defined; however, each chemical compound
should be treated as a potential health hazard. From this viewpoint,
exposure to these chemicals must be reduced to the lowest possible level
by whatever means available. The laboratory is responsible for
maintaining a current awareness file of OSHA regulations regarding the
safe handling of the chemicals specified in this method. A reference
file of material data handling sheets should also be made available to
all
[[Page 176]]
personnel involved in the chemical analysis. Additional references to
laboratory safety are available and have been identified 4-6
for the information of the analyst.
5. Apparatus and Materials
5.1 Sampling equipment, for discrete or composite sampling.
5.1.1 Grab sample bottle--1cL or 1-qt, amber glass, fitted with a
screw cap lined with Teflon. Foil may be substituted for Teflon if the
sample is not corrosive. If amber bottles are not available, protect
samples from light. The bottle and cap liner must be washed, rinsed with
acetone or methylene chloride, and dried before use to minimize
contamination.
5.1.2 Automatic sampler (optional)--The sampler must incorporate
glass sample containers for the collection of a minimum of 250 mL of
sample. Sample containers must be kept refrigerated at 4 [deg]C and
protected from light during compositing. If the sampler uses a
peristaltic pump, a minimum length of compressible silicone rubber
tubing may be used. Before use, however, the compressible tubing should
be thoroughly rinsed with methanol, followed by repeated rinsings with
distilled water to minimize the potential for contamination of the
sample. An integrating flow meter is required to collect flow
proportional composites.
5.2 Glassware (All specifications are suggested. Catalog numbers are
included for illustration only.):
5.2.1 Separatory funnel--2-L, with Teflon stopcock.
5.2.2 Drying column--Chromatographic column, approximately 400 mm
long x 19 mm ID, with coarse frit filter disc.
5.2.3 Chromatographic column--300 long x 10 mm ID, with Teflon
stopcock and coarse frit filter disc at bottom.
5.2.4 Concentrator tube, Kuderna-Danish--10-mL, graduated (Kontes K-
570050-1025 or equivalent). Calibration must be checked at the volumes
employed in the test. Ground glass stopper is used to prevent
evaporation of extracts.
5.2.5 Evaporative flask, Kuderna-Danish--500-mL (Kontes K-570001-
0500 or equivalent). Attach to concentrator tube with springs.
5.2.6 Snyder column, Kuderna-Danish--Three-ball macro (Kontes K-
503000-0121 or equivalent).
5.2.7 Vials--10 to 15-mL, amber glass, with Teflon-lined screw cap.
5.3 Boiling chips--Approximately 10/40 mesh. Heat to 400 [deg]C for
30 min or Soxhlet extract with methylene chloride.
5.4 Water bath--Heated, with concentric ring cover, capable of
temperature control (2 [deg]C). The bath should be
used in a hood.
5.5 Balance--Analytical, capable of accurately weighing 0.0001 g.
5.6 Gas chromatograph--An analytical system complete with gas
chromatograph suitable for on-column injection and all required
accessories including syringes, analytical columns, gases, detector, and
strip-chart recorder. A data system is recommended for measuring peak
areas.
5.6.1 Column 1--1.8 m long x 2 mm ID glass, packed with 1% SP-1000
on Supelcoport (100/120 mesh) or equivalent. Guidelines for the use of
alternate column packings are provide in Section 12.1.
5.6.2 Column 2--1.8 m long x2 mm ID glass, packed with 1.5% OV-1/
2.4% OV-225 on Supelcoport (80/100 mesh) or equivalent. This column was
used to develop the method performance statements in Section 14.
5.6.3 Detector-- Electron capture detector. This detector has proven
effective in the analysis of wastewaters for the parameters listed in
the scope (Section 1.1), and was used to develop the method performance
statements in Section 14. Guidelines for the use of alternate detectors
are provided in Section 12.1.
6. Reagents
6.1 Reagent water-- Reagent water is defined as a water in which an
interferent is not observed at the MDL of the parameters of interest.
6.2 Acetone, hexane, isooctane, methanol, methylene chloride,
petroleum ether (boiling range 30 to 60 [deg]C)--Pesticide quality or
equivalent.
6.3 Sodium sulfate--(ACS) Granular, anhydrous. Purify heating at 400
[deg]C for 4 h in a shallow tray.
6.4 Florisil--PR grade (60/100 mesh). Purchase activated at 1250
[deg]F and store in the dark in glass containers with ground glass
stoppers or foil-lined screw caps. Before use, activate each batch at
least 16 h at 130 [deg]C in a foil-covered glass container and allow to
cool.
6.5 Stock standard solution (1.00 [micro]g/[micro]L)--Stock standard
solutions can be prepared from pure standard materials or purchased as
certified solutions.
6.5.1 Prepare stock standard solutions by accurately weighing about
0.0100 g of pure material. Dissolve the material in isooctane and dilute
to volume in a 120-mL volumetric flask. Larger volumes can be used at
the convenience of the analyst. When compound purity is assayed to be
96% or greater, the weight can be used without correction to calculate
the concentration of the stock standard. Commercially prepared stock
standards can be used at any concentration if they are certified by the
manufacturer or by an independent source.
6.5.2 Transfer the stock standard solutions into Teflon-sealed
screw-cap bottles. Store at 4 [deg]C and protect from light. Stock
standard solutions should be checked frequently for signs of degradation
or evaporation, especially just prior to preparing calibration standards
from them.
[[Page 177]]
6.5.3 Stock standard solutions must be replaced after six months, or
sooner if comparision with check standards indicates a problem.
6.6 Quality control check sample concentrate--See Section 8.2.1.
7. Calibration
7.1 Establish gas chromatographic operating conditions equivalent to
those given in Table 1. The gas chromatographic system can be calibrated
using the external standard technique (Section 7.2) or the internal
standard technique (Section 7.3).
7.2 External standard calibration procedure:
7.2.1 Prepare calibration standards at a minimum of three
concentration levels for each parameter of interest by adding volumes of
one or more stock standards to a volumetric flask and diluting to volume
with isooctane. One of the external standards should be at a
concentration near, but above, the MDL (Table 1) and the other
concentrations should correspond to the expected range of concentrations
found in real samples or should define the working range of the
detector.
7.2.2 Using injections of 2 to 5 [micro]L, analyze each calibration
standard according to Section 12 and tabulate peak height or area
responses against the mass injected. The results can be used to prepare
a calibration curve for each compound. Alternatively, if the ratio of
response to amount injected (calibration factor) is a constant over the
working range (<10% relative standard deviation, RSD), linearity through
the origin can be assumed and the average ratio or calibration factor
can be used in place of a calibration curve.
7.3 Internal standard calibration procedure--To use this approach,
the analyst must select one or more internal standards that are similar
in analytical behavior to the compounds of interest. The analyst must
further demonstrate that the measurement of the internal standard is not
affected by method or matrix interferences. Because of these
limitations, no internal standard can be suggested that is applicable to
all samples.
7.3.1 Prepare calibration standards at a minimum of three
concentration levels for each parameter of interest by adding volumes of
one or more stock standards to a volumetric flask. To each calibration
standard, add a known constant amount of one or more internal standards,
and dilute to volume with isooctane. One of the standards should be at a
concentration near, but above, the MDL and the other concentrations
should correspond to the expected range of concentrations found in real
samples or should define the working range of the detector.
7.3.2 Using injections of 2 to 5 [micro]L, analyze each calibration
standard according to Section 12 and tabulate peak height or area
responses against concentration for each compound and internal standard.
Calculate response factors (RF) for each compound using Equation 1.
[GRAPHIC] [TIFF OMITTED] TC15NO91.119
Equation 1
where:
As=Response for the parameter to be measured.
Ais=Response for the internal standard.
Cis=Concentration of the internal standard ([micro]g/L).
Cs=Concentration of the parameter to be measured ([micro]g/
L).
If the RF value over the working range is a constant (<10% RSD), the RF
can be assumed to be invariant and the average RF can be used for
calculations. Alternatively, the results can be used to plot a
calibration curve of response ratios, As/Ais, vs.
RF.
7.4 The working calibration curve, calibration factor, or RF must be
verified on each working day by the measurement of one or more
calibration standards. If the response for any parameter varies from the
predicted response by more than 15%, a new
calibration curve must be prepared for that compound.
7.5 Before using any cleanup procedure, the analyst must process a
series of calibration standards through the procedure to validate
elution patterns and the absence of interferences from the reagents.
8. Quality Control
8.1 Each laboratory that uses this method is required to operate a
formal quality control program. The minimum requirements of this program
consist of an initial demonstration of laboratory capability and an
ongoing analysis of spiked samples to evaluate and document data
quality. The laboratory must maintain records to document the quality of
data that is generated. Ongoing data quality checks are compared with
established performance criteria to determine if the results of analyses
meet the performance characteristics of the method. When the results of
sample spikes indicate atypical method performance, a quality control
check standard must be analyzed to confirm that the measurements were
performed in an in-control mode of operation.
8.1.1 The analyst must make an initial, one-time, demonstration of
the ability to generate acceptable accuracy and precision with this
method. This ability is established as described in Section 8.2.
[[Page 178]]
8.1.2 In recognition of advances that are occurring in
chromatography, the analyst is permitted certain options (detailed in
Sections 10.4, 11.1, and 12.1) to improve the separations or lower the
cost of measurements. Each time such modification is made to the method,
the analyst is required to repeat the procedure in Section 8.2.
8.1.3 Before processing any samples, the analyst must analyze a
reagent water blank to demonstrate that interferences from the
analytical system and glassware are under control. Each time a set of
samples is extracted or reagents are changed, a reagent water blank must
be processed as a safeguard against laboratory contamination.
8.1.4 The laboratory must, on an ongoing basis, spike and analyze a
minimum of 10% of all samples to monitor and evaluate laboratory data
quality. This procedure is described in Section 8.3.
8.1.5 The laboratory must, on an ongoing basis, demonstrate through
the analyses of quality control check standards that the operation of
the measurement system is in control. This procedure is described in
Section 8.4. The frequency of the check standard analyses is equivalent
to 10% of all samples analyzed but may be reduced if spike recoveries
from samples (Section 8.3) meet all specified quality control criteria.
8.1.6 The laboratory must maintain performance records to document
the quality of data that is generated. This procedure is described in
Section 8.5.
8.2 To establish the ability to generate acceptable accuracy and
precision, the analyst must perform the following operations.
8.2.1 A quality control (QC) check sample concentrate is required
containing each parameter of interest at the following concentrations in
acetone: Hexachloro-substituted parameters, 10 [micro]g/mL; any other
chlorinated hydrocarbon, 100 [micro]g/mL. The QC check sample
concentrate must be obtained from the U.S. Environmental Protection
Agency, Environmental Monitoring and Support Laboratory in Cincinnati,
Ohio, if available. If not available from that source, the QC check
sample concentrate must be obtained from another external source. If not
available from either source above, the QC check sample concentrate must
be prepared by the laboratory using stock standards prepared
independently from those used for calibration.
8.2.2 Using a pipet, prepare QC check samples at the test
concentrations shown in Table 2 by adding 1.00 mL of QC check sample
concentrate to each of four 1-L aliquots of reagent water.
8.2.3 Analyze the well-mixed QC check samples according to the
method beginning in Section 10.
8.2.4 Calculate the average recovery (X) in [micro]g/L, and the
standard deviation of the recovery (s) in [micro]g/L, for each parameter
using the four results.
8.2.5 For each parameter compare s and X with the corresponding
acceptance criteria for precision and accuracy, respectively, found in
Table 2. If s and X for all parameters of interest meet the acceptance
criteria, the system performance is acceptable and analysis of actual
samples can begin. If any individual s exceeds the precision limit or
any individual X falls outside the range for accuracy, the system
performance is unacceptable for that parameter.
Note: The large number of parameters in Table 2 presents a
substantial probability that one or more will fail at least one of the
acceptance criteria when all parameters are analyzed.
8.2.6 When one or more of the parameters tested fail at least one of
the acceptance criteria, the analyst must proceed according to Section
8.2.6.1 or 8.2.6.2.
8.2.6.1 Locate and correct the source of the problem and repeat the
test for all parameters of interest beginning with Section 8.2.2.
8.2.6.2 Beginning with Section 8.2.2, repeat the test only for those
parameters that failed to meet criteria. Repeated failure, however, will
confirm a general problem with the measurement system. If this occurs,
locate and correct the source of the problem and repeat the test for all
compounds of interest beginning with Section 8.2.2.
8.3 The laboratory must, on an ongoing basis, spike at least 10% of
the samples from each sample site being monitored to assess accuracy.
For laboratories analyzing one to ten samples per month, at least one
spike sample per month is required.
8.3.1 The concentration of the spike in the sample should be
determined as follows:
8.3.1.1 If, as in compliance monitoring, the concentration of a
specific parameter in the sample is being checked against a regulatory
concentration limit, the spike should be at that limit or 1 to 5 times
higher than the background concentration determined in Section 8.3.2,
whichever concentration would be larger.
8.3.1.2 If the concentration of a specific parameter in the sample
is not being checked against a limit specific to that parameter, the
spike should be at the test concentration in Section 8.2.2 or 1 to 5
times higher than the background concentration determined in Section
8.3.2, whichever concentration would be larger.
8.3.1.3 If it is impractical to determine background levels before
spiking (e.g., maximum holding times will be exceeded), the spike
concentration should be (1) the regulatory concentration limit, if any;
or, if none by (2) the larger of either 5 times higher than the expected
background concentration or the test concentration in Section 8.2.2.
[[Page 179]]
8.3.2 Analyze one sample aliquot to determine the background
concentration (B) of each parameter. In necessary, prepare a new QC
check sample concentrate (Section 8.2.1) appropriate for the background
concentrations in the sample. Spike a second sample aliquot with 1.0 mL
of the QC check sample concentrate and analyze it to determine the
concentration after spiking (A) of each parameter. Calculate each
percent recovery (P) as 100 (A-B)%/T, where T is the known true value of
the spike.
8.3.3 Compare the percent recovery (P) for each parameter with the
corresponding QC acceptance criteria found in Table 2. These acceptance
criteria were calculated to include an allowance for error in
measurement of both the background and spike concentrations, assuming a
spike to background ratio of 5:1. This error will be accounted for to
the extent that the analyst's spike to background ratio approaches 5:1.
\7\ If spiking was performed at a concentration lower than the test
concentration in Section 8.2.2, the analyst must use either the QC
acceptance criteria in Table 2, or optional QC acceptance criteria
calculated for the specific spike concentration. To calculate optional
acceptance criteria for the recovery of a parameter: (1) Calculate
accuracy (X') using the equation in Table 3, substituting the spike
concentration (T) for C; (2) calculate overall precision (S') using the
equation in Table 3, substituting X' for X; (3) calculate the range for
recovery at the spike concentration as (100 X'/T)
2.44 (100 S'/T)%. \7\
8.3.4 If any individual P falls outside the designated range for
recovery, that parameter has failed the acceptance criteria. A check
standard containing each parameter that failed the criteria must be
analyzed as described in Section 8.4.
8.4. If any parameter fails the acceptance criteria for recovery in
Section 8.3, a QC check standard containing each parameter that failed
must be prepared and analyzed.
Note: The frequency for the required analysis of a QC check standard
will depend upon the number of parameters being simultaneously tested,
the complexity of the sample matrix, and the performance of the
laboratory.
8.4.1 Prepare the QC check standard by adding 1.0 mL of QC check
sample concentrate (Sections 8.2.1 or 8.3.2) to 1 L of reagent water.
The QC check standard needs only to contain the parameters that failed
criteria in the test in Section 8.3.
8.4.2 Analyze the QC check standard to determine the concentration
measured (A) of each parameter. Calculate each percent recovery
(Ps) as 100 (A/T)%, where T is the true value of the standard
concentration.
8.4.3 Compare the percent recovery (Ps) for each
parameter with the corresponding QC acceptance criteria found in Table
2. Only parameters that failed the test in Section 8.3 need to be
compared with these criteria. If the recovery of any such parameter
falls outside the designated range, the laboratory performance for that
parameter is judged to be out of control, and the problem must be
immediately identified and corrected. The analytical result for that
parameter in the unspiked sample is suspect and may not be reported for
regulatory compliance purposes.
8.5 As part of the QC program for the laboratory, method accuracy
for wastewater samples must be assessed and records must be maintained.
After the analysis of five spiked wastewater samples as in Section 8.3,
calculate the average percent recovery (P) and the standard deviation of
the percent recovery (sp). Express the accuracy assessment as
a percent recovery interval from P-2sp to P+2sp.
If P=90% and sp=10%, for example, the accuracy interval is
expressed as 70-110%. Update the accuracy assessment for each parameter
on a regular basis (e.g. after each five to ten new accuracy
measurements).
8.6 It is recommended that the laboratory adopt additional quality
assurance practices for use with this method. The specific practices
that are most productive depend upon the needs of the laboratory and the
nature of the samples. Field duplicates may be analyzed to assess the
precision of the environmental measurements. When doubt exists over the
identification of a peak on the chromatogram, confirmatory techniques
such as gas chromatography with a dissimilar column, specific element
detector, or mass spectrometer must be used. Whenever possible, the
laboratory should analyze standard reference materials and participate
in relevent performance evaluation studies.
9. Sample Collection, Preservation, and Handling
9.1 Grab samples must be collected in glass containers. Conventional
sampling practices 8 should be followed, except that the
bottle must not be prerinsed with sample before collection. Composite
samples should be collected in refrigerated glass containers in
accordance with the requirements of the program. Automatic sampling
equipment must be as free as possible of Tygon tubing and other
potential sources of contamination.
9.2 All samples must be iced or refrigerated at 4 [deg]C from the
time of collection until extraction.
9.3 All samples must be extracted within 7 days of collection and
completely analyzed within 40 days of extraction.2
10. Sample Extraction
10.1 Mark the water meniscus on the side of the sample bottle for
later determination of sample volume. Pour the entire sample into a 2-L
separatory funnel.
[[Page 180]]
10.2 Add 60 mL of methylele chloride to the sample bottle, seal, and
shake 30 s to rinse the inner surface. Transfer the solvent to the
separatory funnel and extract the sample by shaking the funnel for 2 min
with periodic venting to release excess pressure. Allow the organic
layer to separate from the water phase for a minimum of 10 min. If the
emulsion interface between layers is more than one-third the volume of
the solvent layer, the analyst must employ mechanical techniques to
complete the phase separation. The optimum technique depends upon the
sample, but may include stirring, filtration of the emulsion through
glass wool, centrifugation, or other physical methods. Collect the
methylene chloride extract in a 250-mL Erlenmeyer flask.
10.3 Add a second 60-mL volume of methylene chloride to the sample
bottle and repeat the extraction procedure a second time, combining the
extracts in the Erlenmeyer flask. Perform a third extraction in the same
manner.
10.4 Assemble a Kuderna-Danish (K-D) concentrator by attaching a 10-
mL concentrator tube to a 500-mL evaporative flask. Other concentration
devices or techniques may be used in place of the K-D concentrator if
the requirements of Section 8.2 are met.
10.5 Pour the combined extract through a solvent-rinsed drying
column containing about 10 cm of anhydrous sodium sulfate, and collect
the extract in the K-D concentrator. Rinse the Erlenmeyer flask and
column with 20 to 30 mL of methylene chloride to complete the
quantitative transfer.
10.6 Add one or two clean boiling chips to the evaporative flask and
attach a three-ball Snyder column. Prewet the Snyder column by adding
about 1 mL of methylene chloride to the top. Place the K-D apparatus on
a hot water bath (60 to 65 [deg]C) so that the concentrator tube is
partially immersed in the hot water, and the entire lower rounded
surface of the flask is bathed with hot vapor. Adjust the vertical
position of the apparatus and the water temperature as required to
complete the concentration in 15 to 20 min. At the proper rate of
distillation the balls of the column will actively chatter but the
chambers will not flood with condensed solvent. When the apparent volume
of liquid reaches 1 to 2 mL, remove the K-D apparatus and allow it to
drain and cool for at least 10 min.
Note: The dichloribenzenes have a sufficiently high volatility that
significant losses may occur in concentration steps if care is not
exercised. It is important to maintain a constant gentle evaporation
rate and not to allow the liquid volume to fall below 1 to 2 mL before
removing the K-D apparatus from the hot water bath.
10.7 Momentarily remove the Snyder column, add 50 mL of hexane and a
new boiling chip, and reattach the Snyder column. Raise the tempeature
of the water bath to 85 to 90 [deg]C. Concentrate the extract as in
Section 10.6, except use hexane to prewet the column. The elapsed time
of concentration should be 5 to 10 min.
10.8 Romove the Snyder column and rinse the flask and its lower
joint into the concentrator tube with 1 to 2 mL of hexane. A 5-mL
syringe is recommended for this operation. Stopper the concentrator tube
and store refrigerated if further processing will not be performed
immediately. If the extract will be stored longer than two days, it
should be transferred to a Teflon-sealed screw-cap vial. If the sample
extract requires no further cleanup, proceed with gas chromatographic
analysis (Section 12). If the sample requires further cleanup, proceed
to Section 11.
10.9 Determine the original sample volume by refilling the sample
bottle to the mark and transferring the liquid to a 1000-mL graduated
cylinder. Record the sample volume to the nearest 5 mL.
11. Cleanup and Separation
11.1 Cleanup procedures may not be necessary for a relatively clean
sample matrix. If particular circumstances demand the use of a cleanup
procedure, the analyst may use the procedure below or any other
appropriate procedure. However, the analyst first must demonstrate that
the requirements of Section 8.2 can be met using the method as revised
to incorporate the cleanup procedure.
11.2 Florisil column cleanup for chlorinated hydrocarbons:
11.2.1 Adjust the sample extract to 10 mL with hexane.
11.2.2 Place 12 g of Florisil into a chromatographic column. Tap the
column to settle the Florisil and add 1 to 2 cm of anhydrous sodium
sulfate to the top.
11.2.3 Preelute the column with 100 mL of petroleum ether. Discard
the eluate and just prior to exposure of the sodium sulfate layer to the
air, quantitatively transfer the sample extract onto the column by
decantation and subsequent petroleum ether washings. Discard the eluate.
Just prior to exposure of the sodium sulfate layer to the air, begin
eluting the column with 200 mL of petroleum ether and collect the eluate
in a 500-mL K-D flask equipped with a 10-mL concentrator tube. This
fraction should contain all of the chlorinated hydrocarbons.
11.2.4 Concentrate the fraction as in Section 10.6, except use
hexane to prewet the column. When the apparatus is cool, remove the
Snyder column and rinse the flask and its lower joint into the
concentrator tube with hexane. Analyze by gas chromatography (Section
12).
[[Page 181]]
12. Gas Chromatography
12.1 Table 1 summarizes the recommended operating conditions for the
gas chromatograph. Included in this table are retention times and MDL
that can be achieved under these conditions. Examples of the separations
achieved by Columl 2 are shown in Figures 1 and 2. Other packed or
capillary (open-tubular) columns, chromatographic conditions, or
detectors may be used if the requirements of Section 8.2 are met.
12.2 Calibrate the system daily as described in Section 7.
12.3 If the internal standard calibration procedure is being used,
the internal standard must be added to the sample extract and mixed
throughly immediately before injection into the gas chromatograph.
12.4 Inject 2 to 5 [micro]L of the sample extract or standard into
the gas chromatograph using the solvent-flush techlique.9
Smaller (1.0 [micro]L) volumes may be injected if automatic devices are
employed. Record the volume injected to the nearest 0.05 [micro]L, the
total extract volume, and the resulting peak size in area or peak height
units.
12.5 Identify the parameters in the sample by comparing the
retention times of the peaks in the sample chromatogram with those of
the peaks in standard chromatograms. The width of the retention time
window used to make identifications should be based upon measurements of
actual retention time variations of standards over the course of a day.
Three times the standard deviation of a retention time for a compound
can be used to calculate a suggested window size; however, the
experience of the analyst should weigh heavily in the interpretation of
chromatograms.
12.6 If the response for a peak exceeds the working range of the
system, dilute the extract and reanalyze.
12.7 If the measurement of the peak response is prevented by the
presence of interferences, further cleanup is required.
13. Calculations
13.1 Determine the concentration of individual compounds in the
sample.
13.1.1 If the external standard calibration procedure is used,
calculate the amount of material injected from the peak response using
the calibration curve or calibration factor determined in Section 7.2.2.
The concentration in the sample can be calculated from Equation 2.
[GRAPHIC] [TIFF OMITTED] TC15NO91.120
Equation 2
where:
A=Amount of material injected (ng).
Vi=Volume of extract injected ([micro]L).
Vt=Volume of total extract ([micro]L).
Vs=Volume of water extracted (mL).
13.1.2 If the internal standard calibration procedure is used,
calculate the concentration in the sample using the response factor (RF)
determined in Section 7.3.2 and Equation 3.
[GRAPHIC] [TIFF OMITTED] TC15NO91.121
Equation 3
where:
As=Response for the parameter to be measured.
Ais=Response for the internal standard.
Is=Amount of internal standard added to each extract
([micro]g).
Vo=Volume of water extracted (L).
13.2 Report results in [micro]g/L without correction for recovery
data. All QC data obtained should be reported with the sample results.
14. Method Performance
14.1 The method detection limit (MDL) is defined as the minimum
concentration of a substance that can be measured and reported with 99%
confidence that the value is above zero.1 The MDL
concentrations listed in Table 1 were obtained using reagent
water.10 Similar results were achieved using representative
wastewaters. The MDL actually achieved in a given analysis will vary
depending on instrument sensitivity and matrix effects.
14.2 This method has been tested for linearity of spike recovery
from reagent water and has been demonstrated to be applicable over the
concentration range from 4xMDL to 1000xMDL.10
14.3 This method was tested by 20 laboratories using reagent water,
drinking water, surface water, and three industrial wastewaters spiked
at six concentrations over the range 1.0 to 356 [micro]g/L.11
Single operator precision, overall precision, and method accuracy were
found to be directly related to the concentration of the parameter and
essentially independent of the sample matrix. Linear equations to
describe these relationships are presented in Table 3.
References
1. 40 CFR part 136, appendix B.
2. ``Determination of Chlorinated Hydrocarbons In Industrial and
Municipal Wastewaters, ``EPA 6090/4-84-ABC, National Technical
Information Service, PBXYZ, Springfield, Virginia, 22161 November 1984.
3. ASTM Annual Book of Standards, Part 31, D3694-78. ``Standard
Practices for Preparation of Sample Containers and for Preservation of
Organic Constituents,'' American
[[Page 182]]
Society for Testing and Materials, Philadelphia.
4. ``Carcinogens--Working With Carcinogens,'' Department of Health,
Education, and Welfare, Public Health Service, Center for Disease
Control, National Institute for Occupational Safety and Health,
Publication No. 77-206, August 1977.
5. ``OSHA Safety and Health Standards, General Industry,'' (29 CFR
part 1910), Occupational Safety and Health Administration, OSHA 2206
(Revised, January 1976).
6. ``Safety in Academic Chemistry Laboratories,'' American Chemical
Society Publication, Committee on Chemical Safety, 3rd Edition, 1979.
7. Provost, L.P., and Elder, R.S. ``Interpretation of Percent
Recovery Data,''American Laboratory, 15, 58-63 (1983). (The value 2.44
used in the equation in Section 8.3.3 is two times the value 1.22
derived in this report.)
8. ASTM Annual Book of Standards, Part 31, D3370-76. ``Standard
Practices for Sampling Water,'' American Society for Testing and
Materials, Philadelphia.
9. Burke, J.A. ``Gas Chromatography for Pesticide Residue Analysis;
Some Practical Aspects,'' Journal of the Association of Official
Analytical Chemists, 48, 1037 (1965).
10. ``Development of Detection Limits, EPA Method 612, Chlorinated
Hydrocarbons,'' Special letter report for EPA Contract 68-03-2625, U.S.
Environmental Protection Agency, Environmental Monitoring and Support
Laboratory, Cincinnati, Ohio 45268.
11. ``EPA Method Study Method 612--Chlorinated Hydrocarbons,'' EPA
600/4-84-039, National Technical Information Service, PB84-187772,
Springfield, Virginia 22161, May 1984.
12. ``Method Performance for Hexachlorocyclopentadiene by Method
612,'' Memorandum from R. Slater, U.S. Environmental Protection Agency,
Environmental Monitoring and Support Laboratory, Cincinnati, Ohio 45268,
December 7, 1983.
Table 1--Chromatographic Conditions and Method Detection Limits
------------------------------------------------------------------------
Retention time (min) Method
-------------------------- detection
Parameter limit
Column 1 Column 2 ([micro]g/
L)
------------------------------------------------------------------------
1,3-Dichlorobenzene.............. 4.5 6.8 1.19
Hexachloroethane................. 4.9 8.3 0.03
1,4-Dichlorobenzene.............. 5.2 7.6 1.34
1,2-Dichlorobenzene.............. 6.6 9.3 1.14
Hexachlorobutadiene.............. 7.7 20.0 0.34
1,2,4-Trichlorobenzene........... 15.5 22.3 0.05
Hexachlorocyclopentadiene........ nd c 16.5 0.40
2-Chloronaphthalene.............. a 2.7 b 3.6 0.94
Hexachlorobenzene................ a 5.6 b 10.1 0.05
------------------------------------------------------------------------
Column 1 conditions: Supelcoport (100/120 mesh) coated with 1% SP-1000
packed in a 1.8 m x 2 mm ID glass column with 5% methane/95% argon
carrier gas at 25 mL/min. flow rate. Column temperature held
isothermal at 65 [deg]C, except where otherwise indicated.
Column 2 conditions: Supelcoport (80/100 mesh) coated with 1.5% OV-1/
2.4% OV-225 packed in a 1.8 m x 2 mm ID glass column with 5% methane/
95% argon carrier gas at 25 mL/min. flow rate. Column temperature held
isothermal at 75 [deg]C, except where otherwise indicated.
nd=Not determined.
a 150 [deg]C column temperature.
b 165 [deg]C column temperature.
c 100 [deg]C column temperature.
Table 2--QC Acceptance Criteria--Method 612
----------------------------------------------------------------------------------------------------------------
Limit for Range for X
Test conc. s ([micro]g/ Range for
Parameter ([micro]g/ ([micro]g/ L) P, Ps
L) L) (percent)
----------------------------------------------------------------------------------------------------------------
2-Chloronaphthalene............................................. 100 37.3 29.5-126.9 9-148
1,2-Dichlorobenzene............................................. 100 28.3 23.5-145.1 9-160
1,3-Dichlorobenzene............................................. 100 26.4 7.2-138.6 D-150
1,4-Dichlorobenzene............................................. 100 20.8 22.7-126.9 13-137
Hexachlorobenzene............................................... 10 2.4 2.6-14.8 15-159
Hexachlorobutadiene............................................. 10 2.2 D-12.7 D-139
Hexachlorocyclopentadiene....................................... 10 2.5 D-10.4 D-111
Hexachloroethane................................................ 10 3.3 2.4-12.3 8-139
1,2,4-Trichlorobenzene.......................................... 100 31.6 20.2-133.7 5-149
----------------------------------------------------------------------------------------------------------------
s=Standard deviation of four recovery measurements, in [micro]g/L (Section 8.2.4).
X=Average recovery for four recovery measurements, in [micro]g/L (Section 8.2.4).
P, Ps=Percent recovery measured (Section 8.3.2, Section 8.4.2).
D=Detected; result must be greater than zero.
Note: These criteria are based directly upon the method performance data in Table 3. Where necessary, the limits
for recovery have been broadened to assure applicability of the limits to concentrations below those used to
develop Table 3.
[[Page 183]]
Table 3--Method Accuracy and Precision as Functions of Concentration--Method 612
----------------------------------------------------------------------------------------------------------------
Single analyst
Parameter Acccuracy, as recovery, precision, sr' Overall precision, S'
X' ([micro]g/L) ([micro]g/L) ([micro]g/L)
----------------------------------------------------------------------------------------------------------------
2-Chloronaphthalene................... 0.75C+3.21 0.28X-1.17 0.38X-1.39
1,2-Dichlorobenzene................... 0.85C-0.70 0.22X-2.95 0.41X-3.92
1,3-Dichlorobenzene................... 0.72C+0.87 0.21X-1.03 0.49X-3.98
1,4-Dichlorobenzene................... 0.72C+2.80 0.16X-0.48 0.35X-0.57
Hexachlorobenzene..................... 0.87C-0.02 0.14X+0.07 0.36X-0.19
Hexachlorobutadiene................... 0.61C+0.03 0.18X+0.08 0.53X-0.12
Hexachlorocyclopentadiene a........... 0.47C 0.24X 0.50X
Hexachloroethane...................... 0.74C-0.02 0.23X+0.07 0.36X-0.00
1,2,4-Trichlorobenzene................ 0.76C+0.98 0.23X-0.44 0.40X-1.37
----------------------------------------------------------------------------------------------------------------
X'=Expected recovery for one or more measurements of a sample containing a concentration of C, in [micro]g/L.
sr'=Expected single analyst standard deviation of measurements at an average concentration found of X, in
[micro]g/L.
S'=Expected interlaboratory standard deviation of measurements at an average concentration found of X, in
[micro]g/L.
C=True value for the concentration, in [micro]g/L.
X=Average recovery found for measurements of samples containing a concentration of C, in [micro]g/L.
a Estimates based upon the performance in a single laboratory.\12\
[[Page 184]]
[GRAPHIC] [TIFF OMITTED] TC02JY92.036
[[Page 185]]
[GRAPHIC] [TIFF OMITTED] TC02JY92.037
[[Page 186]]
Method 613--2,3,7,8-Tetrachlorodibenzo-p-Dioxin
1. Scope and Application
1.1 This method covers the determination of 2,3,7,8-
tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD). The following parameter may
be determined by this method:
------------------------------------------------------------------------
STORET
Parameter No. GAS No.
------------------------------------------------------------------------
2,3,7,8-TCDD..................................... 34675 1746-01-6
------------------------------------------------------------------------
1.2 This is a gas chromatographic/mass spectrometer (GC/MS) method
applicable to the determination of 2,3,7,8-TCDD in municipal and
industrial discharges as provided under 40 CFR 136.1. Method 625 may be
used to screen samples for 2,3,7,8-TCDD. When the screening test is
positive, the final qualitative confirmation and quantification must be
made using Method 613.
1.3 The method detection limit (MDL, defined in Section 14.1) \1\
for 2,3,7,8-TCDD is listed in Table 1. The MDL for a specific wastewater
may be different from that listed, depending upon the nature of
interferences in the sample matrix.
1.4 Because of the extreme toxicity of this compound, the analyst
must prevent exposure to himself, of to others, by materials knows or
believed to contain 2,3,7,8-TCDD. Section 4 of this method contains
guidelines and protocols that serve as minimum safe-handling standards
in a limited-access laboratory.
1.5 Any modification of this method, beyond those expressly
permitted, shall be considered as a major modification subject to
application and approval of alternate test procedures under 40 CFR 136.4
and 136.5.
1.6 This method is restricted to use by or under the supervision of
analysts experienced in the use of a gas chromatograph/mass spectrometer
and in the interpretation of mass spectra. Each analyst must demonstrate
the ability to generate acceptable results with this method using the
procedure described in Section 8.2.
2. Summary of Method
2.1 A measured volume of sample, approximately 1-L, is spiked with
an internal standard of labeled 2,3,7,8-TCDD and extracted with
methylene chloride using a separatory funnel. The methylene chloride
extract is exchanged to hexane during concentration to a volume of 1.0
mL or less. The extract is then analyzed by capillary column GC/MS to
separate and measure 2,3,7,8-TCDD.\2,3\
2.2 The method provides selected column chromatographic cleanup
proceudres to aid in the elimination of interferences that may be
encountered.
3. Interferences
3.1 Method interferences may be caused by contaminants in solvents,
reagents, glassware, and other sample processing hardware that lead to
discrete artifacts and/or elevated backgrounds at the masses (m/z)
monitored. All of these materials must be routinely demonstrated to be
free from interferences under the conditions of the analysis by running
laboratory reagent blanks as described in Section 8.1.3.
3.1.1 Glassware must be scrupulously cleaned.\4\ Clean all glassware
as soon as possible after use by rinsing with the last solvent used in
it. Solvent rinsing should be followed by detergent washing with hot
water, and rinses with tap water and distilled water. The glassware
should then be drained dry, and heated in a muffle furnace at 400 [deg]C
for 15 to 30 min. Some thermally stable materials, such as PCBs, may not
be eliminated by the treatment. Solvent rinses with acetone and
pesticide quality hexane may be substituted for the muffle furnace
heating. Thorough rinsing with such solvents usually eliminates PCB
interference. Volumetric ware should not be heated in a muffle furnace.
After drying and cooling, glassware should be sealed and stored in a
clean environment to prevent any accumulation of dust or other
contaminants. Store inverted or capped with aluminum foil.
3.1.2 The use of high purity reagents and solvents helps to
mininmize interference problems. Purification of solvents by
distillation in all-glass systems may be required.
3.2 Matrix interferences may be caused by contaminants that are
coextracted from the sample. The extent of matrix interferences will
vary considerably from source to source, depending upon the nature and
diversity of the industrial complex or municipality being sampled.
2,3,7,8-TCDD is often associated with other interfering chlorinated
compounds which are at concentrations several magnitudes higher than
that of 2,3,7,8-TCDD. The cleanup producers in Section 11 can be used to
overcome many of these interferences, but unique samples may require
additional cleanup approaches 1, 5-7 to eliminate false
positives and achieve the MDL listed in Table 1.
3.3 The primary column, SP-2330 or equivalent, resolves 2,3,7,8-TCDD
from the other 21 TCDD insomers. Positive results using any other gas
chromatographic column must be confirmed using the primary column.
4. Safety
4.1 The toxicity or carcinogenicity of each reagent used in this
method has not been precisely defined; however, each chemical compound
should be treated as a potential health hazard. From this viewpoint,
exposure to these chemicals must be reduced to
[[Page 187]]
the lowest possible level by whatever means available. The laboratory is
responsible for maintaining a current awareness file of OSHA regulations
regarding the safe handling of the chemicals specified in this method. A
reference file of material data handling sheets should also be made
available to all personnel involved in the chemical analysis. Additional
references to laboratory safety are available and have been identified
8-10 for the information of the analyst. Benzene and 2,3,7,8-
TCDD have been identified as suspected human or mammalian carcinogens.
4.2 Each laboratory must develop a strict safety program for
handling 2,3,7,8-TCDD. The following laboratory practices are
recommended:
4.2.1 Contamination of the laboratory will be minimized by
conducting all manipulations in a hood.
4.2.2 The effluents of sample splitters for the gas chromatograph
and roughing pumps on the GC/MS should pass through either a column of
activated charcoal or be bubbled through a trap containing oil or high-
boiling alcohols.
4.2.3 Liquid waste should be dissolved in methanol or ethanol and
irradiated with ultraviolet light with a wavelength greater than 290 nm
for several days. (Use F 40 BL lamps or equivalent). Analyze liquid
wastes and dispose of the solutions when 2,3,7,8-TCDD can no longer be
detected.
4.3 Dow Chemical U.S.A. has issued the following precautimns
(revised November 1978) for safe handling of 2,3,7,8-TCDD in the
laboratory:
4.3.1 The following statements on safe handling are as complete as
possible on the basis of available toxicological information. The
precautions for safe handling and use are necessarily general in nature
since detailed, specific recommendations can be made only for the
particular exposure and circumstances of each individual use. Inquiries
about specific operations or uses may be addressed to the Dow Chemical
Company. Assistance in evaluating the health hazards of particular plant
conditions may be obtained from certain consulting laboratories and from
State Departments of Health or of Labor, many of which have an
industrial health service. 2,3,7,8-TCDD is extremely toxic to laboratory
animals. However, it has been handled for years without injury in
analytical and biological laboratories. Techniques used in handling
radioactive and infectious materials are applicable to 2,3,7,8,-TCDD.
4.3.1.1 Protective equipment--Throw- away plas tic gloves, apron or
lab coat, safety glasses, and a lab hood adequate for radioactive work.
4.3.1.2 Training--Workers must be trained in the proper method of
removing contaminated gloves and clothing without contacting the
exterior surfaces.
4.3.1.3 Personal hygiene--Thorough washing of hands and forearms
after each manipulation and before breaks (coffee, lunch, and shift).
4.3.1.4 Confinement--Isolated work area, posted with signs,
segregated glassware and tools, plastic-backed absorbent paper on
benchtops.
4.3.1.5 Waste--Good technique includes mini miz ing contaminated
waste. Plastic bag liners should be used in waste cans. Janitors must be
trained in the safe handling of waste.
4.3.1.6 Disposal of wastes--2,3,7,8-TCDD decomposes above 800
[deg]C. Low-level waste such as absorbent paper, tissues, animal
remains, and plastic gloves may be burned in a good incinerator. Gross
quantities (milligrams) should be packaged securely and disposed through
commercial or governmental channels which are capable of handling high-
level radioactive wastes or extremely toxic wastes. Liquids should be
allowed to evaporate in a good hood and in a disposable container.
Residues may then be handled as above.
4.3.1.7 Decontamination--For personal decontamination, use any mild
soap with plenty of scrubbing action. For decontamination of glassware,
tools, and surfaces, Chlorothene NU Solvent (Trademark of the Dow
Chemical Company) is the least toxic solvent shown to be effective.
Satisfactory cleaning may be accomplished by rinsing with Chlorothene,
then washing with any detergent and water. Dishwater may be disposed to
the sewer. It is prudent to minimize solvent wastes because they may
require special disposal through commercial sources which are expensive.
4.3.1.8 Laundry--Clothing known to be contaminated should be
disposed with the precautions described under Section 4.3.1.6. Lab coats
or other clothing worn in 2,3,7,8-TCDD work areas may be laundered.
Clothing should be collected in plastic bags. Persons who convey the
bags and launder the clothing should be advised of the hazard and
trained in proper handling. The clothing may be put into a washer
without contact if the launderer knows the problem. The washer should be
run through a cycle before being used again for other clothing.
4.3.1.9 Wipe tests--A useful method of determining cleanliness of
work surfaces and tools is to wipe the surface with a piece of filter
paper. Extraction and analysis by gas chromatography can achieve a limit
of sensitivity of 0.1 [micro]g per wipe. Less than 1 [micro]g of
2,3,7,8-TCDD per sample indicates acceptable cleanliness; anything
higher warrants further cleaning. More than 10 [micro]g on a wipe sample
constitutes an acute hazard and requires prompt cleaning before further
use of the equipment or work space. A high (10 [micro]g)
[[Page 188]]
2,3,7,8-TCDD level indicates that unacceptable work practices have been
employed in the past.
4.3.1.10 Inhalation--Any procedure that may produce airborne
contamination must be done with good ventilation. Gross losses to a
ventilation system must not be allowed. Handling of the dilute solutions
normally used in analytical and animal work presents no inhalation
hazards except in the case of an accident.
4.3.1.11 Accidents--Remove contaminated clothing immediately, taking
precautions not to contaminate skin or other articles. Wash exposed skin
vigorously and repeatedly until medical attention is obtained.
5. Apparatus and Materials
5.1 Sampling equipment, for discrete or composite sampling.
5.1.1 Grab sample bottle--1-L or 1-qt, amber glass, fitted with a
screw cap lined with Teflon. Foil may be substituted for Teflon if the
sample is not corrosive. If amber bottles are not available, protect
samples from light. The bottle and cap liner must be washed, rinsed with
acetone or methylene chloride, and dried before use to minimize
contamination.
5.1.2 Automatic sampler (optional)--The sampler must incorporate
glass sample containers for the collection of a minimum of 250 mL of
sample. Sample containers must be kept refrigerated at 4 [deg]C and
protected from light during compositing. If the sampler uses a
peristaltic pump, a minimum length of compressible silicone rubber
tubing may be used. Before use, however, the compressible tubing should
be thoroughly rinsed with methanol, followed by repeated rinsings with
distilled water to minimize the potential for contamination of the
sample. An integrating flow meter is required to collect flow
proportional composites.
5.1.3 Clearly label all samples as ``POISON'' and ship according to
U.S. Department of Transportation regulations.
5.2 Glassware (All specifications are suggested. Catalog numbers are
included for illustration only.):
5.2.1 Separatory funnels--2-L and 125-mL, with Teflon stopcock.
5.2.2 Concentrator tube, Kuderna-Danish--10-mL, graduated (Kontes K-
570050-1025 or equivalent). Calibration must be checked at the volumes
employed in the test. Ground glass stopper is used to prevent
evaporation of extracts.
5.2.3 Evaporative flask, Kuderna-Danish--500-mL (Kontes K-570001-
0500 or equivalent). Attach to concentrator tube with springs.
5.2.4 Snyder column, Kuderna-Danish--Three-ball macro (Kontes K-
503000-0121 or equivalent).
5.2.5 Snyder column, Kuderna-Danish--Two- ball micro (Kontes K-
569001-0219 or equivalent).
5.2.6 Vials--10 to 15-mL, amber glass, with Teflon-lined screw cap.
5.2.7 Chromatographic column--300 mm long x 10 mm ID, with Teflon
stopcock and coarse frit filter disc at bottom.
5.2.8 Chromatographic column--400 mm long x 11 mm ID, with Teflon
stopcock and coarse frit filter disc at bottom.
5.3 Boiling chips--Approximately 10/40 mesh. Heat to 400 [deg]C for
30 min or Soxhlet extract with methylene chloride.
5.4 Water bath--Heated, with concentric ring cover, capable of
temperature control (2 [deg]C). The bath should be
used in a hood.
5.5 GC/MS system:
5.5.1 Gas chromatograph--An analytical system complete with a
temperature programmable gas chromatograph and all required accessories
including syringes, analytical columns, and gases. The injection port
must be designed for capillary columns. Either split, splitless, or on-
column injection techniques may be employed, as long as the requirements
of Section 7.1.1 are achieved.
5.5.2 Column--60 m long x 0.25 mm ID glass or fused silica, coated
with SP-2330 (or equivalent) with a film thickness of 0.2 [micro]m. Any
equivalent column must resolve 2, 3, 7, 8-TCDD from the other 21 TCDD
isomers.16
5.5.3 Mass spectrometer--Either a low resolution mass spectrometer
(LRMS) or a high resolution mass spectrometer (HRMS) may be used. The
mass spectrometer must be equipped with a 70 V (nominal) ion source and
be capable of aquiring m/z abundance data in real time selected ion
monitoring (SIM) for groups of four or more masses.
5.5.4 GC/MS interface--Any GC to MS interface can be used that
achieves the requirements of Section 7.1.1. GC to MS interfaces
constructed of all glass or glass-lined materials are recommended. Glass
surfaces can be deactivated by silanizing with dichlorodimethylsilane.
To achieve maximum sensitivity, the exit end of the capillary column
should be placed in the ion source. A short piece of fused silica
capillary can be used as the interface to overcome problems associated
with straightening the exit end of glass capillary columns.
5.5.5 The SIM data acquired during the chromatographic program is
defined as the Selected Ion Current Profile (SICP). The SICP can be
acquired under computer control or as a real time analog output. If
computer control is used, there must be software available to plot the
SICP and report peak height or area data for any m/z in the SICP between
specified time or scan number limits.
5.6 Balance--Analytical, capable of accurately weighing 0.0001 g.
6. Reagents
6.1 Reagent water--Reagent water is defined as a water in which an
interferent is not observed at the MDL of 2, 3, 7, 8-TCDD.
[[Page 189]]
6.2 Sodium hydroxide solution (10 N)--Dissolve 40 g of NaOH (ACS) in
reagent water and dilute to 100 mL. Wash the solution with methylene
chloride and hexane before use.
6.3 Sodium thiosulfate--(ACS) Granular.
6.4 Sulfuric acid--Concentrated (ACS, sp. gr. 1.84).
6.5 Acetone, methylene chloride, hexane, benzene, ortho-xylene,
tetradecane--Pesticide quality or equivalent.
6.6 Sodium sulfate--(ACS) Granular, anhydrous. Purify by heating at
400 [deg]C for 4 h in a shallow tray.
6.7 Alumina--Neutral, 80/200 mesh (Fisher Scientific Co., No. A-540
or equivalent). Before use, activate for 24 h at 130 [deg]C in a foil-
covered glass container.
6.8 Silica gel--High purity grade, 100/120 mesh (Fisher Scientific
Co., No. S-679 or equivalent).
6.9 Stock standard solutions (1.00 [micro]g/[micro]L)--Stock
standard solutimns can be prepared from pure standard materials or
purchased as certified solutions. Acetone should be used as the solvent
for spiking solutions; ortho-xylene is recommended for calibration
standards for split injectors; and tetradecane is recommended for
splitless or on-colum injectors. Analyze stock internal standards to
verify the absence of native 2,3,7,8-TCDD.
6.9.1 Prepare stock standard solutions of 2,3,7,8-TCDD (mol wt 320)
and either 37C14 2,3,7,8-TCDD (mol wt 328) or
13C112 2,3,7,8-TCDD (mol wt 332) in an isolated
area by accurately weighing about 0.0100 g of pure material. Dissolve
the material in pesticide quality solvent and dilute to volume in a 10-
mL volumetric flask. When compound purity is assayed to be 96% or
greater, the weight can be used without correction to calculate the
concentration of the stock standard. Commercially prepared stock
standards can be used at any concentration if they are certified by the
manufacturer or by an independent source.
6.9.2 Transfer the stock standard solutions into Teflon-sealed
screw-cap bottles. Store in an isolated refrigerator protected from
light. Stock standard solutions should be checked frequently for signs
of degradation or evaporation, especially just prior to preparing
calibration standards or spiking solutions from them.
6.9.3 Stock standard solutions must be replaced after six months, or
sooner if comparison with check standards indicates a problem.
6.10 Internal standard spiking solution (25 ng/mL)--Using stock
standard solution, prepare a spiking solution in acetone of either
13 Cl12 or 37 Cl4 2,3,7,8-
TCDD at a concentration of 25 ng/mL. (See Section 10.2)
6.11 Quality control check sample concentrate--See Section 8.2.1.
7. Calibration
7.1 Establish gas chromatograhic operating conditions equivalent to
those given in Table 1 and SIM conditions for the mass spectrometer as
described in Section 12.2 The GC/MS system must be calibrated using the
internal standard technique.
7.1.1 Using stock standards, prepare calibration standards that will
allow measurement of relative response factors of at least three
concentration ratios of 2,3,7,8-TCDD to internal standard. Each
calibration standard must be prepared to contain the internal standard
at a concentration of 25 ng/mL. If any interferences are contributed by
the internal standard at m/z 320 and 322, its concentration may be
reduced in the calibration standards and in the internal standard
spiking solution (Section 6.10). One of the calibration standards should
contain 2,3,7,8-TCDD at a concentration near, but above, the MDL and the
other 2,3,7,8-TCDD concentrations should correspond to the expected
range of concentrations found in real samples or should define the
working range of the GC/MS system.
7.1.2 Using injections of 2 to 5 [micro]L, analyze each calibration
standardaccording to Section 12 and tabulate peak height or area
response against the concentration of 2,3,7,8-TCDD and internal
standard. Calculate response factors (RF) for 2,3,7,8-TCDD using
Equation 1.
[GRAPHIC] [TIFF OMITTED] TC15NO91.122
Equation 1
where:
As=SIM response for 2,3,7,8-TCDD m/z 320.
Ais=SIM response for the internal standard, m/z 332 for \13\
C12 2,3,7,8-TCDD m/z 328 for 37 Cl4
2,3,7,8-TCDD.
Cis=Concentration of the internal standard ([micro]g/L).
Cs=Concentration of 2,3,7,8-TCDD ([micro]g/L).
If the RF value over the working range is a constant (<10% relative
standard deviation, RSD), the RF can be assumed to be invariant and the
average RF can be used for calculations. Alternatively, the results can
be used to plot a calibration curve of response ratios, As/
Ais, vs. RF.
7.1.3 The working calibration curve or RF must be verified on each
working day by the measurement of one or more 2,3,7,8-TCDD calibration
standards. If the response for 2,3,7,8-TCDD varies from the predicted
response by more than 15%, the test must be
repeated using a fresh calibration standard. Alternatively, a new
calibration curve must be prepared.
[[Page 190]]
7.2 Before using any cleanup procedure, the analyst must process a
series of calibration standards through the procedure to validate
elution patterns and the absence of interferences from the reagents.
8. Quality Control
8.1 Each laboratory that uses this method is required to operate a
formal quality control program. The minimum requirements of this program
consist of an initial demonstration of laboratory capability and an
ongoing analysis of spiked samples to evaluate and document data
quality. The laboratory must maintain records to document the quality of
data that is generated. Ongoing data quality checks are compared with
established performance criteria to determine if the results of analyses
meet the performance characteristics of the method. When results of
sample spikes indicate atypical method performance, a quality control
check standard must be analyzed to confirm that the measurements were
performed in an in-control mode of operation.
8.1.1 The analyst must make an initial, one-time, demonstration of
the ability to generate acceptable accuracy and precision with this
method. This ability is established as described in Section 8.2.
8.1.2 In recognition of advances that are occurring in
chromatography, the analyst is permitted certain options (detailed in
Sections 10.5, 11.1, and 12.1) to improve the separations or lower the
cost of measurements. Each time such a modification is made to the
method, the analyst is required to repeat the procedure in Section 8.2
8.1.3 Before processing any samples, the analyst must analyze a
reagent water blank to demonstrate that interferences from the
analytical system and glassware are under control. Each time a set of
samples is extracted or reagents are changed, a reagent water blank must
be processed as a safeguard against laboratory contamination.
8.1.4 The laboratory must, on an ongoing basis, spike and analyze a
minimum of 10% of all samples with native 2,3,7,8-TCDD to monitor and
evaluate laboratory data quality. This procedure is described in Section
8.3.
8.1.5 The laboratory must, on an ongoing basis, demonstrate through
the analyses of quality control check standards that the operation of
the measurement system is in control. This procedure is described in
Section 8.4. The frequency of the check standard analyses is equivalent
to 10% of all samples analyzed but may be reduced if spike recoveries
from samples (Section 8.3) meet all specified quality control criteria.
8.1.6 The laboratory must maintain performance records to document
the quality of data that is generated. This procedure is described in
Section 8.5.
8.2 To establish the ability to generate acceptable accuracy and
precision, the analyst must perform the following operations.
8.2.1 A quality control (QC) check sample concentrate is required
containing 2,3,7,8-TCDD at a concentration of 0.100 [micro]g/mL in
acetone. The QC check sample concentrate must be obtained from the U.S.
Environmental Protection Agency, Environmental Monitoring and Support
Laboratory in Cincinnati, Ohio, if available. If not available from that
source, the QC check sample concentrate must be obtained from another
external source. If not available from either source above, the QC check
sample concentrate must be prepared by the laboratory using stock
standards prepared independently from those used for calibration.
8.2.2 Using a pipet, prepare QC check samples at a concentration of
0.100 [micro]g/L (100 ng/L) by adding 1.00 mL of QC check sample
concentrate to each of four 1-L aliquots of reagent water.
8.2.3 Analyze the well-mixed QC check samples according to the
method beginning in Section 10.
8.2.4 Calculate the average recovery (X) in [micro]g/L, and the
standard deviation of the recovery (s) in [micro]g/L, for 2,3,7,8-TCDD
using the four results.
8.2.5 Compare s and (X) with the corresponding acceptance criteria
for precision and accuracy, respectively, found in Table 2. If s and X
meet the acceptance criteria, the system performance is acceptable and
analysis of actual samples can begin. If s exceeds the precision limit
or X falls outside the range for accuracy, the system performance is
unacceptable for 2,3,7,8-TCDD. Locate and correct the source of the
problem and repeat the test beginning with Section 8.2.2.
8.3 The laboratory must, on an ongoing basis, spike at least 10% of
the samples from each sample site being monitored to assess accuracy.
For laboratories analyzing one to ten samples per month, at least one
spiked sample per month is required.
8.3.1 The concentration of the spike in the sample should be
determined as follows:
8.3.1.1 If, as in compliance monitoring, the concentration of
2,3,7,8-TCDD in the sample is being checked against a regulatory
concentration limit, the spike should be at that limit or 1 to 5 times
higher than the background concentration determined in Section 8.3.2,
whichever concentration would be larger.
8.3.1.2 If the concentration of 2,3,7,8-TCDD in the sample is not
being checked against a limit specific to that parameter, the spike
should be at 0.100 [micro]g/L or 1 to 5 times higher than the background
concentration determined in Section 8.3.2, whichever concentration would
be larger.
8.3.1.3 If it is impractical to determine background levels before
spiking (e.g., maximum holding times will be exceeded), the
[[Page 191]]
spike concentration should be (1) the regulatory concentration limit, if
any; or, if none (2) the larger of either 5 times higher than the
expected background concentration or 0.100 [micro]g/L.
8.3.2 Analyze one sample aliquot to determine the background
concentration (B) of 2,3,7,8-TCDD. If necessary, prepare a new QC check
sample concentrate (Section 8.2.1) appropriate for the background
concentration in the sample. Spike a second sample aliquot with 1.0 mL
of the QC check sample concentrate and analyze it to determine the
concentration after spiking (A) of 2,3,7,8-TCDD. Calculate percent
recovery (P) as 100(A-B)%T, where T is the known true value of the
spike.
8.3.3 Compare the percent recovery (P) for 2,3,7,8-TCDD with the
corresponding QC acceptance criteria found in Table 2. These acceptance
criteria were calculated to include an allowance for error in
measurement of both the background and spike concentrations, assuming a
spike to background ratio of 5:1. This error will be accounted for to
the extent that the analyst's spike to background ratio approaches
5:1.11 If spiking was performed at a concentration lower than
0.100 [micro]g/L, the analyst must use either the QC acceptance criteria
in Table 2, or optional QC acceptance criteria calculated for the
specific spike concentration. To calculate optional acceptance criteria
for the recovery of 2,3,7,8-TCDD: (1) Calculate accuracy (X') using the
equation in Table 3, substituting the spike concentration (T) for C; (2)
calculate overall precision (S') using the equation in Table 3,
substituting X' for X; (3) calculate the range for recovery at the spike
concentration as (100 X'/T)2.44(100 S'/T)%.
11
8.3.4 If the recovery of 2,3,7,8-TCDD falls outside the designated
range for recovery, a check standard must be analyzed as described in
Section 8.4.
8.4 If the recovery of 2,3,7,8-TCDD fails the acceptance criteria
for recovery in Section 8.3, a QC check standard must be prepared and
analyzed.
Note: The frequency for the required analysis of a QC check standard
will depend upon the complexity of the sample matrix and the performance
of the laboratory.
8.4.1 Prepare the QC check standard by adding 1.0 mL of QC check
sample concentrate (Section 8.2.1 or 8.3.2) to 1 L of reagent water.
8.4.2 Analyze the QC check standard to determine the concentration
measured (A) of 2,3,7,8-TCDD. Calculate the percent recovery
(Ps) as 100 (A/T)%, where T is the true value of the standard
concentration.
8.4.3 Compare the percent recovery (Ps) with the
corresponding QC acceptance criteria found in Table 2. If the recovery
of 2,3,7,8-TCDD falls outside the designated range, the laboratory
performance is judged to be out of control, and the problem must be
immediately identified and corrected. The analytical result for 2,3,7,8-
TCDD in the unspiked sample is suspect and may not be reported for
regulatory compliance purposes.
8.5 As part of the QC program for the laboratory, method accuracy
for wastewater samples must be assessed and records must be maintained.
After the analysis of five spiked wastewater samples as in Section 8.3,
calculate the average percent recovery (P) and the spandard deviation of
the percent recovery (sp). Express the accuracy assessment as
a percent recovery interval from P-2sp to P+2sp.
If P=90% and sp=10%, for example, the accuracy interval is
expressed as 70-110%. Update the accuracy assessment on a regular basis
(e.g. after each five to ten new accuracy measurements).
8.6 It is recommended that the lab o ra tory adopt additional
quality assurance practices for use with this method. The specific
practices that are most productive depend upon the needs of the
laboratory and the nature of the samples. Field duplicates may be
analyzed to assess the precision of the environmental measurements.
Whenever possible, the laboratory should analyze standard reference
materials and participate in relevant performance evaluation studies.
9. Sample Collection, Preservation, and Handling
9.1 Grab samples must be collected in glass containers. Conventional
sampling practices 12 should be followed, except that the
bottle must not be prerinsed with sample before collection. Composite
samples should be collected in refrigerated glass containers in
accordance with the requirements of the program. Automatic sampling
equipment must be as free as possible of Tygon tubing and other
potential sources of contamination.
9.2 All samples must be iced or refrigerated at 4 [deg]C and
protected from light from the time of collection until extraction. Fill
the sample bottles and, if residual chlorine is present, add 80 mg of
sodium thiosulfate per liter of sample and mix well. EPA Methods 330.4
and 330.5 may be used for measurement of residual chlorine.13
Field test kits are available for this purpose.
9.3 Label all samples and containers ``POISON'' and ship according
to applicable U.S. Department of Transportation regulations.
9.4 All samples must be extracted within 7 days of collection and
completely analyzed within 40 days of extraction.2
10. Sample Extraction
Caution: When using this method to analyze for 2,3,7,8-TCDD, all of
the following operations must be performed in a limited-access
laboratory with the analyst wearing full
[[Page 192]]
protective covering for all exposed skin surfaces. See Section 4.2.
10.1 Mark the water meniscus on the side of the sample bottle for
later determination of sample volume. Pour the entire sample into a 2-L
separatory funnel.
10.2 Add 1.00 mL of internal standard spiking solution to the sample
in the separatory funnel. If the final extract will be concentrated to a
fixed volume below 1.00 mL (Section 12.3), only that volume of spiking
solution should be added to the sample so that the final extract will
contain 25 ng/mL of internal standard at the time of analysis.
10.3 Add 60 mL of methylene chloride to the sample bottle, seal, and
shake 30 s to rinse the inner surface. Transfer the solvent to the
separatory funnel and extract the sample by shaking the funnel for 2
min. with periodic venting to release excess pressure. Allow the organic
layer to separate from the water phase for a minimum of 10 min. If the
emulsion interface between layers is more than one-third the vmlume of
the solvent layer, the analyst must employ mechanical techniques to
complete the phase separation. The optimum technique depends upon the
sample, but may include stirring, filtration of the emulsion through
glass wool, centrifugation, or other physical methods. Collect the
methylene chloride extract in a 250-mL Erlenmeyer flask.
10.4 Add a second 60-mL volume of methylene chloride to the sample
bottle and repeat the extraction procedure a second time, combining the
extracts in the Erlenmeyer flask. Perform a third extraction in the same
manner.
10.5 Assemble a Kuderna-Danish (K-D) con cen tra tor by attaching a
10-mL concentrator tube to a 500-mL evaporative flask. Other
concentration devices or techniques may be used in place of the K-D
concentrator if the requirements of Section 8.2 are met.
10.6 Pour the combined extract into the K-D concentrator. Rinse the
Erlenmeyer flask with 20 to 30 mL of methylele chloride to complete the
quantitative transfer.
10.7 Add one or two clean boiling chips to the evaporative flask and
attach a three-ball Snyder column. Prewet the Snyder column by adding
about 1 mL of methylene chloride to the top. Place the K-D apparatus on
a hot water bath (60 to 65 [deg]C) so that the concentrator tube is
partially immersed in the hot water, and the entire lower rounded
surface of the flask is bathed with hot vapor. Adjust the vertical
position of the apparatus and the water temperature as required to
complete the concentration in 15 to 20 min. At the proper rate of
distillation the balls of the column will actively chatter but the
chambers will not flood with condensed solvent. When the apparent volume
of liquid reaches 1 mL, remove the K-D apparatus and allow it to drain
and cool for at least 10 min.
10.8 Momentarily remove the Snyder column, add 50 mL of hexane and a
new boiling chip, and reattach the Snyder column. Raise the temperature
of the water bath to 85 to 90[deg]C. Concentrate the extract as in
Section 10.7, except use hexane to prewet the column. Remove the Snyder
column and rinse the flask and its lower joint into the concentrator
tube with 1 to 2 mL of hexane. A 5-mL syringe is recommended for this
operation. Set aside the K-D glassware for reuse in Section 10.14.
10.9 Pour the hexane extract from the concentrator tube into a 125-
mL separatory funnel. Rinse the concentrator tube four times with 10-mL
aliquots of hexane. Combine all rinses in the 125-mL separatory funnel.
10.10 Add 50 mL of sodium hydroxide solution to the funnel and shake
for 30 to 60 s. Discard the aqueous phase.
10.11 Perform a second wash of the organic layer with 50 mL of
reagent water. Discard the aqueous phase.
10.12 Wash the hexane layer with a least two 50-mL aliquots of
concentrated sulfuric acid. Continue washing the hexane layer with 50-mL
aliquots of concentrated sulfuric acid until the acid layer remains
colorless. Discard all acid fractions.
10.13 Wash the hexane layer with two 50-mL aliquots of reagent
water. Discard the aqueous phases.
10.14 Transfer the hexane extract into a 125-mL Erlenmeyer flask
containing 1 to 2 g of anhydrous sodium sulfate. Swirl the flask for 30
s and decant the hexane extract into the reassembled K-D apparatus.
Complete the quantitative transfer with two 10-mL hexane rinses of the
Erlenmeyer flask.
10.15 Replace the one or two clean boiling chips and concentrate the
extract to 6 to 10 mL as in Section 10.8.
10.16 Add a clean boiling chip to the concentrator tube and attach a
two-ball micro-Snyder column. Prewet the column by adding about 1 mL of
hexane to the top. Place the micro-K-D apparatus on the water bath so
that the concentrator tube is partially immersed in the hot water.
Adjust the vertical position of the apparatus and the water temperature
as required to complete the concentration in 5 to 10 min. At the proper
rate of distillation the balls of the column will actively chatter but
the chambers will not flood. When the apparent volume of liquid reaches
about 0.5 mL, remove the K-D apparatus and allow it to drain and cool
for at least 10 min. Remove the micro-Snyder column and rinse its lower
joint into the concentrator tube with 0.2 mL of hexane.
Adjust the extract volume to 1.0 mL with hexane. Stopper the
concentrator tube and store refrigerated and protected from light if
further processing will not be performed immediately. If the extract
will be stored
[[Page 193]]
longer than two days, it should be transferred to a Teflon-sealed screw-
cap vial. If the sample extract requires no further cleanup, proceed
with GC/MS analysis (Section 12). If the sample requires further
cleanup, proceed to Section 11.
10.17 Determine the original sample volume by refilling the sample
bottle to the mark and transferring the liquid to a 1000-mL graduated
cylinder. Record the sample volume to the nearest 5 mL.
11. Cleanup and Separation
11.1 Cleanup procedures may not be necessary for a relatively clean
sample matrix. If particular circumstances demand the use of a cleanup
procedure, the analyst may use either procedure below or any other
appropriate procedure.1, 5-7 However, the analyst first must
demonstrate that the requirements of Section 8.2 can be met using the
method as revised to incorporate the cleanup procedure. Two cleanup
column options are offered to the analyst in this section. The alumina
column should be used first to overcome interferences. If background
problems are still encountered, the silica gel column may be helpful.
11.2 Alumina column cleanup for 2,3,7,8-TCDD:
11.2.1 Fill a 300 mm long x 10 mm ID chromatographic column with
activated alumina to the 150 mm level. Tap the column gently to settle
the alumina and add 10 mm of anhydrous sodium sulfate to the top.
11.2.2 Preelute the column with 50 mL of hexane. Adjust the elution
rate to 1 mL/min. Discard the eluate and just prior to exposure of the
sodium sulfate layer to the air, quantitatively transfer the 1.0-mL
sample extract onto the column using two 2-mL portions of hexane to
complete the transfer.
11.2.3 Just prior to exposure of the sodium sulfate layer to the
air, add 50 mL of 3% methylene chloride/95% hexane (V/V) and continue
the elution of the column. Discard the eluate.
11.2.4 Next, elute the column with 50 mL of 20% methylene chloride/
80% hexane (V/V) into a 500-mL K-D flask equipped with a 10-mL
concentrator tube. Concentrate the collected fraction to 1.0 mL as in
Section 10.16 and analyze by GC/MS (Section 12).
11.3 Silica gel column cleanup for 2,3,7,8-TCDD:
11.3.1 Fill a 400 mm long x 11 mm ID chromatmgraphic column with
silica gel to the 300 mm level. Tap the column gently to settle the
silica gel and add 10 mm of anhydrous sodium sulfate to the top.
11.3.2 Preelute the column with 50 mL of 20% benzene/80% hexane (V/
V). Adjust the elution rate to 1 mL/min. Discard the eluate and just
prior to exposure of the sodium sulfate layer to the air, quantitatively
transfer the 1.0-mL sample extract onto the column using two 2-mL
portions of 20% benzene/80% hexane to complete the transfer.
11.3.3 Just prior to exposure of the sodium sulfate layer to the
air, add 40 mL of 20% benzene/80% hexane to the column. Collect the
eluate in a clean 500-mL K-D flask equipped with a 10-mL concentrator
tube. Concentrate the collected fraction to 1.0 mL as in Section 10.16
and analyze by GC/MS.
12. GC/MS Analysis
12.1 Table 1 summarizes the recommended operating conditions for the
gas chromatograph. Included in this table are retention times and MDL
that can be achieved under these conditions. Other capillary columns or
chromatographic conditions may be used if the requirements of Sections
5.5.2 and 8.2 are met.
12.2 Analyze standards and samples with the mass spectrometer
operating in the selected ion monitoring (SIM) mode using a dwell time
to give at least seven points per peak. For LRMS, use masses at m/z 320,
322, and 257 for 2,3,7,8-TCDD and either m/z 328 for
37Cl4 2,3,7,8-TCDD or m/z 332 for
13C12 2,3,7,8-TCDD. For HRMS, use masses at m/z
319.8965 and 321.8936 for 2,3,7,8-TCDD and either m/z 327.8847 for
37Cl4 2,3,7,8-TCDD or m/z 331.9367 for
13C12 2,3,7,8-TCDD.
12.3 If lower detection limits are required, the extract may be
carefully evaporated to dryness under a gentle stream of nitrogen with
the concentrator tube in a water bath at about 40 [deg]C. Conduct this
operation immediately before GC/MS analysis. Redissolve the extract in
the desired final volume of ortho-xylene or tetradecane.
12.4 Calibrate the system daily as described in Section 7.
12.5 Inject 2 to 5 [micro]L of the sample extract into the gas
chromatograph. The volume of calibration standard injected must be
measured, or be the same as all sample injection volumes.
12.6 The presence of 2,3,7,8-TCDD is qualitatively confirmed if all
of the following criteria are achieved:
12.6.1 The gas chromatographic column must resolve 2,3,7,8-TCDD from
the other 21 TCDD isomers.
12.6.2 The masses for native 2,3,7,8-TCDD (LRMS-m/z 320, 322, and
257 and HRMS-m/z 320 and 322) and labeled 2,3,7,8-TCDD (m/z 328 or 332)
must exhibit a simultaneous maximum at a retention time that matches
that of native 2,3,7,8-TCDD in the calibration standard, with the
performance specifications of the analytical system.
12.6.3 The chlorine isotope ratio at m/z 320 and m/z 322 must agree
to within10% of that in the calibration standard.
12.6.4 The signal of all peaks must be greater than 2.5 times the
noise level.
12.7 For quantitation, measure the response of the m/z 320 peak for
2,3,7,8-TCDD
[[Page 194]]
and the m/z 332 peak for \13\C12 2,3,7,8-TCDD or the m/z 328
peak for 37Cl4 2,3,7,8-TCDD.
12.8 Co-eluting impurities are suspected if all criteria are
achieved except those in Section 12.6.3. In this case, another SIM
analysis using masses at m/z 257, 259, 320 and either m/a 328 or m/z 322
can be performed. The masses at m/z 257 and m/z 259 are indicative of
the loss of one chlorine and one carbonyl group from 2,3,7,8-TCDD. If
masses m/z 257 and m/z 259 give a chlorine isotope ratio that agrees to
within 10% of the same cluster in the calibration
standards, then the presence of TCDD can be confirmed. Co-eluting DDD,
DDE, and PCB residues can be confirmed, but will require another
injection using the appropriate SIM masses or full repetitive mass
scans. If the response for 37Cl4 2,3,7,8-TCDD at
m/z 328 is too large, PCB contamination is suspected and can be
confirmed by examining the response at both m/z 326 and m/z 328. The
37Cl4 2,3,7,8-TCDD internal standard gives
negligible response at m/z 326. These pesticide residues can be removed
using the alumina column cleanup procedure.
12.9 If broad background interference restricts the sensitivity of
the GC/MS analysis, the analyst should employ additional cleanup
procedures and reanalyze by GC/MS.
12.10 In those circumstances where these procedures do not yield a
definitive conclusion, the use of high resolution mass spectrometry is
suggested.5
13. Calculations
13.1 Calculate the concentration of 2,3,7,8-TCDD in the sample using
the response factor (RF) determined in Section 7.1.2 and Equation 2.
[GRAPHIC] [TIFF OMITTED] TC15NO91.123
Equation 2
where:
As=SIM response for 2,3,7,8-TCDD at m/z 320.
Ais=SIM response for the internal standard at m/z 328 or 332.
Is=Amount of internal standard added to each extract
([micro]g).
Vo=Volume of water extracted (L).
13.2 For each sample, calculate the percent recovery of the internal
standard by comparing the area of the m/z peak measured in the sample to
the area of the same peak in the calibration standard. If the recovery
is below 50%, the analyst should review all aspects of his analytical
technique.
13.3 Report results in [micro]g/L without correction for recovery
data. All QC data obtained should be reported with the sample results.
14. Method Performance
14.1 The method detection limit (MDL) is defined as the minimum
concentration of a substance that can be measured and reported with 99%
confidence that the value is above zero.1 The MDL
concentration listed in Table 1 was obtained using reagent
water.14 The MDL actually achieved in a given analysis will
vary depending on instrument sensitivity and matrix effects.
14.2 This method was tested by 11 laboratories using reagent water,
drinking water, surface water, and three industrial waste waters spiked
at six concentrations over the range 0.02 to 0.20 [micro]g/
L.15 Single operator precision, overall precision, and method
accuracy were found to be directly related to the concentration of the
parameter and essentially independent of the sample matrix. Linear
equations to describe these relationships are presented in Table 3.
References
1. 40 CFR part 136, appendix B.
2. ``Determination of TCDD in Industrial and Municipal
Wastewaters,'' EPA 600/4-82-028, National Technical Information Service,
PB82-196882, Springfield, Virginia 22161, April 1982.
3. Buser, H.R., and Rappe, C. ``High Resolution Gas Chromatography
of the 22 Tetrachlorodibenzo-p-dioxin Isomers,'' Analytical Chemistry,
52, 2257 (1980).
4. ASTM Annual Book of Standards, Part 31, D3694-78. ``Standard
Practices for Preparation of Sample Containers and for Preservation of
Organic Constituents,'' American Society for Testing and Materials,
Philadelphia.
5. Harless, R. L., Oswald, E. O., and Wilkinson, M. K. ``Sample
Preparation and Gas Chromatography/Mass Spectrometry Determination of
2,3,7,8-Tetrachlorodibenzo-p-dioxin,'' Analytical Chemistry, 52, 1239
(1980).
6. Lamparski, L. L., and Nestrick, T. J. ``Determination of Tetra-,
Hepta-, and Octachlorodibenzo-p-dioxin Isomers in Particulate Samples at
Parts per Trillion Levels,'' Analytical Chemistry, 52, 2045 (1980).
7. Longhorst, M. L., and Shadoff, L. A. ``Determination of Parts-
per-Trillion Concentrations of Tetra-, Hexa-, and Oc ta chloro di benzo-
p-dioxins in Human Milk,'' Analytical Chemistry, 52, 2037 (1980).
8. ``Carcinogens--Working with Carcinogens,'' Department of Health,
Education, and Welfare, Public Health Service, Center for Disease
Control, National Institute for Occupational Safety and Health,
Publication No. 77-206, August 1977.
9. ``OSHA Safety and Health Standards, General Industry,'' (29 CFR
part 1910), Occuptional Safety and Health Administration, OSHA 2206
(Revised, January 1976).
[[Page 195]]
10. ``Safety in Academic Chemistry Laboratories,'' American Chemical
Society Publication, Committee on Chemical Safety, 3rd Edition, 1979.
11. Provost, L. P., and Elder, R. S., ``In terpretation of Percent
Recovery Data,'' American Laboratory, 15, 58-63 (1983). (The value 2.44
used in the equation in Section 8.3.3 is two times the value 1.22
derived in this report.)
12. ASTM Annual Book of Standards, Part 31, D3370-76, ``Standard
Practices for Sampling Water,'' American Society for Testing and
Materials, Philadelphia.
13. ``Methods, 330.4 (Titrimetric, DPD-FAS) and 330.5
(Spectrophotometric DPD) for Chlorine, Total Residual,'' Methods for
Chemical Analysis of Water and Wastes, EPA-600/4-79-020, U.S.
Environmental Protection Agency, Environmental Monitoring and Support
Laboratory, Cincinnati, Ohio 45268, March 1979.
14. Wong, A.S. et al. ``The Determination of 2,3,7,8-TCDD in
Industrial and Municipal Wastewaters, Method 613, Part 1--Development
and Detection Limits,'' G. Choudhay, L. Keith, and C. Ruppe, ed.,
Butterworth Inc., (1983).
15. ``EPA Method Study 26, Method 613: 2,3,7,8-Tetrachlorodibenzo-p-
dioxin,'' EPA 600/4-84-037, National Technical Information Service,
PB84-188879, Springfield, Virginia 22161, May 1984.
Table 1--Chromatographic Conditions and Method Detection Limit
------------------------------------------------------------------------
Method
Retention detection
Parameter time limit
(min) ([micro]g/
L)
------------------------------------------------------------------------
2,3,7,8-TCDD..................................... 13.1 0.002
------------------------------------------------------------------------
Column conditions: SP-2330 coated on a 60 m long x 0.25 mm ID glass
column with hydrogen carrier gas at 40 cm/sec linear velocity,
splitless injection using tetradecane. Column temperature held
isothermal at 200[deg]C for 1 min, then programmed at 8[deg]C/min to
250 [deg]C and held. Use of helium carrier gas will approximately
double the retention time.
Table 2--QC Acceptance Criteria--Method 613
----------------------------------------------------------------------------------------------------------------
Limit for
Test conc. s Range for X Range
Parameter ([micro]g/ ([micro]g/ ([micro]g/L) for P,
L) L) Ps (%)
----------------------------------------------------------------------------------------------------------------
2,3,7,8-TCDD................................................... 0.100 0.0276 0.0523-0.1226 45-129
----------------------------------------------------------------------------------------------------------------
s=Standard deviation of four recovery measurements, in [micro]g/L (Section 8.2.4).
X=Average recovery for four recovery measurements, in [micro]g/L (Section 8.2.4).
P, Ps=Percent recovery measured (Section 8.3.2, Section 8.4.2).
Note: These criteria are based directly upon the method performance data in Table 3. Where necessary, the limits
for recovery have been broadened to assure applicability of the limits to concentrations below those used to
develop Table 3.
Table 3--Method Accuracy and Precision as Functions of Concentration--Method 613
----------------------------------------------------------------------------------------------------------------
Accuracy, as Single analyst,
Parameter recovery, X ' precision, sr ' Overall precision,
([micro]g/L) ([micro]/L) S ' ([micro]/g/L)
----------------------------------------------------------------------------------------------------------------
2,3,7,8-TCDD........................................ 0.86C+0.00145 0.13X+0.00129 0.19X+0.00028
----------------------------------------------------------------------------------------------------------------
X'=Expected recovery for one or more measurements. of a sample containing a concentration of C, in [micro]g/L.
sr'=Expected single analyst standard deviation of measurements at an average concentration found of X, in
[micro]g/L.
S'=Expected interlaboratory standard deviation of measurements at an average concentration found of X, in
[micro]g/L.
C=True value for the concentration, in [micro]g/L.
X=Average recovery found for measurements of samples containing a concentration of C, in [micro]g/L.
Method 624--Purgeables
1. Scope and Application
1.1 This method covers the determination of a number of purgeable
organics. The following parameters may be determined by this method:
------------------------------------------------------------------------
STORET
Parameter No. CAS No.
------------------------------------------------------------------------
Benzene.......................................... 34030 71-43-2
Bromodichloromethane............................. 32101 75-27-4
Bromoform........................................ 32104 75-25-2
Bromomethane..................................... 34413 74-83-9
Carbon tetrachloride............................. 32102 56-23-5
Chlorobenzene.................................... 34301 108-90-7
Chloroethane..................................... 34311 75-00-3
2-Chloroethylvinyl ether......................... 34576 110-75-8
Chloroform....................................... 32106 67-66-3
Chloromethane.................................... 34418 74-87-3
Dibromochloromethane............................. 32105 124-48-1
1,2-Dichlorobenzene.............................. 34536 95-50-1
1,3-Dichlorobenzene.............................. 34566 541-73-1
1,4-Dichlorobenzene.............................. 34571 106-46-7
1,1-Dichloroethane............................... 34496 75-34-3
1,2-Dichloroethane............................... 34531 107-06-2
1,1-Dichloroethane............................... 34501 75-35-4
trans-1,2-Dichloroethene......................... 34546 156-60-5
1,2-Dichloropropane.............................. 34541 78-87-5
cis-1,3-Dichloropropene.......................... 34704 10061-01-5
trans-1,3-Dichloropropene........................ 34699 10061-02-6
Ethyl benzene.................................... 34371 100-41-4
Methylene chloride............................... 34423 75-09-2
1,1,2,2-Tetrachloroethane........................ 34516 79-34-5
Tetrachloroethene................................ 34475 127-18-4
Toluene.......................................... 34010 108-88-3
1,1,1-Trichloroethene............................ 34506 71-55-6
1,1,2-Trichloroethene............................ 34511 79-00-5
Trichloroethane.................................. 39180 79-01-6
Trichlorofluoromethane........................... 34488 75-69-4
Vinyl chloride................................... 39175 75-01-4
------------------------------------------------------------------------
[[Page 196]]
1.2 The method may be extended to screen samples for acrolein
(STORET No. 34210, CAS No. 107-02-8) and acrylonitrile (STORET No.
34215, CAS No. 107-13-1), however, the preferred method for these two
compounds in Method 603.
1.3 This is a purge and trap gas chro ma to graphic/ mass
spectrometer (GC/MS) method applicable to the determination of the
compounds listed above in municipal and industrial discharges as
provided under 40 CFR 136.1.
1.4 The method detection limit (MDL, defined in Section 14.1)\1\ for
each parameter is listed in Table 1. The MDL for a specific wastewater
may differ from those listed, depending upon the nature of interferences
in the sample matrix.
1.5 Any modification to this method, beyond those expressly
permitted, shall be considered as a major modification subject to
application and approval of alternate test procedures under 40 CFR 136.4
and 136.5. Depending upon the nature of the modification and the extent
of intended use, the applicant may be required to demonstrate that the
modifications will produce equivalent results when applied to relevant
wastewaters.
1.6 This method is restricted to use by or under the supervision of
analysts experienced in the operation of a purge and trap system and a
gas chromatograph/mass spectrometer and in the interpretation of mass
spectra. Each analyst must demonstrate the ability to generate
acceptable results with this method using the procedure described in
Section 8.2.
2. Summary of Method
2.1 An inert gas is bubbled through a 5-mL water sample contained in
a specially-designed purging chamber at ambient temperature. The
purgeables are efficiently transferred from the aqueous phase to the
vapor phase. The vapor is swept through a sorbent trap where the
purgeables are trapped. After purging is completed, the trap is heated
and backflushed with the inert gas to desorb the purgeables onto a gas
chromatographic column. The gas chromatograph is temperature programmed
to separate the purgeables which are then detected with a mass
spectrometer.2, 3
3. Interferences
3.1 Impurities in the purge gas, organic compounds outgassing from
the plumbing ahead of the trap, and solvent vapors in the laboratory
account for the majority of contamination problems. The analytical
system must be demonstated to be free from contamination under the
conditions of the analysis by running laboratory reagent blanks as
described in Section 8.1.3. The use of non-Teflon plastic tubing, non-
Teflon thread sealants, or flow controllers with rubber components in
the purge and trap system should be avoided.
3.2 Samples can be contaminated by diffusion of volatile organics
(particularly fluorocarbons and methylene chloride) through the septum
seal into the sample during shipment and storage. A field reagent blank
prepared from reagent water and carried through the sampling and
handling protocol can serve as a check on such contamination.
3.3 Contamination by carry-over can occur whenever high level and
low level samples are sequentially analyzed. To reduce carry-over, the
purging device and sample syringe must be rinsed with reagent water
between sample analyses. Whenever an unusually concentrated sample is
encountered, it should be followed by an analysis of reagent water to
check for cross contamination. For samples containing large amounts of
water-soluble materials, suspended solids, high boiling compounds or
high pureeable levels, it may be necessary to wash the purging device
with a detergent solution, rinse it with distilled water, and then dry
it in a 105 [deg]C oven between analyses. The trap and other parts of
the system are also subject to contamination; therefore, frequent
bakeout and purging of the entire system may be required.
4. Safety
4.1 The toxicity or carcinogenicity of each reagent used in this
method has not been precisely defined; however, each chemical compound
should be treated as a potential health hazard. From this viewpoint,
exposure to these chemicals must be reduced to the lowest possible level
by whatever means available. The laboratory is responsible for
maintaining a current awareness file of OSHA regulations regarding the
safe handling of the chemicals specified in this methmd. A reference
file of material data handling sheets should also be made available to
all personnel involved in the chemical analysis. Additional references
to laboratory safety are available and have been
identified4-6 for the information of the analyst.
4.2. The following parameters covered by this method have been
tentatively classified as known or suspected, human or mammalian
carcinogens: benzene, carbon tetrachloride, chloroform, 1,4-
dichlorobenzene, and vinyl chloride. Primary standards of these toxic
compounds should be prepared in a hood. A NIOSH/MESA approved toxic gas
respirator should be worn when the analyst handles high concentrations
of these toxic compounds.
5. Apparatus and Materials
5.1 Sampling equipment, for discrete sampling.
[[Page 197]]
5.1.1 Vial--25-mL capacity or larger, equipped with a screw cap with
a hole in the center (Pierce 13075 or equivalent). Detergent
wash, rinse with tap and distilled water, and dry at 105 [deg]C before
use.
5.1.2 Septum--Teflon-faced silicane (Pierce 12722 or
equivalent). Detergent wash, rinse with tap and distilled water, and dry
at 105 [deg]C for 1 h before use.
5.2 Purge and trap system--The purge and trap system consists of
three separate pieces of equipment: A purging device, trap, and
desorber. Several complete systems are now commercially available.
5.2.1 The purging device must be designed to accept 5-mL samples
with a water column at least 3 cm deep. The gaseous head space between
the water column and the trap must have a total volume of less than 15
mL. The purge gas must pass though the water column as finely divided
bubbles with a diameter of less than 3 mm at the origin. The purge gas
must be introduced no more than 5 mm from the base of the water column.
The purging device illustrated in Figure 1 meets these design criteria.
5.2.2 The trap must be at least 25 cm long and have an inside
diameter of at least 0.105 in. The trap must be packed to contain the
following minimum lengths of adsorbents: 1.0 cm of methyl silicone
coated packing (Section 6.3.2), 15 cm of 2,6-dyphenylene oxide polymer
(Section 6.3.1), and 8 cm of silica gel (Section 6.3.3). The minimum
specifications for the trap are illustrated in Figure 2.
5.2.3 The desorber should be capable of rapidly heating the trap to
180 [deg]C. The polymer section of the trap should not be heated higher
than 180 [deg]C and the remaining sections should not exceed 200 [deg]C.
The desorber illustrated in Figure 2 meets these design criteria.
5.2.4 The purge and trap system may be assembled as a separate unit
or be coupled to a gas chromatograph as illustrated in Figures 3 and 4.
5.3 GC/MS system:
5.3.1 Gas chromatograph--An analytical system complete with a
temperature programmable gas chromatograph suitable for on-column
injection and all required accessories including syringes, analytical
columns, and gases.
5.3.2 Column--6 ft long x 0.1 in ID stainless steel or glass, packed
with 1% SP-1000 on Carbopack B (60/80 mesh) or equivalent. This column
was used to develop the method performance statements in Section 14.
Guidelines for the use of alternate column packings are provided in
Section 11.1.
5.3.3 Mass spectrometer--Capable of scanning from 20 to 260 amu
every 7 s or less, utilizing 70 V (nominal) electron energy in the
electron impact ionization mode, and producing a mass spectrum which
meets all the criteria in Table 2 when 50 ng of 4-bromo flu o ro ben
zene (BFB) is injected through the GC inlet.
5.3.4 GC/MS interface--Any GC to MS interface that gives acceptable
calibration points at 50 ng or less per injection for each of the
parameters of interest and achieves all acceptable performance criteria
(Section 10) may be used. GC to MS interfaces constructed of all glass
or glass-lined materials are recommended. Glass can be deactivated by
silanizing with dichlorodimethylsilane.
5.3.5 Data system--A computer system must be interfaced to the mass
spectrometer that allows the continuous acquisition and storage on
machine-readable media of all mass spectra obtained throughout the
duration of the chromatographic program. The computer must have software
that allows searching any GC/MS data file for specific m/z (masses) and
plotting such m/z abundances versus time or scan number. This type of
plot is defined as an Extracted Ion Current Profile (EICP). Software
must also be available that allows integrating the abundance in any EICP
between specified time or scan number limits.
5.4 Syringes--5-mL, glass hypodermic with Luerlok tip (two each), if
applicable to the purging device.
5.5 Micro syringes--25-[micro]L, 0.006 in. ID needle.
5.6 Syringe valve--2-way, with Luer ends (three each).
5.7 Syringe--5-mL, gas-tight with shut-off valve.
5.8 Bottle--15-mL, screw-cap, with Teflon cap liner.
5.9 Balance--Analytical, capable of accurately weighing 0.0001 g.
6. Reagents
6.1 Reagent water--Reagent water is defined as a water in which an
interferent is not observed at the MDL of the parameters of interest.
6.1.1 Reagent water can be generated by passing tap water through a
carbon filter bed containing about 1 lb of activated carbon (Filtrasorb-
300, Calgon Corp., or equivalent).
6.1.2 A water purification system (Millipore Super-Q or equivalent)
may be used to generate reagent water.
6.1.3 Reagent water may also be prepared by boiling water for 15
min. Subsequently, while maintaining the temperature at 90 [deg]C,
bubble a contaminant-free inert gas through the water for 1 h. While
still hot, transfer the water to a narrow mouth screw-cap bottle and
seal with a Teflon-lined septum and cap.
6.2 Sodium thiosulfate--(ACS) Granular.
6.3 Trap materials:
6.3.1 2,6-Diphenylene oxide polymer--Tenax, (60/80 mesh),
chromatographic grade or equivalent.
6.3.2 Methyl silicone packing--3% OV-1 on Chromosorb-W (60/80 mesh)
or equivalent.
[[Page 198]]
6.3.3 Silica gel--35/60 mesh, Davison, grade-15 or equivalent.
6.4 Methanol--Pesticide quality or equivalent.
6.5 Stock standard solutions--Stock stand ard solutions may be
prepared from pure standard materials or purchased as certi fied
solutions. Prepare stock standard solutions in methanol using assayed
liquids or gases as appropriate. Because of the toxicity of some of the
compounds, primary dilutions of these materials should be prepared in a
hood. A NIOSH/MESA approved toxic gas respirator should be used when the
analyst handles high concentrations of such materials.
6.5.1 Place about 9.8 mL of methanol into a 10-mL ground glass
stoppered volumetric flask. Allow the flask to stand, unstoppered, for
about 10 min or until all alcohol wetted surfaces have dried. Weigh the
flask to the nearest 0.1 mg.
6.5.2 Add the assayed reference material:
6.5.2.1 Liquids--Using a 100-[micro]L syringe, immediately add two
or more drops of assayed reference material to the flask, then reweigh.
Be sure that the drops fall directly into the alcohol without contacting
the neck of the flask.
6.5.2.2 Gases--To prepare standards for any of the four halocarbons
that boil below 30 [deg]C (bromomethane, chloroethane, chloromethane,
and vinyl chloride), fill a 5-mL valved gas-tight syringe with the
reference standard to the 5.0-mL mark. Lower the needle to 5 mm above
the methanol meniscus. Slowly introduce the reference standard above the
surface of the liquid (the heavy gas will rapidly dissolve in the
methanol).
6.5.3 Reweigh, dilute to volume, stopper, then mix by inverting the
flask several times. Calculate the concentration in [micro]g/[micro]L
from the net gain in weight. When compound purity is assayed to be 96%
or greater, the weight may be used without correction to calculate the
concentration of the stock standard. Commercially prepared stock
standards may be used at any concentration if they are certified by the
manufacturer or by an independent source.
6.5.4 Transfer the stock standard solution into a Teflon-sealed
screw-cap bottle. Store, with minimal headspace, at -10 to -20 [deg]C
and protect from light.
6.5.5 Prepare fresh standards weekly for the four gases and 2-
chloroethylvinyl ether. All other standards must be replaced after one
month, or sooner if comparison with check standards indicates a problem.
6.6 Secondary dilution standards--Using stock solutions, prepare
secondary dilution standards in methanol that contain the compounds of
interest, either singly or mixed together. The secondary dilution
standards should be prepared at concentrations such that the aqueous
calibration standards prepared in Section 7.3 will bracket the working
range of the analytical system. Secondary dilution standards should be
stored with minimal headspace and should be checked frequently for signs
of degradation or evaporation, especially just prior to preparing
calibration standards from them.
6.7 Surrogate standard spiking solution--Select a minimum of three
surrogate compounds from Table 3. Prepare stock standard solutions for
each surrogate standard in methanol as described in Section 6.5. Prepare
a surrogate standard spiking solution from these stock standards at a
concentration of 15 [micro]g/mL in water. Store the solutions at 4
[deg]C in Teflon-sealed glass containers with a minimum of headspace.
The solutions should be checked frequently for stability. The addition
of 10 [micro]L of this solution of 5 mL of sample or standard is
equivalent to a concentration of 30 [micro]g/L of each surrogate
standard.
6.8 BFB Standard--Prepare a 25 [micro]g/mL solution of BFB in
methanol.
6.9 Quality control check sample concentrate--See Section 8.2.1.
7. Calibration
7.1 Assemble a purge and trap system that meets the specifications
in Section 5.2. Condition the trap overnight at 180 [deg]C by
backflushing with an inert gas flow of at least 20 mL/min. Condition the
trap for 10 min once daily prior to use.
7.2 Connect the purge and trap system to a gas chromatograph. The
gas chromatograph must be operated using temperature and flow rate
conditions equivalent to those given in Table 1.
7.3 Internal standard calibration procedure--To use this approach,
the analyst must select three or more internal standards that are
similar in analytical behavior to the compounds of interest. The analyst
must further demonstrate that the measurement of the internal standard
is not affected by method or matrix interferences. Some recommended
internal standards are listed in Table 3.
7.3.1 Prepare calibration standards at a minimum of three
concentration levels for each parameter by carefully adding 20.0
[micro]L of one or more secondary dilution standards to 50, 250, or 500
mL of reagent water. A 25-[micro]L syringe with a 0.006 in. ID needle
should be used for this operation. One of the calibration standards
should be at a concentration near, but above, the MDL (Table 1) and the
other concentrations should correspond to the expected range of
concentrations found in real samples or should define the working range
of the GC/MS system. These aqueous standards can be stored up to 24 h,
if held in sealed vials with zero headspace as described in Section 9.2.
If not so stored, they must be discarded after 1 h.
7.3.2 Prepare a spiking solution containing each of the internal
standards using the procedures described in Sections 6.5 and
[[Page 199]]
6.6. It is recommended that the secondary dilution standard be prepared
at a concentration of 15 [micro]g/mL of each internal standard compound.
The addition of 10 [micro]L of this standard to 5.0 mL of sample or
calibration standard would be equivalent to 30 [micro]g/L.
7.3.3 Analyze each calibration standard according to Section 11,
adding 10 [micro]L of internal standard spiking solution directly to the
syringe (Section 11.4). Tabulate the area response of the characteristic
m/z against concentration for each compound and internal standard, and
calculate response factors (RF) for each compound using Equation 1.
[GRAPHIC] [TIFF OMITTED] TC15NO91.124
Equation 1
where:
As=Area of the characteristic m/z for the parameter to be
measured.
Ais=Area of the characteristic m/z for the inernal standard.
Cis=Concentration of the internal standard.
Cs=Concentration of the parameter to be measured.
If the RF value over the working range is a constant (<35% RSD), the RF
can be assumed to be invariant and the average RF can be used for
calculations. Alternatively, the results can be used to plot a
calibration curve of response ratios, As/Ais, vs.
RF.
7.4 The working calibration curve or RF must be verified on each
working day by the measurement of a QC check sample.
7.4.1 Prepare the QC check sample as described in Section 8.2.2.
7.4.2 Analyze the QC check sample according to the method beginning
in Section 10.
7.4.3 For each parameter, compare the response (Q) with the
corresponding calibration acceptance criteria found in Table 5. If the
responses for all parameters of interest fall within the designated
ranges, analysis of actual samples can begin. If any individual Q falls
outside the range, proceed according to Section 7.4.4.
Note: The large number of parameters in Table 5 present a
substantial probability that one or more will not meet the calibration
acceptance criteria when all parameters are analyzed.
7.4.4 Repeat the test only for those parameters that failed to meet
the calibration acceptance criteria. If the response for a parameter
does not fall within the range in this second test, a new calibration
curve or RF must be prepared for that parameter according to Section
7.3.
8. Quality Control
8.1 Each laboratory that uses this method is required to operate a
formal quality control program. The minimum requirements of this program
consist of an initial demonstration of laboratory capability and an
ongoing analysis of spiked samples to evaluate and document data
quality. The laboratory must maintain records to document the quality of
data that is generated. Ongoing data quality checks are compared with
established performance criteria to determine if the results of analyses
meet the performance characteristics of the method. When results of
sample spikes indicate atypical method performance, a quality control
check standard must be analyzed to confirm that the measurements were
performed in an in-control mode of operation.
8.1.1 The analyst must make an initial, one-time, demonstration of
the ability to generate acceptable accuracy and precision with this
method. This ability is established as described in Section 8.2.
8.1.2 In recognition of advances that are occurring in
chromatography, the analyst is permitted certain options (detailed in
Section 11.1) to improve the separations or lower the cost of
measurements. Each time such a modification is made to the method, the
analyst is required to repeat the procedure in Section 8.2.
8.1.3 Each day, the analyst must analyze a reagent water blank to
demonstrate that interferences from the analytical system are under
control.
8.1.4 The laboratory must, on an ongoing basis, spike and analyze a
minimum of 5% of all samples to monitor and evaluate laboratory data
quality. This procedure is described in Section 8.3.
8.1.5 The laboratory must, on an ongoing basis, demonstrate through
the analyses of quality control check standards that the operation of
the measurement system is in control. This procedure is described in
Section 8.4. The frequency of the check standard analyses is equivalent
to 5% of all samples analyzed but may be reduced if spike recoveries
from samples (Section 8.3) meet all specified quality control criteria.
8.1.6 The laboratory must spike all samples with surrogate standards
to monitor continuing laboratory performance. This procedure is
described in Section 8.5.
8.1.7 The laboratory must maintain performance records to document
the quality of data that is generated. This procedure is described in
Section 8.6.
8.2 To establish the ability to generate acceptable accuracy and
precision, the analyst must perform the following operations.
8.2.1 A quality control (QC) check sample concentrate is required
containing each parameter of interest at a concentration of 10 [micro]g/
mL in methanol. The QC check sample concentrate must be obtained from
the U.S. Environmental Protection Agency, Environmental Monitoring and
Support Laboratory in Cincinnati, Ohio, if available. If not available
from that source, the QC check sample
[[Page 200]]
concentrate must be obtained from another external source. If not
available from either source above, the QC check sample concentrate must
be prepared by the laboratory using stock standards prepared
independently from those used for calibration.
8.2.2 Prepare a QC check sample to contain 20 [micro]g/L of each
parameter by adding 200 [micro]L of QC check sample concentrate to 100
mL of reagent water.
8.2.3 Analyze four 5-mL aliquots of the well-mixed QC check sample
according to the method beginning in Section 10.
8.2.4 Calculate the average recovery (X) in [micro]g/L, and the
standard deviation of the recovery (s) in [micro]g/L, for each parameter
of interest using the four results.
8.2.5 For each parameter compare s and X with the corresponding
acceptance criteria for precision and accuracy, respectively, found in
Table 5. If s and X for all parameters of interest meet the acceptance
criteria, the system performance is acceptable and analysis of actual
samples can begin. If any individual s exceeds the precision limit or
any individual X falls outside the range for accuracy, the system
performance is unacceptable for that parameter.
Note: The large number of parameters in Table 5 present a
substantial probability that one or more will fail at least one of the
acceptance criteria when all parameters are analyzed.
8.2.6 When one or more of the parameters tested fail at least one of
the acceptance criteria, the analyst must proceed according to Section
8.2.6.1 or 8.2.6.2.
8.2.6.1 Locate and correct the source of the problem and repeat the
test for all parameters of interest beginning with Section 8.2.3.
8.2.6.2 Beginning with Section 8.2.3, repeat the test only for those
parameters that failed to meet criteria. Repeated failure, however, will
confirm a general problem with the measurement system. If this occurs,
locate and correct the source of the problem and repeat the test for all
compounds of interest beginning with Section 8.2.3.
8.3 The laboratory must, on an ongoing basis, spike at least 5% of
the samples from each sample site being monitored to assess accuracy.
For laboratories analyzing 1 to 20 samples per month, at least one
spiked sample per month is required.
8.3.1 The concentration of the spike in the sample should be
determined as follows:
8.3.1.1 If, as in compliance monitoring, the concentration of a
specific parameter in the sample is being checked against a regulatory
concentration limit, the spike should be at that limit or 1 to 5 times
higher than the background concentration determined in Section 8.3.2,
whichever concentration would be larger.
8.3.1.2 If the concentration of a specific parameter in the sample
is not being checked against a limit specific to that parameter, the
spike should be at 20 [micro]g/L or 1 to 5 times higher than the
background concentration determined in Section 8.3.2, whichever
concentration would be larger.
8.3.2 Analyze one 5-mL sample aliquot to determine the background
concentration (B) of each parameter. If necessary, prepare a new QC
check sample concentrate (Section 8.2.1) appropriate for the background
concentrations in the sample. Spike a second 5-mL sample aliquot with 10
[micro]L of the QC check sample concentrate and analyze it to determine
the concentration after spiking (A) of each parameter. Calculate each
percent recovery (P) as 100(A-B)%/T, where T is the known true value of
the spike.
8.3.3 Compare the percent recovery (P) for each parameter with the
corresponding QC acceptance criteria found in Table 5. These acceptance
criteria wer calculated to include an allowance for error in measurement
of both the background and spike concentrations, assuming a spike to
background ratio of 5:1. This error will be accounted for to the extent
that the analyst's spike to background ratio approaches 5:1.7
If spiking was performed at a concentration lower than 20 [micro]g/L,
the analyst must use either the QC acceptance criteria in Table 5, or
optional QC acceptance criteria calculated for the specific spike
concentration. To calculate optional acceptance criteria for the
recoveryof a parameter: (1) Calculate accuracy (X') using the equation
in Table 6, substituting the spike concentration (T) for C; (2)
calculate overall precision (S') using the equation in Table 6,
substituting X' for X; (3) calculate the range for recovery at the spike
concentration as (100 X'/T) (2.44(100 S'/
T)%.7
8.3.4 If any individual P falls outside the designated range for
recovery, that parameter has failed the acceptance criteria. A check
standard containing each parameter that failed the criteria must be
analyzed as described in Section 8.4.
8.4 If any parameter fails the acceptance criteria for recovery in
Section 8.3, a QC check standard containing each parameter that failed
must be prepared and analyzed.
Note: The frequency for the required anlaysis of a QC check standard
will depend upon the number of parameters being simultaneously tested,
the complexity of the sample matrix, and the performance of the
laboratory. If the entire list of parameters in Table 5 must be measured
in the sample in Section 8.3, the probability that the analysis of a QC
check standard will be required is high. In this case the QC check
standard should be routinely analyzed with the spiked sample.
8.4.1 Prepare the QC check standard by adding 10 [micro]L of QC
check sample concentrate (Section 8.2.1 or 8.3.2) to 5 mL of reagent
water. The QC check standard needs only to
[[Page 201]]
contain the parameters that failed criteria in the test in Section 8.3.
8.4.2 Analyze the QC check standard to determine the concentration
measured (A) of each parameter. Calculate each percent recovery
(PS) as 100 (A/T)%, where T is the true value of the standard
concentration.
8.4.3 Compare the percent recovery (PS) for each
parameter with the corresponding QC acceptance criteria found in Table
5. Only parameters that failed the test in Section 8.3 need to be
compared with these criteria. If the recovery of any such parameter
falls outside the designated range, the laboratory performance for that
parameter is judged to be out of control, and the problem must be
immediately identified and corrected. The analytical result for that
parameter in the unspiked sample is suspect and may not be reported for
regulatory compliance purposes.
8.5 As a quality control check, the laboratory must spike all
samples with the surrogate standard spiking solutions as described in
Section 11.4, and calculate the percent recovery of each surrogate
compound.
8.6 As part of the QC program for the laboratory, method accuracy
for wastewater samples must be assessed and records must be maintained.
After the analysis of five spiked wastewater samples as in Section 8.3,
calculate the average percent recovery (P) and the standard deviation of
the percent recovery (sp). Express the accuracy assessment as
a percent recovery interval from P--2sp to P +
2sp. If P=90% and sp=10%, for example, the
accuracy interval is expressed as 70-110%. Update the accuracy
assessment for each parameter a regular basis (e.g. after each five to
ten new accuracy measurements).
8.7 It is recommended that the laboratory adopt additional quality
assurance practices for use with this method. The specific practices
that are most productive depend upon the needs of the laboratory and the
nature of the samples. Field duplicates may be analyzed to assess the
precision of the environmental measurements. Whenever possible, the
laboratory should analyze standard reference materials and participate
in relevant performance evaluation studies.
9. Sample Collection, Preservation, and Handling
9.1 All samples must be iced or refrigerated from the time of
collection until analysis. If the sample contains residual chlorine, add
sodium thiosulfate preservative (10 mg/40 mL is sufficient for up to 5
ppm Cl2) to the empty sample bottle just prior to shipping to
the sampling site. EPA Methods 330.4 and 330.5 may be used for
measurement of residual chlorine.\8\ Field test kits are available for
this purpose.
9.2 Grab samples must be collected in glass containers having a
total volume of at least 25 mL. Fill the sample bottle just to
overflowing in such a manner that no air bubbles pass through the sample
as the bottle is being filled. Seal the bottle so that no air bubbles
are entrapped in it. If preservative has been added, shake vigorously
for 1 min. Maintain the hermetic seal on the sample bottle until time of
analysis.
9.3 Experimental evidence indicates that some aromatic compounds,
notably benzene, toluene, and ethyl benzene are susceptible to rapid
biological degradation under certain environmental conditions.\3\
Refrigeration alone may not be adequate to preserve these compounds in
wastewaters for more than seven days. For this reason, a separate sample
should be collected, acidified, and analyzed when these aromatics are to
be determined. Collect about 500 mL of sample in a clean container.
Adjust the pH of the sample to about 2 by adding 1+1 HCl while stirring
vigorously, Check pH with narrow range (1.4 to 2.8) pH paper. Fill a
sample container as described in Section 9.2.
9.4 All samples must be analyzed within 14 days of collection.\3\
10. Daily GC/MS Performance Tests
10.1 At the beginning of each day that analyses are to be performed,
the GC/MS system must be checked to see if acceptable performance
criteria are achieved for BFB.\9\ The performance test must be passed
before any samples, blanks, or standards are analyzed, unless the
instrument has met the DFTPP test described in Method 625 earlier in the
day.\10\
10.2 These performance tests require the following instrumental
parameters:
Electron Energy: 70 V (nominal)
Mass Range: 20 to 260 amu
Scan Time: To give at least 5 scans per peak but not to exceed 7 s
per scan.
10.3 At the beginning of each day, inject 2 [micro]L of BFB solution
directly on the column. Alternatively, add 2 [micro]L of BFB solution to
5.0 mL of reagent water or standard solution and analyze the solution
according to section 11. Obtain a background-corrected mass spectrum of
BFB and confirm that all the key m/z criteria in Table 2 are achieved.
If all the criteria are not achieved, the analyst must retune the mass
spectrometer and repeat the test until all criteria are achieved.
11. Sample Purging and Gas Chromatography
11.1 Table 1 summarizes the recommended operating conditions for the
gas chromatograph. Included in this table are retention times and MDL
that can be achieved under these conditions. An example of the
separations achieved by this column is shown in Figure 5. Other packed
columns or chromatographic conditions may be used if the requirements of
Section 8.2 are met.
[[Page 202]]
11.2 After achieving the key m/z abundance criteria in Section 10,
calibrate the system daiy as described in Section 7.
11.3 Adjust the purge gas (helium) flow rate to 40 mL/min. Attach
the trap inlet to the purging device, and set the purge and trap system
to purge (Figure 3). Open the syringe valve located on the purging
device sample introduction needle.
11.4 Allow the sample to come to ambient temperature prior to
introducing it into the syringe. Remove the plunger from a 5-mL syringe
and attach a closed syringe valve. Open the sample bottle (or standard)
and carefully pour the sample into the syringe barrel to just short of
overflowing. Replace the syringe plunger and compress the sample. Open
the syringe valve and vent any residual air while adjusting the sample
volume to 5.0 mL. Since this process of taking an aliquot destroys the
validity of the sample for future analysis, the analyst should fill a
second syringe at this time to protect against possible loss of data.
Add 10.0 [micro]L of the surrogate spiking solution (Section 6.7) and
10.0 [micro]L of the internal standard spiking solution (Section 7.3.2)
through the valve bore, then close the valve. The surrogate and internal
standards may be mixed and added as a single spiking solution.
11.5 Attach the syringe-syringe valve assembly to the syringe valve
on the purging device. Open the syringe valves and inject the sample
into the purging chamber.
11.6 Close both valves and purge the sample for 11.00.1 min at ambient temperature.
11.7 After the 11-min purge time, attach the trap to the
chromatograph, adjust the purge and trap system to the desorb mode
(Figure 4), and begin to temperature program the gas chromatograph.
Introduce the trapped materials to the GC column by rapidly heating the
trap to 180 [deg]C while backflushing the trap with an inert gas between
20 and 60 mL/min for 4 min. If rapid heating of the trap cannot be
achieved, the GC cloumn must be used as a secondary trap by cooling it
to 30 [deg]C (subambient temperature, if problems persist) instead of
the initial program temperature of 45 [deg]C.
11.8 While the trap is being desorbed into the gas chromatograph,
empty the purging chamber using the sample introduction syringe. Wash
the chamber with two 5-mL flushes of reagent water.
11.9 After desorbing the sample for 4 min, recondition the trap by
returning the purge and trap system to the purge mode. Wait 15 s then
close the syringe valve on the purging device to begin gas flow through
the trap. The trap temperature should be maintained at 180 [deg]C. After
approximately 7 min, turn off the trap heater and open the syringe valve
to stop the gas flow through the trap. When the trap is cool, the next
sample can be analyzed.
11.10 If the response for any m/z exceeds the working range of the
system, prepare a dilution of the sample with reagent water from the
aliquot in the second syringe and reanalyze.
12. Qualitative Identification
12.1 Obtain EICPs for the primary m/z (Table 4) and at least two
secondary masses for each parameter of interest. The following criteria
must be met to make a qualitative identification:
12.1.1 The characteristic masses of each parameter of interest must
maximize in the same or within one scan of each other.
12.1.2 The retention time must fall within 30
s of the retention time of the authentic compound.
12.1.3 The relative peak heights of the three characteristic masses
in the EICPs must fall within 20% of the relative
intensities of these masses in a reference mass spectrum. The reference
mass spectrum can be obtained from a standard analyzed in the GC/MS
system or from a reference library.
12.2 Structural isomers that have very similar mass spectra and less
than 30 s difference in retention time, can be explicitly identified
only if the resolution between authentic isomers in a standard mix is
acceptable. Acceptable resolution is achieved if the baseline to valley
height between the isomers is less than 25% of the sum of the two peak
heights. Otherwise, structural isomers are identified as isomeric pairs.
13. Calculations
13.1 When a parameter has been identified, the quantitation of that
parameter should be based on the integrated abundance from the EICP of
the primary characteristic m/z given in Table 4. If the sample produces
an interference for the primary m/z, use a secondary characteristic m/z
to quantitate.
Calculate the concentration in the sample using the response factor
(RF) determined in Section 7.3.3 and Equation 2.
[GRAPHIC] [TIFF OMITTED] TC15NO91.125
Equation 2
where:
AS=Area of the characteristic m/z for the parameter or
surrogate standard to be measured.
Ais=Area of the characteristic m/z for the internal standard.
Cis=Concentration of the internal standard.
13.2 Report results in [micro]g/L without correction for recovery
data. All QC data obtained should be reported with the sample results.
[[Page 203]]
14. Method Performance
14.1 The method detection limit (MDL) is defined as the minimum
concentration of a substance that can be measured and reported with 99%
confidence that the value is above zero.\1\ The MDL concentrations
listed in Table 1 were obtained using reagent water.\11\ Similar results
were achieved using representative wastewaters. The MDL actually
achieved in a given analysis will vary depending on instrument
sensitivity and matrix effects.
14.2 This method was tested by 15 laboratories using reagent water,
drinking water, surface water, and industrial wastewaters spiked at six
concentrations over the range 5-600 [micro]g/L.12Single
operator precision, overall precision, and method accuracy were found to
be directly related to the concentration of the parameter and
essentially independent of the sample matrix. Linear equations to
describe these relationships are presented in Table 5.
References
1. 40 CFR part 136, appendix B.
2. Bellar, T.A., and Lichtenberg, J.J. ``Determining Volatile
Organics at Microgram-per-Litre Levels by Gas Chromatography,'' Journal
American Water Works Association, 66, 739 (1974).
3. Bellar, T.A., and Lichtenberg, J.J. ``Semi-Automated Headspace
Analysis of Drinking Waters and Industrial Waters for Purgeable Volatile
Organic Compounds, '' Measurement of Organic Pollutants in Water and
Wastewater, C.E. Van Hall, editor, American Society for Testing and
Materials, Philadelphia, PA. Special Technical Publication 686, 1978.
4. ``Carcinogens--Working With Carcinogens,'' Department of Health,
Education, and Welfare, Public Health Service, Center for Disease
Control, National Institute for Occupational Safety and Health,
Publication No. 77-206, August 1977.
5. ``OSHA Safety and Health Standards, General Industry,'' (29 CFR
part 1910), Occupational Safety and Health Administration, OSHA 2206
(Revised, January 1976).
6. ``Safety in Academic Chemistry Laboratories,'' American Chemical
Society Publication, Committee on Chemical Safety, 3rd Edition, 1979.
7. Provost, L.P., and Elder, R.S. ``Interpretation of Percent
Recovery Data,'' American Laboratory, 15, 58-63 (1983). (The value 2.44
used in the equation in Section 8.2.3 is two times the value 1.22
derived in this report.)
8. ``Methods 330.4 (Titrimetric, DPD-FAS) and 330.5
(Spectrophotometric, DPD) for Chlorine, Total Residual,'' Methods for
Chemical Analysis of Water and Wastes, EPA-600/4-79-020, U.S.
Environmental Protection Agency, Environmental Monitoring and Support
Laboratory, Cincinnati, Ohio 45268, March 1979.
9. Budde, W.L., and Eichelberger, J.W. ``Performance Tests for the
Evaluation of Computerized Eas Chromatography/Mass Spectrometry
Equipment and Laboratories,'' EPA-600/4-80-025, U.S. Environmental
Protection Agency, Environmental Monitoring and Support Laboratory,
Cincinnati, Ohio 45268, April 1980.
10. Eichelberger, J.W., Harris, L.E., and Budde, W.L. ``Reference
Compound to Calibrate Ion Abundance Measurement in Gas Chromatography--
Mass Spectrometry Systems,'' Analytical Chemistry, 47, 995-1000 (1975).
11. ``Method Detection Limit for Methods 624 and 625,'' Olynyk, P.,
Budde, W.L., and Eichelberger, J.W. Unpublished report, May 14, 1980.
12. ``EPA Method Study 29 EPA Method 624--Purgeables,'' EPA 600/4-
84-054, National Technical Information Service, PB84-209915,
Springfield, Virginia 22161, June 1984.
13.``Method Performance Data for Method 624,'' Memorandum from R.
Slater and T. Pressley, U.S. Environmental Protection Agency,
Environmental Monitoring and Support Laboratory, Cincinnati, Ohio 45268,
January 17, 1984.
Table 1--Chromatographic Conditions and Method Detection Limits
------------------------------------------------------------------------
Method
detection
Parameter Retention limit
time (min) ([micro]g/
L)
------------------------------------------------------------------------
Chloromethane................................... 2.3 nd
Bromomethane.................................... 3.1 nd
Vinyl chloride.................................. 3.8 nd
Chloroethane.................................... 4.6 nd
Methylene chloride.............................. 6.4 2.8
Trichlorofluoromethane.......................... 8.3 nd
1,1-Dichloroethene.............................. 9.0 2.8
1,1-Dichloroethane.............................. 10.1 4.7
trans-1,2-Dichloroethene........................ 10.8 1.6
Chloroform...................................... 11.4 1.6
1,2-Dichloroethane.............................. 12.1 2.8
1,1,1-Trichloroethane........................... 13.4 3.8
Carbon tetrachloride............................ 13.7 2.8
Bromodichloromethane............................ 14.3 2.2
1,2-Dichloroproane.............................. 15.7 6.0
cis-1,3-Dichloropropene......................... 15.9 5.0
Trichloroethene................................. 16.5 1.9
Benzene......................................... 17.0 4.4
Dibromochloromethane............................ 17.1 3.1
1,1,2-Trichloroethane........................... 17.2 5.0
trans-1,3-Dichloropropene....................... 17.2 nd
2-Chloroethylvinlyl ether....................... 18.6 nd
Bromoform....................................... 19.8 4.7
1,1,2,2-Tetrachloroethane....................... 22.1 6.9
Tetrachloroethene............................... 22.2 4.1
Toluene......................................... 23.5 6.0
Chlorobenzene................................... 24.6 6.0
Ethyl benzene................................... 26.4 7.2
1,3-Dichlorobenzene............................. 33.9 nd
1,2-Dichlorobenzene............................. 35.0 nd
[[Page 204]]
1,4-Dichlorobenzene............................. 35.4 nd
------------------------------------------------------------------------
Column conditions: Carbopak B (60/80 mesh) coated with 1% SP-1000 packed
in a 6 ft by 0.1 in. ID glass column with helium carrier gas at 30 mL/
min. flow rate. Column temperature held at 45[deg]C for 3 min., then
programmed at 8[deg]C/min. to 220[deg]C and held for 15 min.
nd=not determined.
Table 2--BFB Key m/z Abundance Criteria
------------------------------------------------------------------------
Mass m/z Abundance criteria
------------------------------------------------------------------------
50........................................ 15 to 40% of mass 95.
75........................................ 30 to 60% of mass 95.
95........................................ Base Peak, 100% Relative
Abundance.
96........................................ 5 to 9% of mass 95.
173....................................... <2% of mass 174.
174....................................... 50% of mass 95.
175....................................... 5 to 9% of mass 174.
176....................................... 95% but <101% of
mass 174.
177....................................... 5 to 9% of mass 176.
------------------------------------------------------------------------
Table 3--Suggested Surrogate and Internal Standards
------------------------------------------------------------------------
Retention
Compound time Primary Secondary
(min)a m/z masses
------------------------------------------------------------------------
Benzene d-6............................ 17.0 84 ...........
4-Bromofluorobenzene................... 28.3 95 174, 176
1,2-Dichloroethane d-4................. 12.1 102 ...........
1,4-Difluorobenzene.................... 19.6 114 63, 88
Ethylbenzene d-5....................... 26.4 111 ...........
Ethylbenzene d-10...................... 26.4 98 ...........
Fluorobenzene.......................... 18.4 96 70
Pentafluorobenzene..................... 23.5 168 ...........
Bromochloromethane..................... 9.3 128 49, 130, 51
2-Bromo-1-chloropropane................ 19.2 77 79, 156
1, 4-Dichlorobutane.................... 25.8 55 90, 92
------------------------------------------------------------------------
a For chromatographic conditions, see Table 1.
Table 4--Characteristic Masses for Purgeable Organics
------------------------------------------------------------------------
Parameter Primary Secondary
------------------------------------------------------------------------
Chloromethane........................ 50 52.
Bromomethane......................... 94 96.
Vinyl chloride....................... 62 64.
Chloroethane......................... 64 66.
Methylene chloride................... 84 49, 51, and 86.
Trichlorofluoromethane............... 101 103.
1,1-Dichloroethene................... 96 61 and 98.
1,1-Dichloroethane................... 63 65, 83, 85, 98, and 100.
trans-1,2-Dichloroethene............. 96 61 and 98.
Chloroform........................... 83 85.
1,2-Dichloroethane................... 98 62, 64, and 100.
1,1,1-Trichloroethane................ 97 99, 117, and 119.
Carbon tetrachloride................. 117 119 and 121.
Bromodichloromethane................. 127 83, 85, and 129.
1,2-Dichloropropane.................. 112 63, 65, and 114.
trans-1,3-Dichloropropene............ 75 77.
Trichloroethene...................... 130 95, 97, and 132.
Benzene.............................. 78 ........................
Dibromochloromethane................. 127 129, 208, and 206.
1,1,2-Trichloroethane................ 97 83, 85, 99, 132, and
134.
cis-1,3-Dichloropropene.............. 75 77.
2-Chloroethylvinyl ether............. 106 63 and 65.
Bromoform............................ 173 171, 175, 250, 252, 254,
and 256.
1,1,2,2-Tetrachloroethane............ 168 83, 85, 131, 133, and
166.
Tetrachloroethene.................... 164 129, 131, and 166.
Toluene.............................. 92 91.
Chlorobenzene........................ 112 114.
Ethyl benzene........................ 106 91.
1,3-Dichlorobenzene.................. 146 148 and 113.
1,2-Dichlorobenzene.................. 146 148 and 113.
1,4-Dichlorobenzene.................. 146 148 and 113.
------------------------------------------------------------------------
Table 5--Calibration and QC Acceptance Criteria--Method 624a
----------------------------------------------------------------------------------------------------------------
Limit for
Range for Q s Range for X Range for P,
Parameter ([micro]/g/L) ([micro]/ ([micro]/g/L) Ps (%)
g/L)
----------------------------------------------------------------------------------------------------------------
Benzene.............................................. 12.8-27.2 6.9 15.2-26.0 37-151
Bromodichloromethane................................. 13.1-26.9 6.4 10.1-28.0 35-155
Bromoform............................................ 14.2-25.8 5.4 11.4-31.1 45-169
Bromomethane......................................... 2.8-37.2 17.9 D-41.2 D-242
Carbon tetrachloride................................. 14.6-25.4 5.2 17.2-23.5 70-140
Chlorobenzene........................................ 13.2-26.8 6.3 16.4-27.4 37-160
Chloroethane......................................... 7.6-32.4 11.4 8.4-40.4 14-230
2-Chloroethylvinyl ether............................. D-44.8 25.9 D-50.4 D-305
Chloroform........................................... 13.5-26.5 6.1 13.7-24.2 51-138
Chloromethane........................................ D-40.8 19.8 D-45.9 D-273
Dibromochloromethane................................. 13.5-26.5 6.1 13.8-26.6 53-149
1,2-Dichlorobenzene.................................. 12.6-27.4 7.1 11.8-34.7 18-190
1,3-Dichlorobenzene.................................. 14.6-25.4 5.5 17.0-28.8 59-156
1,4-Dichlorobenzene.................................. 12.6-27.4 7.1 11.8-34.7 18-190
1,1-Dichloroethane................................... 14.5-25.5 5.1 14.2-28.5 59-155
1,2-Dichloroethane................................... 13.6-26.4 6.0 14.3-27.4 49-155
1,1-Dichlorothene.................................... 10.1-29.9 9.1 3.7-42.3 D-234
trans-1,2-Dichloroethene............................. 13.9-26.1 5.7 13.6-28.5 54-156
[[Page 205]]
1,2-Dichloropropane.................................. 6.8-33.2 13.8 3.8-36.2 D-210
cis-1,3-Dichloropropene.............................. 4.8-35.2 15.8 1.0-39.0 D-227
trans-1,3-Dichloropropene............................ 10.0-30.0 10.4 7.6-32.4 17-183
Ethyl benzene........................................ 11.8-28.2 7.5 17.4-26.7 37-162
Methylene chloride................................... 12.1-27.9 7.4 D-41.0 D-221
1,1,2,2-Tetrachloroethane............................ 12.1-27.9 7.4 13.5-27.2 46-157
Tetrachloroethene.................................... 14.7-25.3 5.0 17.0-26.6 64-148
Toluene.............................................. 14.9-25.1 4.8 16.6-26.7 47-150
1,1,1-Trichloroethane................................ 15.0-25.0 4.6 13.7-30.1 52-162
1,1,2-Trichloroethane................................ 14.2-25.8 5.5 14.3-27.1 52-150
Trichloroethene...................................... 13.3-26.7 6.6 18.6-27.6 71-157
Trichlorofluoromethane............................... 9.6-30.4 10.0 8.9-31.5 17-181
Vinyl chloride....................................... 0.8-39.2 20.0 D-43.5 D-251
----------------------------------------------------------------------------------------------------------------
Q= Concentration measured in QC check sample, in [micro]g/L (Section 7.5.3).
s= Standard deviation of four recovery measurements, in [micro]g/L (Section 8.2.4).
X= Average recovery of four recovery measurements, in [micro]g/L (Section 8.2.4).
P, Ps= Percent recovery measured, (Section 8.3.2, Section 8.4.2).
D= Detected; result must be greater than zero.
a Criteria were calculated assuming a QC check sample concentration of 20 [micro]g/L.
Note: These criteria are based directly upon the method performance data in Table 6. Where necessary, the limits
for recovery have been broadened to assure applicability of the limits to concentrations below those used to
develop Table 6.
Table 6--Method Accuracy and Precision as Functions of Concentration--Method 624
----------------------------------------------------------------------------------------------------------------
Single analyst
Parameter Accuracy, as recovery, precision, sr' Overall precision, S'
X' ([micro]g/L) ([micro]g/L) ([micro]g/L)
----------------------------------------------------------------------------------------------------------------
Benzene............................... 0.93C+2.00 0.26X-1.74 0.25X-1.33
Bromodichloromethane.................. 1.03C-1.58 0.15X+0.59 0.20X+1.13
Bromoform............................. 1.18C-2.35 0.12X+0.36 0.17X+1.38
Bromomethane a........................ 1.00C 0.43X 0.58X
Carbon tetrachloride.................. 1.10C-1.68 0.12X+0.25 0.11X+0.37
Chlorobenzene......................... 0.98C+2.28 0.16X-0.09 0.26X-1.92
Chloroethane.......................... 1.18C+0.81 0.14X+2.78 0.29X+1.75
2-Chloroethylvinyl ether a............ 1.00C 0.62X 0.84X
Chloroform............................ 0.93C+0.33 0.16X+0.22 0.18X+0.16
Chloromethane......................... 1.03C+0.81 0.37X+2.14 0.58X+0.43
Dibromochloromethane.................. 1.01C-0.03 0.17X-0.18 0.17X+0.49
1,2-Dichlorobenzene b................. 0.94C+4.47 0.22X-1.45 0.30X-1.20
1,3-Dichlorobenzene................... 1.06C+1.68 0.14X-0.48 0.18X-0.82
1,4-Dichlorobenzene b................. 0.94C+4.47 0.22X-1.45 0.30X-1.20
1,1-Dichloroethane.................... 1.05C+0.36 0.13X-0.05 0.16X+0.47
1,2-Dichloroethane.................... 1.02C+0.45 0.17X-0.32 0.21X-0.38
1,1-Dichloroethene.................... 1.12C+0.61 0.17X+1.06 0.43X-0.22
trans-1,2,-Dichloroethene............. 1.05C+0.03 0.14X+0.09 0.19X+0.17
1,2-Dichloropropane a................. 1.00C 0.33X 0.45X
cis-1,3-Dichloropropene a............. 1.00C 0.38X 0.52X
trans-1,3-Dichloropropene a........... 1.00C 0.25X 0.34X
Ethyl benzene......................... 0.98C+2.48 0.14X+1.00 0.26X-1.72
Methylene chloride.................... 0.87C+1.88 0.15X+1.07 0.32X+4.00
1,1,2,2-Tetrachloroethane............. 0.93C+1.76 0.16X+0.69 0.20X+0.41
Tetrachloroethene..................... 1.06C+0.60 0.13X-0.18 0.16X-0.45
Toluene............................... 0.98C+2.03 0.15X-0.71 0.22X-1.71
1,1,1-Trichloroethane................. 1.06C+0.73 0.12X-0.15 0.21X-0.39
1,1,2-Trichloroethane................. 0.95C+1.71 0.14X+0.02 0.18X+0.00
Trichloroethene....................... 1.04C+2.27 0.13X+0.36 0.12X+0.59
Trichloroflouromethane................ 0.99C+0.39 0.33X-1.48 0.34X-0.39
Vinyl chloride........................ 1.00C 0.48X 0.65X
----------------------------------------------------------------------------------------------------------------
X'=Expected recovery for one or more measurements of a sample containing a concentration of C, in [micro]g/L.
Sr=Expected single analyst standard deviation of measurements at an average concentration found ofX, in [micro]g/
L.
S'=Expected interlaboratory standard deviation of measurements at an average concentration found ofX, in
[micro]g/L.
C=True value for the concentration, in [micro]g/L.
X=Average recovery found for measurements of samples containing a concentration of C, in [micro]g/L.
a Estimates based upon the performance in a single laboratory.13
b Due to chromatographic resolution problems, performance statements for these isomers are based upon the sums
of their concentrations.
[[Page 206]]
[GRAPHIC] [TIFF OMITTED] TC02JY92.038
[[Page 207]]
[GRAPHIC] [TIFF OMITTED] TC02JY92.039
[[Page 208]]
[GRAPHIC] [TIFF OMITTED] TC02JY92.040
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[GRAPHIC] [TIFF OMITTED] TC02JY92.041
Method 625--Base/Neutrals and Acids
1. Scope and Application
1.1 This method covers the determination of a number of organic
compounds that are partitioned into an organic solvent and are amenable
to gas chromatography. The parameters listed in Tables 1 and 2 may be
qualitatively and quantitatively determined using this method.
1.2 The method may be extended to include the parameters listed in
Table 3. Benzidine can be subject to oxidative losses during solvent
concentration. Under the alkaline conditions of the extraction step,
[alpha]-BHC, [gamma]-BHC, endosulfan I and II, and endrin are subject to
decomposition. Hexachlorocyclopentadiene is subject to thermal
decomposition in the inlet of the gas chromatograph, chemical reaction
in acetone solution, and photochemical decomposition. N-
nitrosodimethylamine is difficult to separate from the solvent under the
chromatographic conditions described. N-nitrosodiphenylamine decomposes
in the gas chromatographic inlet and cannot be separated from
diphenylamine. The preferred method for each of these parameters is
listed in Table 3.
1.3 This is a gas chromatographic/mass spectrometry (GC/MS) method
2, 14 applicable to the determination of the compounds listed
in Tables 1, 2, and 3 in municipal and industrial discharges as provided
under 40 CFR 136.1.
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1.4 The method detection limit (MDL, defined in Section 16.1) \1\
for each parameter is listed in Tables 4 and 5. The MDL for a specific
wastewater may differ from those listed, depending upon the nature of
interferences in the sample matrix.
1.5 Any modification to this method, beyond those expressly
permitted, shall be considered as a major modification subject to
application and approval of alternate test procedures under 40 CFR 136.4
and 136.5. Depending upon the nature of the modification and the extent
of intended use, the applicant may be required to demonstrate that the
modifications will produce equivalent results when applied to relevant
wastewaters.
1.6 This method is restricted to use by or under the supervision of
analysts experienced in the use of a gas chromatograph/mass spectrometer
and in the interpretation of mass spectra. Each analyst must demonstrate
the ability to generate acceptable results with this method using the
procedure described in Section 8.2.
2. Summary of Method
2.1 A measured volume of sample, approximately 1-L, is serially
extracted with methylene chloride at a pH greater than 11 and again at a
pH less than 2 using a separatory funnel or a continuous extractor.\2\
The methylene chloride extract is dried, concentrated to a volume of 1
mL, and analyzed by GC/MS. Qualitative identification of the parameters
in the extract is performed using the retention time and the relative
abundance of three characteristic masses (m/z). Quantitative analysis is
performed using internal standard techniques with a single
characteristic m/z.
3. Interferences
3.1 Method interferences may be caused by contaminants in solvents,
reagents, glassware, and other sample processing hardware that lead to
discrete artifacts and/or elevated baselines in the total ion current
profiles. All of these materials must be routinely demonstrated to be
free from interferences under the conditions of the analysis by running
laboratory reagent blanks as described in Section 8.1.3.
3.1.1 Glassware must be scrupulously cleaned.3 Clean all
glassware as soon as possible after use by rinsing with the last solvent
used in it. Solvent rinsing should be followed by detergent washing with
hot water, and rinses with tap water and distilled water. The glassware
should then be drained dry, and heated in a muffle furnace at 400 [deg]C
for 15 to 30 min. Some thermally stable materials, such as PCBs, may not
be eliminated by this treatment. Solvent rinses with acetone and
pesticide quality hexane may be substituted for the muffle furnace
heating. Thmrough rinsing with such solvents usually eliminates PCB
interference. Volumetric ware should not be heated in a muffle furnace.
After drying and cooling, glassware should be sealed and stored in a
clean environment to prevent any accumulation of dust or other
contaminants. Store inverted or capped with aluminum foil.
3.1.2 The use of high purity reagents and solvents helps to minimize
interference problems. Purification of solvents by distillation in all-
glass systems may be required.
3.2 Matrix interferences may be caused by contaminants that are co-
extracted from the sample. The extent of matrix interferences will vary
considerably from source to source, depending upon the nature and
diversity of the industrial complex or municipality being sampled.
3.3 The base-neutral extraction may cause significantly reduced
recovery of phenol, 2-methylphenol, and 2,4-dimethylphenol. The analyst
must recognize that results obtained under these conditions are minimum
concentrations.
3.4 The packed gas chromatographic columns recommended for the basic
fraction may not exhibit sufficient resolution for certain isomeric
pairs including the following: anthracene and phenanthrene; chrysene and
ben zo (a) an thra cene; and ben zo (b) flu o ran thene and ben zo (k)
flu o ran thene. The gas chromatographic reten tion time and mass
spectra for these pairs of compounds are not suf fi ciently different to
make an unambiguous identification. Alternative techniques should be
used to identify and quantify these specific compounds, such as Method
610.
3.5 In samples that contain an inordinate number of interferences,
the use of chemical ionization (CI) mass spectrometry may make
identification easier. Tables 6 and 7 give characteristic CI ions for
most of the compounds covered by this method. The use of CI mass
spectrometry to support electron ionization (EI) mass spectrometry is
encouraged but not required.
4. Safety
4.1 The toxicity or carcinogenicity of each reagent used in this
method have not been precisely defined; however, each chemical compound
should be treated as a potential health hazard. From this viewpoint,
exposure to these chemicals must be reduced to the lowest possible level
by whatever means available. The laboratory is responsible for
maintaining a current awareness file of OSHA regulations regarding the
safe handling of the chemicals specified in this method. A reference
file of material data handling sheets should also be made available to
all personnel involved in the chemical analysis. Additional references
to laboratory safety are available and have been identified
4-6 for the information of the analyst.
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4.2 The following parameters covered by this method have been
tentatively classified as known or suspected, human or mammalian
carcinogens: benzo(a)anthracene, benzidine, 3,3'-dichlorobenzidine,
benzo(a)pyrene, [alpha]-BHC, [beta]-BHC, [delta]-BHC, [gamma]-BHC,
dibenzo(a,h)anthracene, N-nitrosodimethylamine, 4,4'-DDT, and
polychlorinated biphenyls (PCBs). Primary standards of these toxic
compounds should be prepared in a hood. A NIOSH/MESA approved toxic gas
respirator should be worn when the analyst handles high concentrations
of these toxic compounds.
5. Apparatus and Materials
5.1 Sampling equipment, for discrete or composit sampling.
5.1.1 Grab sample bottle--1-L or 1-gt, amber glass, fitted with a
screw cap lined with Teflon. Foil may be substituted for Teflon if the
sample is not corrosive. If amber bottles are not available, protect
samples from light. The bottle and cap liner must be washed, rinsed with
acetone or methylene chloride, and dried before use to minimize
contamination.
5.1.2 Automatic sampler (optional)--The sampler must incorporate
glass sample containers for the collection of a minimum of 250 mL of
sample. Sample containers must be kept refrigerated at 4 [deg]C and
protected from light during compositing. If the sampler uses a
peristaltic pump, a minimum length of compressible silicone rubber
tubing may be used. before use, however, the compressible tubing should
be throughly rinsed with methanol, followed by repeated rinsings with
distilled water to minimize the potential for contamination of the
sample. An integrating flow meter is required to collect flow
proportional composites.
5.2 Glassware (All specifications are suggested. Catalog numbers are
included for illustration only.):
5.2.1 Separatory funnel--2-L, with Teflon stopcock.
5.2.2 Drying column--Chromatographic column, 19 mm ID, with coarse
frit
5.2.3 Concentrator tube, Kuderna-Danish--10-mL, graduated (Kontes K-
570050-1025 or equivalent). Calibration must be checked at the volumes
employed in the test. Ground glass stopper is used to prevent
evaporation of extracts.
5.2.4 Evaporative flask, Kuderna-Danish--500-mL (Kontes K-57001-0500
or equivalent). Attach to concentrator tube with springs.
5.2.5 Snyder column, Kuderna-Danish--Three all macro (Kontes K-
503000-0121 or equivalent).
5.2.6 Snyder column, Kuderna-Danish--Two- ball macro (Kontes K-
569001-0219 or equivalent).
5.2.7 Vials--10 to 15-mL, amber glass, with Teflon-lined screw cap.
5.2.8 Continuous liquid--liquid extractor--Equipped with Teflon or
glass connecting joints and stopcocks requiring no lubrication.
(Hershberg-Wolf Extractor, Ace Glass Company, Vineland, N.J., P/N 6841-
10 or equivalent.)
5.3 Boiling chips--Approximately 10/40 mesh. Heat to 400 [deg]C for
30 min of Soxhlet extract with methylene chloride.
5.4 Water bath--Heated, with concentric ring cover, capable of
temperature control (2[deg]C). The bath should be
used in a hood.
5.5 Balance--Analytical, capable of accurately weighing 0.0001 g.
5.6 GC/MS system:
5.6.1 Gas Chromatograph--An analytical system complete with a
temperature programmable gas chromatograph and all required accessores
including syringes, analytical columns, and gases. The injection port
must be designed for on-column injection when using packed columns and
for splitless injection when using capillary columns.
5.6.2 Column for base/neutrals--1.8 m long x 2 mm ID glass, packed
with 3% SP-2250 on Supelcoport (100/120 mesh) or equivalent. This column
was used to develop the method performance statements in Section 16.
Guide lines for the use of alternate column pack ings are provided in
Section 13.1.
5.6.3 Column for acids--1.8 m long x 2 mm ID glass, packed with 1%
SP-1240DA on Supelcoport (100/120 mesh) or equivalent. This column was
used to develop the method performance statements in Section 16.
Guidelines for the use of alternate column packings are given in Section
13.1.
5.6.4 Mass spectrometer--Capable of scanning from 35 to 450 amu
every 7 s or less, utilizing a 70 V (nominal) electron energy in the
electron impact ionization mode, and producing a mass spectrum which
meets all the criteria in Table 9 when 50 ng of decafluorotriphenyl
phosphine (DFTPP; bis(perfluorophenyl) phenyl phosphine) is injected
through the GC inlet.
5.6.5 GC/MS interface--Any GC to MS interface that gives acceptable
calibration points at 50 ng per injection for each of the parameters of
interest and achieves all acceptable performance criteria (Section 12)
may be used. GC to MS interfaces constructed of all glass or glass-lined
materials are recommended. Glass can be deactivated by silanizing with
dichlorodimethylsilane.
5.6.6 Data system--A computer system must be interfaced to the mass
spectrometer that allows the contiluous acquisition and storage on
machine-readable media of all mass spectra obtained throughout the
duration of the chromatographic program. The computer must have software
that allows searching any GC/MS data file for specific m/z and plotting
such m/z abundances versus time or scan number. This type of plot is
defined as an Extracted Ion Current Profile (EICP). Software must also
be available that
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allows integrating the abundance in any EICP between specified time or
scan number limits.
6. Reagents
6.1 Reagent water--Reagent water is defined as a water in which an
interferent is not observed at the MDL of the parameters of interest.
6.2 Sodium hydroxide solution (10 N)--Dissolve 40 g of NaOH (ACS) in
reagent water and dilute to 100 mL.
6.3 Sodium thiosulfate--(ACS) Granular.
6.4 Sulfuric acid (1+1)--Slowly, add 50 mL of
H2SO4 (ACS, sp. gr. 1.84) to 50 mL of reagent
water.
6.5 Acetone, methanol, methlylene chloride--Pesticide quality or
equivalent.
6.6 Sodium sulfate--(ACS) Granular, anhydrous. Purify by heating at
400 [deg]C for 4 h in a shallow tray.
6.7 Stock standard solutions (1.00 [micro]g/[micro]L)--standard
solutions can be prepared from pure standard materials or purchased as
certified solutions.
6.7.1 Prepare stock standard solutions by accurately weighing about
0.0100 g of pure material. Dissolve the material in pesticide quality
acetone or other suitable solvent and dilute to volume in a 10-mL
volumetric flask. Larger volumes can be used at the convenience of the
analyst. When compound purity is assayed to be 96% or greater, the
weight may be used without correction to calculate the concentration of
the stock standard. Commercially prepared stock standards may be used at
any concentration if they are certified by the manufacturer or by an
independent source.
6.7.2 Transfer the stock standard solutions into Teflon-sealed
screw-cap bottles. Store at 4 [deg]C and protect from light. Stock
standard solutions should be checked frequently for signs of degradation
or evaporation, especially just prior to preparing calibration standards
from them.
6.7.3 Stock standard solutions must be replaced after six months, or
sooner if comparison with quality control check samples indicate a
problem.
6.8 Surrogate standard spiking solution--Select a minimum of three
surrogate compounds from Table 8. Prepare a surrogate standard spiking
solution containing each selected surrogate compound at a concentration
of 100 [micro]g/mL in acetone. Addition of 1.00 mL of this solution to
1000 mL of sample is equivalent to a concentration of 100 [micro]g/L of
each surrogate standard. Store the spiking solution at 4 [deg]C in
Teflon-sealed glass container. The solution should be checked frequently
for stability. The solution must be replaced after six months, or sooner
if comparison with quality control check standards indicates a problem.
6.9 DFTPP standard--Prepare a 25 [micro]g/mL solution of DFTPP in
acetone.
6.10 Quality control check sample concentrate--See Section 8.2.1.
7. Calibration
7.1 Establish gas chromatographic operating parameters equivalent to
those indicated in Table 4 or 5.
7.2 Internal standard calibration procedure--To use this approach,
the analyst must select three or more internal standards that are
similar in analytical behavior to the compounds of interest. The analyst
must further demonstrate that the measurement of the internal standards
is not affected by method or matrix interferences. Some recommended
internal standards are listed in Table 8. Use the base peak m/z as the
primary m/z for quantification of the standards. If interferences are
noted, use one of the next two most intense m/z quantities for
quantification.
7.2.1 Prepare calibration standards at a minimum of three
concentration levels for each parameter of interest by adding
appropriate volumes of one or more stock standards to a volumetric
flask. To each calibration standard or standard mixture, add a known
constant amount of one or more internal standards, and and dilute to
volume with acetone. One of the calibration standards should be at a
concentration near, but above, the MDL and the other concentrations
should correspond to the expected range of concentrations found in real
samples or should define the working range of the GC/MS system.
7.2.2 Using injections of 2 to 5 [micro]L, analyze each calibration
standard according to Section 13 and tabulate the area of the primary
characteristic m/z (Tables 4 and 5) against concentration for each
compound and internal standard. Calculate response factors (RF) for each
compound using Equation 1.
[GRAPHIC] [TIFF OMITTED] TC15NO91.126
Equation 1
where:
As=Area of the characteristic m/z for the parameter to be
measured.
Ais=Area of the characteristic m/z for the internal standard.
Cis=Concentration of the internal standard ([micro]g/L).
Cs=Concentration of the parameter to be measured ([micro]g/
L).
If the RF value over the working range is a constant (<35% RSD), the RF
can be assumed to be invariant and the average RF can be used for
calculations. Alternatively, the results can be used to plot a
calibration curve of response ratios, As/Ais, vs.
RF.
7.3 The working calibration curve or RF must be verified on each
working day by the
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measurement of one or more calibration standards. If the response for
any parameter varies from the predicted response by more than 20%, the test must be repeated uning a fresh calibration
standard. Alternatively, a new calibration curve must be prepared for
that compound.
8. Quality Control
8.1 Each laboratory that uses this method is required to operate a
formal quality control program. The minimum requirements of this program
consist of an initial demonstration of laboratory capability and an
ongoing analysis of spiked samples to evaluate and document data
quality. The laboratory must maintain records to document the quality of
data that is generated. Ongoing data quality checks are compared with
established performance criteria to determine if the results of analyses
meet the performance characteristics of the method. When results of
sample spikes indicate atypical method performance, a quality control
check standard must be analyzed to confirm that the measurements were
performed in an in-control mode of operation.
8.1.1 The analyst must make an initial, one-time, demonstration of
the ability to generate acceptable accuracy and precision with this
method. This ability is established as described in Section 8.2.
8.1.2 In recognition of advances that are occuring in
chromatography, the analyst is permitted certain options (detailed in
Sections 10.6 and 13.1) to improve the separations or lower the cost of
measurements. Each time such a modification is made to the method, the
analyst is required to repeat the procedure in Section 8.2.
8.1.3 Before processing any samples, the analyst must analyze a
reagent water blank to demonstrate that interferences from the
analytical system and glassware are under control. Each time a set of
samples is extracted or reagents are changed, a reagent water blank must
be processed as a safeguard against laboratory contamination.
8.1.4 The laboratory must, on an ongoing basis, spike and analyze a
minimum of 5% of all samples to monitor and evaluate laboratory data
quality. This procedure is described in Section 8.3.
8.1.5 The laboratory must, on an ongoing basis, demonstrate through
the analyses of quality control check standards that the operation of
the measurement system is in control. This procedure is described in
Section 8.4. The frequency of the check standard analyses is equivalent
to 5% of all samples analyzed but may be reduced if spike recoveries
from samples (Section 8.3) meet all specified quality control criteria.
8.1.6 The laboratory must maintain performance records to document
the quality of data that is generated. This procedure is described in
Section 8.5.
8.2 To establish the ability to generate acceptable accuracy and
precision, the analyst must perform the following operations.
8.2.1 A quality control (QC) check sample concentrate is required
containing each parameter of interest at a concentration of 100
[micro]g/mL in acetone. Multiple solutions may be required. PCBs and
multicomponent pesticides may be omitted from this test. The QC check
sample concentrate must be obtained from the U.S. Environmental
Protection Agency, Environmental Monitoring and Support Laboratory in
Cincinnati, Ohio, if available. If not available from that source, the
QC check sample concentrate must be obtained from another external
source. If not available from either source above, the QC check sample
concentrate must be prepared by the laboratory using stock standards
prepared independently from those used for calibration.
8.2.2 Using a pipet, prepare QC check samples at a concentration of
100 [micro]g/L by adding 1.00 mL of QC check sample concentrate to each
of four 1-L aliquots of reagent water.
8.2.3 Analyze the well-mixed QC check samples according to the
method beginning in Section 10 or 11.
8.2.4 Calculate the average recovery (X) in [micro]g/L, and the
standard deviation of the recovery (s) in [micro]g/L, for each parameter
using the four results.
8.2.5 For each parameter compare s and X with the corresponding
acceptance criteria for precision and accuracy, respectively, found in
Table 6. If s and X for all parameters of interest meet the acceptance
criteria, the system performance is acceptable and analysis of actual
samples can begin. If any individual s exceeds the precision limit or
any individual X falls outside the range for accuracy, the system
performance is unacceptable for that parameter.
Note: The large number of parameters in Table 6 present a
substantial probability that one or more will fail at least one of the
acceptance criteria when all parameters are analyzed.
8.2.6 When one or more of the parameters tested fail at least one of
the acceptance criteria, the analyst must proceed according to Section
8.2.6.1 or 8.2.6.2.
8.2.6.1 Locate and correct the source of the problem and repeat the
test for all parameters of interest beginning with Section 8.2.2.
8.2.6.2 Beginning with Section 8.2.2, repeat the test only for those
parameters that failed to meet criteria. Repeated failure, however, will
confirm a general problem with the measurement system. If this occurs,
locate and correct the source of the problem and repeat the test for all
compounds of interest beginning with Section 8.2.2.
8.3 The laboratory must, on an ongoing basis, spike at least 5% of
the samples from each sample site being monitored to assess
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accuracy. For laboratories analyzing 1 to 20 samples per month, at least
one spiked sample per month is required.
8.3.1. The concentration of the spike in the sample should be
determined as follows:
8.3.1 If, as in compliance monitoring, the concentration of a
specific parameter in the sample is being checked against a regulatory
concentration limit, the spike should be at that limit or 1 to 5 times
higher than the background concentration determined in Section 8.3.2,
whichever concentration would be larger.
8.3.1.2 If the concentration of a specific parameter in the sample
is not being checked against a limit specific to that parameter, the
spike should be at 100 [micro]g/L or 1 to 5 times higher than the
background concentration determined in Section 8.3.2, whichever
concentration would be larger.
8.3.1.3 If it is impractical to determine background levels before
spiking (e.g., maximum holding times will be exceeded), the spike
concentration should be (1) the regulatory concentration limit, if any;
or, if none (2) the larger of either 5 times higher than the expected
background concentration or 100 [micro]g/L.
8.3.2 Analyze one sample aliquot to determine the background
concentration (B) of each parameter. If necessary, prepare a new QC
check sample concentrate (Section 8.2.1) appropriate for the background
concentrations in the sample. Spike a second sample aliquot with 1.0 mL
of the QC check sample concentrate and analyze it to determine the
concentration after spiking (A) of each parameter. Calculate each
percent recovery (P) as 100(A-B)%/T, where T is the known true value of
the spike.
8.3.3 Compare the percent recovery (P) for each parameter with the
corresponding QC acceptance criteria found in Table 6. These acceptance
criteria were calculated to include an allowance for error in
measurement of both the background and spike concentrations, assuming a
spike to background ratio of 5:1. This error will be accounted for to
the extent that the analyst's spike to background ratio approaches
5:1.7 If spiking was performed at a concentration lower than
100 [micro]g/L, the analyst must use either the QC acceptance criteria
in Table 6, or optional QC acceptance criteria calculated for the
specific spike concentration. To calculate optional acceptance criteria
for the recovery of a parameter: (1) Calculate accuracy (X') using the
equation in Table 7, substituting the spike concentration (T) for C; (2)
calculate overall precision (S') using the equation in Table 7,
substituting X' for X; (3) calculate the range for recovery at the spike
concentration as (100 X'/T)2.44(100 S'/
T)%7
8.3.4 If any individual P falls outside the designated range for
recovery, that parameter has failed the acceptance criteria. A check
standard containing each parameter that failed the criteria must be
analyzed as described in Section 8.4.
8.4 If any parameter fails the acceptance criteria for recovery in
Section 8.3, a QC check standard containing each parameter that failed
must be prepared and analyzed.
Note: The frequency for the required analysis of a QC check standard
will depend upon the number of parameters being simultaneously tested,
the complexity of the sample matrix, and the performance of the
laboratory. If the entire list of single-component parameters in Table 6
must be measured in the sample in Section 8.3, the probability that the
analysis of a QC check standard will be required is high. In this case
the QC check standard should be routinely analyzed with the spike
sample.
8.4.1 Prepare the QC check standard by adding 1.0 mL of QC check
sample concentrate (Section 8.2.1 or 8.3.2) to 1 L of reagent water. The
QC check standard needs only to contain the parameters that failed
criteria in the test in Section 8.3.
8.4.2 Analyze the QC check standard to determine the concentration
measured (A) of each parameter. Calculate each percent recovery
(PS) as 100 (A/T)%, where T is the true value of the standard
concentration.
8.4.3 Compare the percent recovery (Ps) for each
parameter with the corresponding QC acceptance criteria found in Table
6. Only parameters that failed the test in Section 8.3 need to be
compared with these criteria. If the recovery of any such parameter
falls outside the designated range, the laboratory performance for that
parameter is judged to be out of control, and the problem must be
immediately identified and corrected. The analytical result for that
parameter in the unspiked sample is suspect and may not be reported for
regulatory compliance purposes.
8.5 As part of the QC program for the laboratory, method accuracy
for wastewater samples must be assessed and records must be maintained.
After the analysis of five spiked wastewater samples as in Section 8.3,
calculate the average percent recovery (P) and the standard deviation of
the percent recovery (sp). Express the accuracy assessment as
a percent interval from P-2sp to P+2sp. If P=90%
and sp=10%, for example, the accuracy interval is expressed
as 70-110%. Update the accuracy assessment for each parameter on a
regular basis (e.g. after each five to ten new accuracy measurements).
8.6 As a quality control check, the laboratory must spike all
samples with the surrogate standard spiking solution as described in
Section 10.2, and calculate the percent recovery of each surrogate
compound.
8.7 It is recommended that the laboratory adopt additional quality
assurance practices for use with this method. The specific practices
that are most productive depend upon the needs of the laboratory and the
nature of
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the samples. Field duplicates may be analyzed to assess the precision of
the environmental measurements. Whenever possible, the laboratory should
analyze standard reference materials and participate in relevant
performance evaluation studies.
9. Sample Collection, Preservation, and Handling
9.1 Grab samples must be collected in glass containers. Conventional
sampling practices 8 should be followed, except that the
bottle must not be prerinsed with sample before collection. Composite
samples should be collected in refrigerated glass containers in
accordance with the requirements of the program. Automatic sampling
equipment must be as free as possible of Tygon tubing and other
potential sources of contamination.
9.2 All sampling must be iced or refrigerated at 4 [deg]C from the
time of collection until extraction. Fill the sample bottles and, if
residual chlorine is present, add 80 mg of sodium thiosulfate per liter
of sample and mix well. EPA Methods 330.4 and 330.5 may be used for
measurement of residual chlorine.9 Field test kits are
available for this purpose.
9.3 All samples must be extracted within 7 days of collection and
completely analyzed within 40 days of extraction.
10. Separatory Funnel Extraction
10.1 Samples are usually extracted using separatory funnel
techniques. If emulsions will prevent achieving acceptable solvent
recovery with separatory funnel extractions, continuous extraction
(Section 11) may be used. The separatory funnel extraction scheme
described below assumes a sample volume of 1 L. When sample volumes of 2
L are to be extracted, use 250, 100, and 100-mL volumes of methylene
chloride for the serial extraction of the base/neutrals and 200, 100,
and 100-mL volumes of methylene chloride for the acids.
10.2 Mark the water meniscus on the side of the sample bottle for
later determination of sample volume. Pour the entire sample into a 2-L
separatory funnel. Pipet 1.00 mL of the surrogate standard spiking
solution into the separatory funnel and mix well. Check the pH of the
sample with wide-range pH paper and adjust to pH11 with
sodium hydroxide solution.
10.3 Add 60 mL of methylene chloride to the sample bottle, seal, and
shake for 30 s to rinse the inner surface. Transfer the solvent to the
separatory funnel and extract the sample by shaking the funnel for 2
min. with periodic venting to release excess pressure. Allow the organic
layer to separate from the water phase for a minimum of 10 min. If the
emulsion interface between layers is more than one-third the volume of
the solvent layer, the analyst must employ mechanical techniques to
complete the phase separation. The optimum technique depends upon the
sample, but may include stirring, filtration of the emulsion through
glass wool, centrifugation, or other physical methods. Collect the
methylene chloride extract in a 250-mL Erlenmeyer flask. If the emulsion
cannot be broken (recovery of less than 80% of the methylene chloride,
corrected for the water solubility of methylene chloride), transfer the
sample, solvent, and emulsion into the extraction chamber of a
continuous extractor and proceed as described in Section 11.3.
10.4 Add a second 60-mL volume of methylene chloride to the sample
bottle and repeat the extraction procedure a second time, combining the
extracts in the Erlenmeyer flask. Perform a third extraction in the same
manner. Label the combined extract as the base/neutral fraction.
10.5 Adjust the pH of the aqueous phase to less than 2 using
sulfuric acid. Serially extract the acidified aqueous phase three times
with 60-mL aliquots of methylene chloride. Collect and combine the
extracts in a 250-mL Erlenmeyer flask and label the combined extracts as
the acid fraction.
10.6 For each fraction, assemble a Kuderna-Danish (K-D) concentrator
by attaching a 10-mL concentrator tube to a 500-mL evaporative flask.
Other concentration devices or techniques may be used in place of the K-
D concentrator if the requirements of Section 8.2 are met.
10.7 For each fraction, pour the combined extract through a solvent-
rinsed drying column containing about 10 cm of anhydrous sodium sulfate,
and collect the extract in the K-D concentrator. Rinse the Erlenmeyer
flask and column with 20 to 30 mL of methylene chloride to complete the
quantitative transfer.
10.8 Add one or two clean boiling chips and attach a three-ball
Snyder column to the evaporative flask for each fraction. Prewet each
Snyder column by adding about 1 mL of methylene chloride to the top.
Place the K-D apparatus on a hot water bath (60 to 65 [deg]C) so that
the concentrator tube is partially immersed in the hot water, and the
entire lower rounded surface of the flask is bathed with hot vapor.
Adjust the vertical position of the apparatus and the water temperature
as required to complete the concentration in 15 to 20 min. At the proper
rate of distillation the balls of the column will actively chatter but
the chambers will not flood with condensed solvent. When the apparent
volume of liquid reaches 1 mL, remove the K-D apparatus from the water
bath and allow it to drain and cool for at least 10 min. Remove the
Snyder column and rinse the flask and its lower joint into the
concentrator tube with 1 to 2 mL of methylene chloride. A 5-mL syringe
is recommended for this operation.
[[Page 216]]
10.9 Add another one or two clean boiling chips to the concentrator
tube for each fraction and attach a two-ball micro-Snyder column. Prewet
the Snyder column by adding about 0.5 mL of methylene chloride to the
top. Place the K-D apparatus on a hot water bath (60 to 65 [deg]C) so
that the concentrator tube is partially immersed in hot water. Adjust
the vertical position of the apparatus and the water temperature as
required to complete the concentration in 5 to 10 min. At the proper
rate of distillation the balls of the column will actively chatter but
the chambers will not flood with condensed solvent. When the apparent
volume of liquid reaches about 0.5 mL, remove the K-D apparatus from the
water bath and allow it to drain and cool for at least 10 min. Remove
the Snyder column and rinse the flask and its lower joint into the
concentrator tube with approximately 0.2 mL of acetone or methylene
chloride. Adjust the final volume to 1.0 mL with the solvent. Stopper
the concentrator tube and store refrigerated if further processing will
not be performed immediately. If the extracts will be stored longer than
two days, they should be transferred to Teflon-sealed screw-cap vials
and labeled base/neutral or acid fraction as appropriate.
10.10 Determine the original sample volume by refilling the sample
bottle to the mark and transferring the liquid to a 1000-mL graduated
cylinder. Record the sample volume to the nearest 5 mL.
11. Continuous Extraction
11.1 When experience with a sample from a given source indicates
that a serious emulsion problem will result or an emulsion is
encountered using a separatory funnel in Section 10.3, a continuous
extractor should be used.
11.2 Mark the water meniscus on the side of the sample bottle for
later determination of sample volume. Check the pH of the sample with
wide-range pH paper and adjust to pH 11 with sodium hydroxide
solution. Transfer the sample to the continuous extractor and using a
pipet, add 1.00 mL of surrogate standard spiking solution and mix well.
Add 60 mL of methylene chloride to the sample bottle, seal, and shake
for 30 s to rinse the inner surface. Transfer the solvent to the
extractor.
11.3 Repeat the sample bottle rinse with an additional 50 to 100-mL
portion of methylene chloride and add the rinse to the extractor.
11.4 Add 200 to 500 mL of methylene chloride to the distilling
flask, add sufficient reagent water to ensure proper operation, and
extract for 24 h. Allow to cool, then detach the distilling flask. Dry,
concentrate, and seal the extract as in Sections 10.6 through 10.9.
11.5 Charge a clean distilling flask with 500 mL of methylene
chloride and attach it to the continuous extractor. Carefully, while
stirring, adjust the pH of the aqueous phase to less than 2 using
sulfuric acid. Extract for 24 h. Dry, concentrate, and seal the extract
as in Sections 10.6 through 10.9.
12. Daily GC/MS Performance Tests
12.1 At the beginning of each day that analyses are to be performed,
the GC/MS system must be checked to see if acceptable performance
criteria are achieved for DFTPP.10 Each day that benzidine is
to be determined, the tailing factor criterion described in Section 12.4
must be achieved. Each day that the acids are to be determined, the
tailing factor criterion in Section 12.5 must be achieved.
12.2 These performance tests require the following instrumental
parameters:
Electron Energy: 70 V (nominal)
Mass Range: 35 to 450 amu
Scan Time: To give at least 5 scans per peak but not to exceed 7 s per
scan.
12.3 DFTPP performance test--At the beginning of each day, inject 2
[micro]L (50 ng) of DFTPP standard solution. Obtain a background-
corrected mass spectra of DFTPP and confirm that all the key m/z
criteria in Table 9 are achieved. If all the criteria are not achieved,
the analyst must retune the mass spectrometer and repeat the test until
all criteria are achieved. The performance criteria must be achieved
before any samples, blanks, or standards are analyzed. The taililg
factor tests in Sections 12.4 and 12.5 may be performed simultaneously
with the DFTPP test.
12.4 Column performance test for base/neutrals--At the beginning of
each day that the base/neutral fraction is to be analyzed for benzidine,
the benzidine tailing factor must be calculated. Inject 100 ng of
benzidine either separately or as a part of a standard mixture that may
contain DFTPP and calculate the tailing factor. The benzidine tailing
factor must be less than 3.0. Calculation of the tailing factor is
illustrated in Figure 13.\11\ Replace the column packing if the tailing
factor criterion cannot be achieved.
12.5 Column performance test for acids--At the beginning of each day
that the acids are to be determined, inject 50 ng of pentachlorophenol
either separately or as a part of a standard mix that may contain DFTPP.
The tailing factor for pentachlorophenol must be less than 5.
Calculation of the tailing factor is illustrated in Figure 13.\11\
Replace the column packing if the tailing factor criterion cannot be
achieved.
13. Gas Chromatography/Mass Spectrometry
13.1 Table 4 summarizes the recommended gas chromatographic
operating conditions for the base/neutral fraction. Table 5 summarizes
the recommended gas chromatographic
[[Page 217]]
operating conditions for the acid fraction. Included in these tables are
retention times and MDL that can be achieved under these conditions.
Examples of the separations achieved by these columns are shown in
Figures 1 through 12. Other packed or capillary (open-tubular) columns
or chromatographic conditions may be used if the requirements of Section
8.2 are met.
13.2 After conducting the GC/MS performance tests in Section 12,
calibrate the system daily as described in Section 7.
13.3 The internal standard must be added to sample extract and mixed
thoroughly immediately before it is injected into the instrument. This
procedure minimizes losses due to adsorption, chemical reaction or
evaporation.
13.4 Inject 2 to 5 [micro]L of the sample extract or standard into
the GC/MS system using the solvent-flush technique.\12\ Smaller (1.0
[micro]L) volumes may be injected if automatic devices are employed.
Record the volume injected to the nearest 0.05 [micro]L.
13.5 If the response for any m/z exceeds the working range of the
GC/MS system, dilute the extract and reanalyze.
13.6 Perform all qualitative and quantitative measurements as
described in Sections 14 and 15. When the extracts are not being used
for analyses, store them refrigerated at 4[deg]C, protected from light
in screw-cap vials equipped with unpierced Teflon-lined septa.
14. Qualitative Identification
14.1 Obtain EICPs for the primary m/z and the two other masses
listed in Tables 4 and 5. See Section 7.3 for masses to be used with
internal and surrogate standards. The following criteria must be met to
make a qualitative identification:
14.1.1 The characteristic masses of each parameter of interest must
maximize in the same or within one scan of each other.
14.1.2 The retention time must fall within 30
s of the retention time of the authentic compound.
14.1.3 The relative peak heights of the three characteristic masses
in the EICPs must fall within 20% of the relative
intensities of these masses in a reference mass spectrum. The reference
mass spectrum can be obtained from a standard analyzed in the GC/MS
system or from a reference library.
14.2 Structural isomers that have very similar mass spectra and less
than 30 s difference in retention time, can be explicitly identified
only if the resolution between authentic isomers in a standard mix is
acceptable. Acceptable resolution is achieved if the baseline to valley
height between the isomers is less than 25% of the sum of the two peak
heights. Otherwise, structural isomers are identified as isomeric pairs.
15. Calculations
15.1 When a parameter has been identified, the quantitation of that
parameter will be based on the integrated abundance from the EICP of the
primary characteristic m/z in Tables 4 and 5. Use the base peak m/z for
internal and surrogate standards. If the sample produces an interference
for the primary m/z, use a secondary characteristic m/z to quantitate.
Calculate the concentration in the sample using the response factor
(RF) determined in Section 7.2.2 and Equation 3.
[GRAPHIC] [TIFF OMITTED] TC15NO91.127
Equation 3
where:
As=Area of the characteristic m/z for the parameter or
surrogate standard to be measured.
Ais=Area of the characteristic m/z for the internal standard.
Is=Amount of internal standard added to each extract
([micro]g).
Vo=Volume of water extracted (L).
15.2 Report results in [micro]g/L without correction for recovery
data. All QC data obtained should be reported with the sample results.
16. Method Performance
16.1 The method detection limit (MDL) is defined as the minimum
concentration of a substance that can be measured and reported with 99%
confidence that the value is above zero.1 The MDL
concentrations listed in Tables 4 and 5 were obtained using reagent
water.13 The MDL actually achieved in a given analysis will
vary depending on instrument sensitivity and matrix effects.
16.2 This method was tested by 15 laboratories using reagent water,
drinking water, surface water, and industrial wastewaters spiked at six
concentrations over the range 5 to 1300 [micro]g/L.14 Single
operator precision, overall precision, and method accuracy were found to
be directly related to the concentration of the parameter and
essentially independent of the sample matrix. Linear equations to
describe these relationships are presented in Table 7.
17. Screening Procedure for 2,3,7,8-Tetrachlorodibenzo-p-dioxin
(2,3,7,8-TCDD)
17.1 If the sample must be screened for the presence of 2,3,7,8-
TCDD, it is recommended that the reference material not be handled in
the laboratory unless extensive safety precautions are employed. It is
sufficient to analyze the base/neutral extract by selected ion
monitoring (SIM) GC/MS techniques, as follows:
17.1.1 Concentrate the base/neutral extract to a final volume of 0.2
ml.
[[Page 218]]
17.1.2 Adjust the temperature of the base/neutral column (Section
5.6.2) to 220 [deg]C.
17.1.3 Operate the mass spectrometer to acquire data in the SIM mode
using the ions at m/z 257, 320 and 322 and a dwell time no greater than
333 milliseconds per mass.
17.1.4 Inject 5 to 7 [micro]L of the base/neutral extract. Collect
SIM data for a total of 10 min.
17.1.5 The possible presence of 2,3,7,8-TCDD is indicated if all
three masses exhibit simultaneous peaks at any point in the selected ion
current profiles.
17.1.6 For each occurrence where the possible presence of 2,3,7,8-
TCDD is indicated, calculate and retain the relative abundances of each
of the three masses.
17.2 False positives to this test may be caused by the presence of
single or coeluting combinations of compounds whose mass spectra contain
all of these masses.
17.3 Conclusive results of the presence and concentration level of
2,3,7,8-TCDD can be obtained only from a properly equipped laboratory
through the use of EPA Method 613 or other approved alternate test
procedures.
References
1. 40 CFR part 136, appendix B.
2. ``Sampling and Analysis Procedures for Screening of Industrial
Effluents for Priority Pollutants,'' U.S. Environmental Protection
Agency, Environmental Monitoring and Support Laboratory, Cincinnati,
Ohio 45268, March 1977, Revised April 1977. Available from Effluent
Guidelines Division, Washington, DC 20460.
3. ASTM Annual Book of Standards, Part 31, D3694-78. ``Standard
Practices for Preparation of Sample Containers and for Preservation of
Organic Constituents,'' American Society for Testing and Materials,
Philadelphia.
4. ``Carcinogens--Working With Carcinogens,'' Department of Health,
Education, and Welfare, Public Health Service, Center for Disease
Control, National Institute for Occupational Safety and Health,
Publication No. 77-206, August 1977.
5. ``OSHA Safety and Health Standards, General Industry,'' (29 CFR
part 1910), Occupational Safety and Health Administration, OSHA 2206
(Revised, January 1976).
6. ``Safety in Academic Chemistry Laboratories,''American Chemical
Society Publication, Committee on Chemical Safety, 3rd Edition, 1979.
7. Provost, L.P., and Elder, R.S. ``Interpretation of Percent
Recovery Data,'' American Laboratory, 15, 58-63 (1983). (The value 2.44
used in the equation in Section 8.3.3 is two times the value 1.22
derived in this report.)
8. ASTM Annual Book of Standards, Part 31, D3370-76. ``Standard
Practices for Sampling Water,'' American Society for Testing and
Materials, Philadelphia.
9. ``Methods 330.4 (Titrimetric, DPD-FAS) and 330.5
(Spectrophotometric, DPD) for Chlorine, Total Residual,'' Methods for
Chemical Analysis of Water and Wastes, EPA-600/4-79-020, U.S.
Environmental Protection Agency, Environmental Monitoring and Support
Laboratory, Cincinnati, Ohio 45268, March 1979.
10. Eichelberger, J.W., Harris, L.E., and Budde, W.L. ``Reference
Compound to Calibrate Ion Abundance Measurement in Gas Chromatography-
Mass Spectometry,'' Analytical Chemistry, 47, 995 (1975).
11. McNair, N.M. and Bonelli, E.J. ``Basic Chromatography,''
Consolidated Printing, Berkeley, California, p. 52, 1969.
12. Burke, J.A. ``Gas Chromatography for Pesticide Residue Analysis;
Some Practical Aspects,'' Journal of the Association of Official
Analytical Chemists, 48, 1037 (1965).
13. Olynyk, P., Budde, W.L., and Eichelberger, J.W. ``Method
Detection Limit for Methods 624 and 625,'' Unpublished report, May 14,
1980.
14. ``EPA Method Study 30, Method 625, Base/Neutrals, Acids, and
Pesticides,'' EPA 600/4-84-053, National Technical Information Service,
PB84-206572, Springfield, Virginia 22161, June 1984.
Table 1--Base/Neutral Extractables
------------------------------------------------------------------------
STORET
Parameter No. CAS No.
------------------------------------------------------------------------
Acenaphthene..................................... 34205 83-32-9
Acenaphthylene................................... 34200 208-96-8
Anthracene....................................... 34220 120-12-7
Aldrin........................................... 39330 309-00-2
Benzo(a)anthracene............................... 34526 56-55-3
Benzo(b)fluoranthene............................. 34230 205-99-2
Benzo(k)fluoranthene............................. 34242 207-08-9
Benzo(a)pyrene................................... 34247 50-32-8
Benzo(ghi)perylene............................... 34521 191-24-2
Benzyl butyl phthalate........................... 34292 85-68-7
[beta]-BHC....................................... 39338 319-85-7
[delta]-BHC...................................... 34259 319-86-8
Bis(2-chloroethyl) ether......................... 34273 111-44-4
Bis(2-chloroethoxy)methane....................... 34278 111-91-1
Bis(2-ethylhexyl) phthalate...................... 39100 117-81-7
Bis(2-chloroisopropyl) ether a................... 34283 108-60-1
4-Bromophenyl phenyl ether a..................... 34636 101-55-3
Chlordane........................................ 39350 57-74-9
2-Chloronaphthalele.............................. 34581 91-58-7
4-Chlorophenyl phenyl ether...................... 34641 7005-72-3
Chrysene......................................... 34320 218-01-9
4,4'-DDD......................................... 39310 72-54-8
4,4'-DDE......................................... 39320 72-55-9
4,4'-DDT......................................... 39300 50-29-3
Dibenzo(a,h)anthracene........................... 34556 53-70-3
Di-n-butylphthalate.............................. 39110 84-74-2
1,3-Dichlorobenzene.............................. 34566 541-73-1
1,2-Dichlorobenzene.............................. 34536 95-50-1
1,4-Dichlorobenzene.............................. 34571 106-46-7
3,3'-Dichlorobenzidine........................... 34631 91-94-1
Dieldrin......................................... 39380 60-57-1
Diethyl phthalate................................ 34336 84-66-2
Dimethyl phthalate............................... 34341 131-11-3
2,4-Dinitrotoluene............................... 34611 121-14-2
2,6-Dinitrotoluene............................... 34626 606-20-2
Di-n-octylphthalate.............................. 34596 117-84-0
Endosulfan sulfate............................... 34351 1031-07-8
[[Page 219]]
Endrin aldehyde.................................. 34366 7421-93-4
Fluoranthene..................................... 34376 206-44-0
Fluorene......................................... 34381 86-73-7
Heptachlor....................................... 39410 76-44-8
Heptchlor epoxide................................ 39420 1024-57-3
Hexachlorobenzene................................ 39700 118-74-1
Hexachlorobutadiene.............................. 34391 87-68-3
Hexachloroethane................................. 34396 67-72-1
Indeno(1,2,3-cd)pyrene........................... 34403 193-39-5
Isophorone....................................... 34408 78-59-1
Naphthalene...................................... 34696 91-20-3
Nitrobenzene..................................... 34447 98-95-3
N-Nitrosodi-n-propylamine........................ 34428 621-64-7
PCB-1016......................................... 34671 12674-11-2
PCB-1221......................................... 39488 11104-28-2
PCB-1232......................................... 39492 11141-16-5
PCB-1242......................................... 39496 53469-21-9
PCB-1248......................................... 39500 12672-29-6
PCB-1254......................................... 39504 11097-69-1
PCB-1260......................................... 39508 11096-82-5
Phenanthrene..................................... 34461 85-01-8
Pyrene........................................... 34469 129-00-0
Toxaphene........................................ 39400 8001-35-2
1,2,4-Trichlorobenzene........................... 34551 120-82-1
------------------------------------------------------------------------
a The proper chemical name is 2,2'-oxybis(1-chloropropane).
Table 2--Acid Extractables
------------------------------------------------------------------------
STORET
Parameter No. CAS No.
------------------------------------------------------------------------
4-Chloro-3-methylphenol.......................... 34452 59-50-7
2-Chlorophenol................................... 34586 95-57-8
2,4-Dichlorophenol............................... 34601 120-83-2
2,4-Dimethylphenol............................... 34606 105-67-9
2,4-Dinitrophenol................................ 34616 51-28-5
2-Methyl-4,6-dinitrophenol....................... 34657 534-52-1
2-Nitrophenol.................................... 34591 88-75-5
4-Nitrophenol.................................... 34646 100-02-7
Pentachlorophenol................................ 39032 87-86-5
Phenol........................................... 34694 108-95-2
2,4,6-Trichlorophenol............................ 34621 88-06-2
------------------------------------------------------------------------
Table 3--Additional Extractable Parameters a
------------------------------------------------------------------------
STORET
Parameter No. CAS No. Method
------------------------------------------------------------------------
Benzidine................................ 39120 92-87-5 605
[beta]-BHC............................... 39337 319-84-6 608
[delta]-BHC.............................. 39340 58-89-8 608
Endosulfan I............................. 34361 959-98-8 608
Endosulfan II............................ 34356 33213-65-9 608
Endrin................................... 39390 72-20-8 608
Hexachlorocylopentadiene................. 34386 77-47-4 612
N-Nitrosodimethylamine................... 34438 62-75-9 607
N-Nitrosodiphenylamine................... 34433 86-30-6 607
------------------------------------------------------------------------
a See Section 1.2.
Table 4--Chromatographic Conditions, Method Detection Limits, and Characteristic Masses for Base/Neutral Extractables
--------------------------------------------------------------------------------------------------------------------------------------------------------
Method Characteristic masses
Retention detection -------------------------------------------------------------
Parameter time limit Electron impact Chemical ionization
(min) ([micro]g/ -------------------------------------------------------------
L) Primary Secondary Secondary Methane Methane Methane
--------------------------------------------------------------------------------------------------------------------------------------------------------
1,3-Dichlorobenzene................................................ 7.4 1.9 146 148 113 146 148 150
1,4-Dichlorobenzene................................................ 7.8 4.4 146 148 113 146 148 150
Hexachloroethane................................................... 8.4 1.6 117 201 199 199 201 203
Bis(2-chloroethyl) ether a......................................... 8.4 5.7 93 63 95 63 107 109
1,2-Dichlorobenzene................................................ 8.4 1.9 146 148 113 146 148 150
Bis(2-chloroisopropyl) ether a..................................... 9.3 5.7 45 77 79 77 135 137
N-Nitrosodi-n-propylamine.......................................... ......... .......... 130 42 101 ........ ........ ........
Nitrobenzene....................................................... 11.1 1.9 77 123 65 124 152 164
Hexachlorobutadiene................................................ 11.4 0.9 225 223 227 223 225 227
1,2,4-Trichlorobenzene............................................. 11.6 1.9 180 182 145 181 183 209
Isophorone......................................................... 11.9 2.2 82 95 138 139 167 178
Naphthalene........................................................ 12.1 1.6 128 129 127 129 157 169
Bis(2-chloroethoxy) methane........................................ 12.2 5.3 93 95 123 65 107 137
Hexachlorocyclopentadiene a........................................ 13.9 .......... 237 235 272 235 237 239
2-Chloronaphthalene................................................ 15.9 1.9 162 164 127 163 191 203
Acenaphthylene..................................................... 17.4 3.5 152 151 153 152 153 181
Acenaphthene....................................................... 17.8 1.9 154 153 152 154 155 183
Dimethyl phthalate................................................. 18.3 1.6 163 194 164 151 163 164
2,6-Dinitrotoluene................................................. 18.7 1.9 165 89 121 183 211 223
Fluorene........................................................... 19.5 1.9 166 165 167 166 167 195
4-Chlorophenyl phenyl ether........................................ 19.5 4.2 204 206 141 ........ ........ ........
2,4-Dinitrotoluene................................................. 19.8 5.7 165 63 182 183 211 223
Diethyl phthalate.................................................. 20.1 1.9 149 177 150 177 223 251
N-Nitrosodiphenylamine b........................................... 20.5 1.9 169 168 167 169 170 198
Hexachlorobenzene.................................................. 21.0 1.9 284 142 249 284 286 288
[beta]-BHC b....................................................... 21.1 .......... 183 181 109 ........ ........ ........
4-Bromophenyl phenyl ether......................................... 21.2 1.9 248 250 141 249 251 277
[delta]-BHC b...................................................... 22.4 .......... 183 181 109 ........ ........ ........
Phenanthrene....................................................... 22.8 5.4 178 179 176 178 179 207
Anthracene......................................................... 22.8 1.9 178 179 176 178 179 207
[beta]-BHC......................................................... 23.4 4.2 181 183 109 ........ ........ ........
[[Page 220]]
Heptachlor......................................................... 23.4 1.9 100 272 274 ........ ........ ........
[delta]-BHC........................................................ 23.7 3.1 183 109 181 ........ ........ ........
Aldrin............................................................. 24.0 1.9 66 263 220 ........ ........ ........
Dibutyl phthalate.................................................. 24.7 2.5 149 150 104 149 205 279
Heptachlor epoxide................................................. 25.6 2.2 353 355 351 ........ ........ ........
Endosulfan I b..................................................... 26.4 .......... 237 339 341 ........ ........ ........
Fluoranthene....................................................... 26.5 2.2 202 101 100 203 231 243
Dieldrin........................................................... 27.2 2.5 79 263 279 ........ ........ ........
4,4'-DDE........................................................... 27.2 5.6 246 248 176 ........ ........ ........
Pyrene............................................................. 27.3 1.9 202 101 100 203 231 243
Endrin b........................................................... 27.9 .......... 81 263 82 ........ ........ ........
Endosulfan II b.................................................... 28.6 .......... 237 339 341 ........ ........ ........
4,4'-DDD........................................................... 28.6 2.8 235 237 165 ........ ........ ........
Benzidine b........................................................ 28.8 44 184 92 185 185 213 225
4,4'-DDT........................................................... 29.3 4.7 235 237 165 ........ ........ ........
Endosulfan sulfate................................................. 29.8 5.6 272 387 422 ........ ........ ........
Endrin aldehyde.................................................... ......... .......... 67 345 250 ........ ........ ........
Butyl benzyl phthalate............................................. 29.9 2.5 149 91 206 149 299 327
Bis(2-ethylhexyl) phthalate........................................ 30.6 2.5 149 167 279 149 ........ ........
Chrysene........................................................... 31.5 2.5 228 226 229 228 229 257
Benzo(a)anthracene................................................. 31.5 7.8 228 229 226 228 229 257
3,3'-Dichlorobenzidine............................................. 32.2 16.5 252 254 126 ........ ........
Di-n-octyl phthalate............................................... 32.5 2.5 149
Benzo(b)fluoranthene............................................... 34.9 4.8 252 253 125 252 253 281
Benzo(k)fluoranthene............................................... 34.9 2.5 252 253 125 252 253 281
Benzo(a)pyrene..................................................... 36.4 2.5 252 253 125 252 253 281
Indeno(1,2,3-cd) pyrene............................................ 42.7 3.7 276 138 277 276 277 305
Dibenzo(a,h)anthracene............................................. 43.2 2.5 278 139 279 278 279 307
Benzo(ghi)perylene................................................. 45.1 4.1 276 138 277 276 277 305
N-Nitrosodimethylamine b........................................... ......... .......... 42 74 44 ........ ........ ........
Chlordane c........................................................ 19-30 .......... 373 375 377 ........ ........ ........
Toxaphene c........................................................ 25-34 .......... 159 231 233 ........ ........ ........
PCB 1016 c......................................................... 18-30 .......... 224 260 294 ........ ........ ........
PCB 1221 c......................................................... 15-30 30 190 224 260 ........ ........ ........
PCB 1232 c......................................................... 15-32 .......... 190 224 260 ........ ........ ........
PCB 1242 c......................................................... 15-32 .......... 224 260 294 ........ ........ ........
PCB 1248 c......................................................... 12-34 .......... 294 330 262 ........ ........ ........
PCB 1254 c......................................................... 22-34 36 294 330 362 ........ ........ ........
PCB 1260 c......................................................... 23-32 .......... 330 362 394 ........ ........ ........
--------------------------------------------------------------------------------------------------------------------------------------------------------
a The proper chemical name is 2,2'-bisoxy(1-chloropropane).
b See Section 1.2.
c These compounds are mixtures of various isomers (See Figures 2 through 12). Column conditions: Supelcoport (100/120 mesh) coated with 3% SP-2250
packed in a 1.8 m long x 2 mm ID glass column with helium carrier gas at 30 mL/min. flow rate. Column temperature held isothermal at 50 [deg]C for 4
min., then programmed at 8 [deg]C/min. to 270 [deg]C and held for 30 min.
Table 5--Chromatographic Conditions, Method Detection Limits, and Characteristic Masses for Acid Extractables
--------------------------------------------------------------------------------------------------------------------------------------------------------
Method Characteristic masses
Retention detection -------------------------------------------------------------
Parameter time limit Electron Impact Chemical ionization
(min) ([micro]g/ -------------------------------------------------------------
L) Primary Secondary Secondary Methane Methane Methane
--------------------------------------------------------------------------------------------------------------------------------------------------------
2-Chlorophenol..................................................... 5.9 3.3 128 64 130 129 131 157
2-Nitrophenol...................................................... 6.5 3.6 139 65 109 140 168 122
Phenol............................................................. 8.0 1.5 94 65 66 95 123 135
2,4-Dimethylphenol................................................. 9.4 2.7 122 107 121 123 151 163
2,4-Dichlorophenol................................................. 9.8 2.7 162 164 98 163 165 167
2,4,6-Trichlorophenol.............................................. 11.8 2.7 196 198 200 197 199 201
4-Chloro-3-methylphenol............................................ 13.2 3.0 142 107 144 143 171 183
2,4-Dinitrophenol.................................................. 15.9 42 184 63 154 185 213 225
2-Methyl-4,6-dinitrophenol......................................... 16.2 24 198 182 77 199 227 239
Pentachlorophenol.................................................. 17.5 3.6 266 264 268 267 265 269
[[Page 221]]
4-Nitrophenol...................................................... 20.3 2.4 65 139 109 140 168 122
--------------------------------------------------------------------------------------------------------------------------------------------------------
Column conditions: Supelcoport (100/120 mesh) coated with 1% SP-1240DA packed in a 1.8 m long x 2mm ID glass column with helium carrier gas at 30 mL/
min. flow rate. Column temperature held isothermal at 70 [deg]C for 2 min. then programmed at 8 [deg]C/min. to 200 [deg]C.
Table 6--QC Acceptance Criteria--Method 625
----------------------------------------------------------------------------------------------------------------
Test
conclusion Limits for Range for Range for
Parameter ([micro]g/ s ([micro]g/ X([micro]g/ P, Ps
L) L) L) (Percent)
----------------------------------------------------------------------------------------------------------------
Acenaphthene................................................ 100 27.6 60.1-132.3 47-145
Acenaphthylene.............................................. 100 40.2 53.5-126.0 33-145
Aldrin...................................................... 100 39.0 7.2-152.2 D-166
Anthracene.................................................. 100 32.0 43.4-118.0 27-133
Benzo(a)anthracene.......................................... 100 27.6 41.8-133.0 33-143
Benzo(b)fluoranthene........................................ 100 38.8 42.0-140.4 24-159
Benzo(k)fluoranthene........................................ 100 32.3 25.2-145.7 11-162
Benzo(a)pyrene.............................................. 100 39.0 31.7-148.0 17-163
Benzo(ghi)perylene.......................................... 100 58.9 D-195.0 D-219
Benzyl butyl phthalate...................................... 100 23.4 D-139.9 D-152
[beta]-BHC.................................................. 100 31.5 41.5-130.6 24-149
[delta]-BHC................................................. 100 21.6 D-100.0 D-110
Bis(2-chloroethyl) ether.................................... 100 55.0 42.9-126.0 12-158
Bis(2-chloroethoxy)methane.................................. 100 34.5 49.2-164.7 33-184
Bis(2-chloroisopropyl) ether a.............................. 100 46.3 62.8-138.6 36-166
Bis(2-ethylhexyl) phthalate................................. 100 41.1 28.9-136.8 8-158
4-Bromophenyl phenyl ether.................................. 100 23.0 64.9-114.4 53-127
2-Chloronaphthalene......................................... 100 13.0 64.5-113.5 60-118
4-Chlorophenyl phenyl ether................................. 100 33.4 38.4-144.7 25-158
Chrysene.................................................... 100 48.3 44.1-139.9 17-168
4,4'-DDD.................................................... 100 31.0 D-134.5 D-145
4,4'-DDE.................................................... 100 32.0 19.2-119.7 4-136
4,4'-DDT.................................................... 100 61.6 D-170.6 D-203
Dibenzo(a,h)anthracene...................................... 100 70.0 D-199.7 D-227
Di-n-butyl phthalate........................................ 100 16.7 8.4-111.0 1-118
1,2-Dichlorobenzene......................................... 100 30.9 48.6-112.0 32-129
1,3-Dichlorobenzene......................................... 100 41.7 16.7-153.9 D-172
1,4,-Dichlorobenzene........................................ 100 32.1 37.3-105.7 20-124
3,3'-Dhlorobenzidine........................................ 100 71.4 8.2-212.5 D-262
Dieldrin.................................................... 100 30.7 44.3-119.3 29-136
Diethyl phthalate........................................... 100 26.5 D-100.0 D-114
Dimethyl phthalate.......................................... 100 23.2 D-100.0 D-112
2,4-Dinitrotoluene.......................................... 100 21.8 47.5-126.9 39-139
2,6-Dinitrotoluene.......................................... 100 29.6 68.1-136.7 50-158
Di-n-octyl phthalate........................................ 100 31.4 18.6-131.8 4-146
Endosulfan sulfate.......................................... 100 16.7 D-103.5 D-107
Endrin aldehyde............................................. 100 32.5 D-188.8 D-209
Fluoranthene................................................ 100 32.8 42.9-121.3 26-137
Fluorene.................................................... 100 20.7 71.6-108.4 59-121
Heptachlor.................................................. 100 37.2 D-172.2 D-192
Heptachlor epoxide.......................................... 100 54.7 70.9-109.4 26-155
Hexachlorobenzene........................................... 100 24.9 7.8-141.5 D-152
Hexachlorobutadiene......................................... 100 26.3 37.8-102.2 24-116
Hexachloroethane............................................ 100 24.5 55.2-100.0 40-113
Indeno(1,2,3-cd)pyrene...................................... 100 44.6 D-150.9 D-171
Isophorone.................................................. 100 63.3 46.6-180.2 21-196
Naphthalene................................................. 100 30.1 35.6-119.6 21-133
Nitrobenzene................................................ 100 39.3 54.3-157.6 35-180
N-Nitrosodi-n-propylamine................................... 100 55.4 13.6-197.9 D-230
PCB-1260.................................................... 100 54.2 19.3-121.0 D-164
Phenanthrene................................................ 100 20.6 65.2-108.7 54-120
Pyrene...................................................... 100 25.2 69.6-100.0 52-115
1,2,4-Trichlorobenzene...................................... 100 28.1 57.3-129.2 44-142
4-Chloro-3-methylphenol..................................... 100 37.2 40.8-127.9 22-147
2-Chlorophenol.............................................. 100 28.7 36.2-120.4 23-134
[[Page 222]]
2,4-Dichlorophenol.......................................... 100 26.4 52.5-121.7 39-135
2,4-Dimethylphenol.......................................... 100 26.1 41.8-109.0 32-119
2,4-Dinitrophenol........................................... 100 49.8 D-172.9 D-191
2-Methyl-4,6-dinitrophenol.................................. 100 93.2 53.0-100.0 D-181
2-Nitrophenol............................................... 100 35.2 45.0-166.7 29-182
4-Nitrophenol............................................... 100 47.2 13.0-106.5 D-132
Pentachlorophenol........................................... 100 48.9 38.1-151.8 14-176
Phenol...................................................... 100 22.6 16.6-100.0 5-112
2,4,6-Trichlorophenol....................................... 100 31.7 52.4-129.2 37-144
----------------------------------------------------------------------------------------------------------------
s=Standard deviation for four recovery measurements, in [micro]g/L (Section 8.2.4).
X=Average recovery for four recovery measurements, in [micro]g/L (Section 8.2.4).
P, Ps=Percent recovery measured (Section 8.3.2, Section 8.4.2).
D=Detected; result must be greater than zero.
Note: These criteria are based directly upon the method performance data in Table 7. Where necessary, the limits
for recovery have been broadened to assure applicability of the limts to concentrations below those used to
develop Table 7.
a The proper chemical name is 2,2'oxybis(1-chloropropane).
Table 7--Method Accuracy and Precision as Functions of Concentration--Method 625
----------------------------------------------------------------------------------------------------------------
Accuracy, as Single analyst Overall
Parameter recovery, X' precision, sr' precision, S'
([micro]g/L) ([micro]g/L) ([micro]g/L)
----------------------------------------------------------------------------------------------------------------
Acenaphthene.................................................... 0.96C=0.19 0.15X-0.12 0.21X-0.67
Acenaphthylene.................................................. 0.89C=0.74 0.24X-1.06 0.26X-0.54
Aldrin.......................................................... 0.78C=1.66 0.27X-1.28 0.43X=1.13
Anthracene...................................................... 0.80C=0.68 0.21X-0.32 0.27X-0.64
Benzo(a)anthracene.............................................. 0.88C-0.60 0.15X=0.93 0.26X-0.28
Benzo(b)fluoranthene............................................ 0.93C-1.80 0.22X=0.43 0.29X=0.96
Benzo(k)fluoranthene............................................ 0.87C-1.56 0.19X=1.03 0.35X=0.40
Benzo(a)pyrene.................................................. 0.90C-0.13 0.22X=0.48 0.32X=1.35
Benzo(ghi)perylene.............................................. 0.98C-0.86 0.29X=2.40 0.51X-0.44
Benzyl butyl phthalate.......................................... 0.66C-1.68 0.18X=0.94 0.53X=0.92
[beta]-BHC...................................................... 0.87C-0.94 0.20X-0.58 0.30X-1.94
[delta]-BHC..................................................... 0.29C-1.09 0.34X=0.86 0.93X-0.17
Bis(2-chloroethyl) ether........................................ 0.86C-1.54 0.35X-0.99 0.35X=0.10
Bis(2-chloroethoxy)methane...................................... 1.12C-5.04 0.16X=1.34 0.26X=2.01
Bis(2-chloroisopropyl) ether a.................................. 1.03C-2.31 0.24X=0.28 0.25X=1.04
Bis(2-ethylhexyl) phthalate..................................... 0.84C-1.18 0.26X=0.73 0.36X=0.67
4-Bromophenyl phenyl ether...................................... 0.91C-1.34 0.13X=0.66 0.16X=0.66
2-Chloronaphthalene............................................. 0.89C=0.01 0.07X=0.52 0.13X=0.34
4-Chlorophenyl phenyl ether..................................... 0.91C=0.53 0.20X-0.94 0.30X-0.46
Chrysene........................................................ 0.93C-1.00 0.28X=0.13 0.33X-0.09
4,4'-DDD........................................................ 0.56C-0.40 0.29X-0.32 0.66X-0.96
4,4'-DDE........................................................ 0.70C-0.54 0.26X-1.17 0.39X-1.04
4,4'-DDT........................................................ 0.79C-3.28 0.42X=0.19 0.65X-0.58
Dibenzo(a,h)anthracene.......................................... 0.88C=4.72 0.30X=8.51 0.59X=0.25
Di-n-butyl phthalate............................................ 0.59C=0.71 0.13X=1.16 0.39X=0.60
1,2-Dichlorobenzene............................................. 0.80C=0.28 0.20X=0.47 0.24X=0.39
1,3-Dichlorobenzene............................................. 0.86C-0.70 0.25X=0.68 0.41X=0.11
1,4-Dichlorobenzene............................................. 0.73C-1.47 0.24X=0.23 0.29X=0.36
3,3'-Dichlorobenzidine.......................................... 1.23C-12.65 0.28X=7.33 0.47X=3.45
Dieldrin........................................................ 0.82C-0.16 0.20X-0.16 0.26X-0.07
Diethyl phthalate............................................... 0.43C=1.00 0.28X=1.44 0.52X=0.22
Dimethyl phthalate.............................................. 0.20C=1.03 0.54X=0.19 1.05X-0.92
2,4-Dinitrotoluene.............................................. 0.92C-4.81 0.12X=1.06 0.21X=1.50
2,6-Dinitrotoluene.............................................. 1.06C-3.60 0.14X=1.26 0.19X=0.35
Di-n-octyl phthalate............................................ 0.76C-0.79 0.21X=1.19 0.37X=1.19
Endosulfan sulfate.............................................. 0.39C=0.41 0.12X=2.47 0.63X-1.03
Endrin aldehyde................................................. 0.76C-3.86 0.18X=3.91 0.73X-0.62
Fluoranthene.................................................... 0.81C=1.10 0.22X-0.73 0.28X-0.60
Fluorene........................................................ 0.90C-0.00 0.12X=0.26 0.13X=0.61
Heptachlor...................................................... 0.87C-2.97 0.24X-0.56 0.50X-0.23
Heptachlor epoxide.............................................. 0.92C-1.87 0.33X-0.46 0.28X=0.64
Hexachlorobenzene............................................... 0.74C=0.66 0.18X-0.10 0.43X-0.52
Hexachlorobutadiene............................................. 0.71C-1.01 0.19X=0.92 0.26X=0.49
Hexachloroethane................................................ 0.73C-0.83 0.17X=0.67 0.17X=0.80
Indeno(1,2,3-cd)pyrene.......................................... 0.78C-3.10 0.29X=1.46 0.50X=0.44
Isophorone...................................................... 1.12C=1.41 0.27X=0.77 0.33X=0.26
Naphthalene..................................................... 0.76C=1.58 0.21X-0.41 0.30X-0.68
[[Page 223]]
Nitrobenzene.................................................... 1.09C-3.05 0.19X=0.92 0.27X=0.21
N-Nitrosodi-n-propylamine....................................... 1.12C-6.22 0.27X=0.68 0.44X=0.47
PCB-1260........................................................ 0.81C-10.86 0.35X=3.61 0.43X=1.82
Phenanthrene.................................................... 0.87C-0.06 0.12X=0.57 0.15X=0.25
Pyrene.......................................................... 0.84C-0.16 0.16X=0.06 0.15X=0.31
1,2,4-Trichlorobenzene.......................................... 0.94C-0.79 0.15X=0.85 0.21X=0.39
4-Chloro-3-methylphenol......................................... 0.84C=0.35 0.23X=0.75 0.29X=1.31
2-Chlorophenol.................................................. 0.78C=0.29 0.18X=1.46 0.28X=0.97
2,4-Dichlorophenol.............................................. 0.87C=0.13 0.15X=1.25 0.21X=1.28
2,4-Dimethylphenol.............................................. 0.71C=4.41 0.16X=1.21 0.22X=1.31
2,4-Dinitrophenol............................................... 0.81C-18.04 0.38X=2.36 0.42X=26.29
2-Methyl-4,6-Dinitrophenol...................................... 1.04C-28.04 0.05X=42.29 0.26X=23.10
2-Nitrophenol................................................... 1.07C-1.15 0.16X=1.94 0.27X=2.60
4-Nitrophenol................................................... 0.61C-1.22 0.38X=2.57 0.44X=3.24
Pentachlorophenol............................................... 0.93C=1.99 0.24X=3.03 0.30X=4.33
Phenol.......................................................... 0.43C=1.26 0.26X=0.73 0.35X=0.58
2,4,6-Trichlorophenol........................................... 0.91C-0.18 0.16X=2.22 0.22X=1.81
----------------------------------------------------------------------------------------------------------------
X'=Expected recovery for one or more measurements of a sample containing a concentration of C, in [micro]g/L.
sr'=Expected single analyst standard deviation of measurements at an average concentration found of X, in
[micro]g/L.
S'= Expected interlaboratory standard deviation of measurements at an average concentration found of X, in
[micro]g/L.
C= True value for the concentration, in [micro]g/L.
X= Average recovery found for measurements of samples containing a concentration of C, in [micro]g/L.
a The proper chemical name is 2,2'oxybis(1-chloropropane).
Table 8--Suggested Internal and Surrogate Standards
------------------------------------------------------------------------
Base/neutral fraction Acid fraction
------------------------------------------------------------------------
Aniline-d5................................ 2-Fluorophenol.
Anthracene-d10............................ Pentafluorophenol.
Benzo(a)anthracene-d12.................... Phenol-d5
4,4'-Dibromobiphenyl...................... 2-Perfluoromethyl phenol.
4,4'-Dibromooctafluorobiphenyl............
Decafluorobiphenyl........................
2,2 \1\-Difluorobiphenyl.................. ............................
4-Fluoroaniline........................... ............................
1-Fluoronaphthalene....................... ............................
2-Fluoronaphthalene....................... ............................
Naphthalene-d8............................ ............................
Nitrobenzene-d5........................... ............................
2,3,4,5,6-Pentafluorobiphenyl............. ............................
Phenanthrene-d10.......................... ............................
Pyridine-d5............................... ............................
------------------------------------------------------------------------
Table 9--DFTPP Key Masses and Abundance Criteria
------------------------------------------------------------------------
Mass m/z Abundance criteria
------------------------------------------------------------------------
51 30-60 percent of mass 198.
68 Less than 2 percent of mass 69.
70 Less than 2 percent of mass 69.
127 40-60 percent of mass 198.
197 Less than 1 percent of mass 198.
198 Base peak, 100 percent relative abundance.
199 5-9 percent of mass 198.
275 10-30 percent of mass 198.
365 Greater than 1 percent of mass 198.
441 Present but less than mass 443.
442 Greater than 40 percent of mass 198.
443 17-23 percent of mass 442.
------------------------------------------------------------------------
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Attachment 1 to Method 625
Introduction
To support measurement of several semivolatile pollutants, EPA has
developed this attachment to EPA Method 625.\1\ The modifications listed
in this attachment are approved only for monitoring wastestreams from
the Centralized Waste Treatment Point Source Category (40 CFR Part 437)
and the Landfills Point Source Category (40 CFR Part 445). EPA Method
625 (the Method) involves sample extraction with methylene chloride
followed by analysis of the extract using either packed or capillary
column gas chromatography/mass spectrometry (GC/MS). This attachment
addresses the addition of the semivolatile pollutants listed in Tables 1
and 2, to all applicable standard, stock, and spiking solutions utilized
for the determination of semivolatile organic compounds by EPA Method
625.
---------------------------------------------------------------------------
\1\ EPA Method 625: Base/Neutrals and Acids, 40 CFR Part 136,
Appendix A.
---------------------------------------------------------------------------
1.0 EPA METHOD 625 MODIFICATION SUMMARY
The additional semivolatile organic compounds listed in Tables 1 and
2 are added to all applicable calibration, spiking, and other solutions
utilized in the determination of base/neutral and acid compounds by EPA
Method 625. The instrument is to be calibrated with these compounds,
using a capillary column, and all procedures and quality control tests
stated in the Method must be performed.
2.0 SECTION MODIFICATIONS
Note: All section and figure numbers in this Attachment reference
section and figure numbers in EPA Method 625 unless noted otherwise.
Sections not listed here remain unchanged.
Section 6.7 The stock standard solutions described in this section are
modified such that the analytes in Tables 1 and 2 of this
attachment are required in addition to those specified in the
Method.
Section 7.2 The calibration standards described in this section are
modified to include the analytes in Tables 1 and 2 of this
attachment.
Section 8.2 The precision and accuracy requirements are modified to
include the analytes listed in Tables 1 and 2 of this
attachment. Additional performance criteria are supplied in
Table 5 of this attachment.
Section 8.3 The matrix spike is modified to include the analytes listed
in Tables 1 and 2 of this attachment.
Section 8.4 The QC check standard is modified to include the analytes
listed in Tables 1 and 2 of this attachment. Additional
performance criteria are supplied in Table 5 of this
attachment.
Section 16.0 Additional method performance information is supplied with
this attachment.
Table 1--Base/Neutral Extractables
------------------------------------------------------------------------
Parameter CAS No.
------------------------------------------------------------------------
acetophenone 1............................................. 98-86-2
alpha-terpineol 3.......................................... 98-55-5
aniline 2.................................................. 62-53-3
carbazole 1................................................ 86-74-8
o-cresol 1................................................. 95-48-7
n-decane 1................................................. 124-18-5
2,3-dichloroaniline 1...................................... 608-27-5
n-octadecane 1............................................. 593-45-3
pyridine 2................................................. 110-86-1
------------------------------------------------------------------------
CAS = Chemical Abstracts Registry.
1 Analysis of this pollutant is approved only for the Centralized Waste
Treatment industry.
2 Analysis of this pollutant is approved only for the Centralized Waste
Treatment and Landfills industries.
3 Analysis of this pollutant is approved only for the Landfills
industry.
Table 2--Acid Extractables
------------------------------------------------------------------------
Parameter CAS No.
------------------------------------------------------------------------
p-cresol 1................................................. 106-44-5
------------------------------------------------------------------------
CAS = Chemical Abstracts Registry.
1 Analysis of this pollutant is approved only for the Centralized Waste
Treatment and Landfills industries.
Table 3--Chromatographic Conditions,\1\ Method Detection Limits (MDLs), and Characteristic m/z's for Base/
Neutral Extractables
----------------------------------------------------------------------------------------------------------------
Characteristic m/z's
Retention MDL --------------------------------------
Analyte time (min) ([micro]g/ Electron impact
\2\ L) --------------------------------------
Primary Secondary Secondary
----------------------------------------------------------------------------------------------------------------
pyridine \3\................................... 4.93 4.6 79 52 51
N-Nitro sodimethylamine........................ 4.95 ........... 42 74 44
aniline \3\.................................... 10.82 3.3 93 66 65
Bis(2-chloroethyl)ether........................ 10.94 ........... 93 63 95
n-decane \4\................................... 11.11 5.0 57 ........... ...........
1,3-Dichlorobenzene............................ 11.47 ........... 146 148 113
1,4-Dichlorobenzene............................ 11.62 ........... 146 148 113
1,2-Dichlorobenzene............................ 12.17 ........... 146 148 113
[[Page 237]]
o-creso \1\.................................... 12.48 4.7 108 107 79
Bis(2-chloro- isopropyl)ether.................. 12.51 ........... 45 77 79
acetophenone \4\............................... 12.88 3.4 105 77 51
N-Nitrosodi-n-propylamine...................... 12.97 ........... 130 42 101
Hexachloroethane............................... 13.08 ........... 117 201 199
Nitrobenzene................................... 13.40 ........... 77 123 65
Isophorone..................................... 14.11 ........... 82 95 138
Bis (2-chloro ethoxy)methane................... 14.82 ........... 93 95 123
1,2,4-Trichlorobenzene......................... 15.37 ........... 180 182 145
alpha-terpineol................................ 15.55 5.0 59 ........... ...........
Naphthalene.................................... 15.56 ........... 128 129 127
Hexachlorobutadiene............................ 16.12 ........... 225 223 227
Hexachlorocyclopentadiene...................... 18.47 ........... 237 235 272
2,3-dichloroaniline \4\........................ 18.82 2.5 161 163 90
2-Chloronaphthalene............................ 19.35 ........... 162 164 127
Dimethyl phthalate............................. 20.48 ........... 163 194 164
Acenaphthylene................................. 20.69 ........... 152 151 153
2,6-Dinitrotoluene............................. 20.73 ........... 165 89 121
Acenaphthene................................... 21.30 ........... 154 153 152
2,4-Dinitrotoluene............................. 22.00 ........... 165 63 182
Diethylphthalate............................... 22.74 ........... 149 177 150
4-Chlorophenyl phenyl ether.................... 22.90 ........... 204 206 141
Fluorene....................................... 22.92 ........... 166 165 167
N-Nitro sodiphenylamine........................ 23.35 ........... 169 168 167
4-Bromophenyl phenyl ether..................... 24.44 ........... 248 250 141
Hexachlorobenzene.............................. 24.93 ........... 284 142 249
n-octadecane \4\............................... 25.39 2.0 57 ........... ...........
Phenanthrene................................... 25.98 ........... 178 179 176
Anthracene..................................... 26.12 ........... 178 179 176
Carbazole \4\.................................. 26.66 4.0 167 ........... ...........
Dibutyl phthalate.............................. 27.84 ........... 149 150 104
Fluoranthene................................... 29.82 ........... 202 101 100
Benzidine...................................... 30.26 ........... 184 92 185
Pyrene......................................... 30.56 ........... 202 101 100
Butyl benzyl phthalate......................... 32.63 ........... 149 91 206
3,3'-Dichlorobenzidine......................... 34.28 ........... 252 254 126
Benzo(a)anthracene............................. 34.33 ........... 228 229 226
Bis(2-ethyl hexyl)phthalate.................... 34.36 ........... 149 167 279
Chrysene....................................... 34.44 ........... 228 226 229
Di-n-octyl-phthalate........................... 36.17 ........... 149 ........... ...........
Benzo(b)fluoranthene........................... 37.90 ........... 252 253 125
Benzo(k)fluoranthene........................... 37.97 ........... 252 253 125
Benzo(a)pyrene................................. 39.17 ........... 252 253 125
Dibenzo(a,h) anthracene........................ 44.91 ........... 278 139 279
Indeno(1,2,3-c,d)pyrene........................ 45.01 ........... 276 138 277
Benzo(ghi)perylene............................. 46.56 ........... 276 138 277
----------------------------------------------------------------------------------------------------------------
\1\ The data presented in this table were obtained under the following conditions:
Column--30 5 meters x 0.25 .02 mm i.d., 94% methyl, 5% phenyl, 1%
vinyl, bonded phase fused silica capillary column (DB-5).
Temperature program--Five minutes at 30 [deg]C; 30-280 [deg]C at 8 [deg]C per minute; isothermal at 280 [deg]C
until benzo(ghi)perylene elutes.
Gas velocity--305 cm/sec at 30 [deg]C.
\2\ Retention times are from Method 1625, Revision C, using a capillary column, and are intended to be
consistent for all analytes in Tables 4 and 5 of this attachment.
\3\ Analysis of this pollutant is approved only for the Centralized Waste Treatment and Landfills industries.
\4\ Analysis of this pollutant is approved only for the Centralized Waste Treatment industry.
Table 4--Chromatographic Conditions,\1\ Method Detection Limits (MDLs), and Characteristic m/z's for Acid
Extractables
----------------------------------------------------------------------------------------------------------------
Characteristic m/z's
Retention MDL --------------------------------------
Analyte time \2\ ([micro]g/ Electron impact
(min) L) --------------------------------------
Primary Secondary Secondary
----------------------------------------------------------------------------------------------------------------
Phenol......................................... 10.76 ........... 94 65 66
2-Chlorophenol................................. 11.08 ........... 128 64 130
[[Page 238]]
p-cresol \3\................................... 12.92 7.8 108 107 77
2-Nitrophenol.................................. 14.38 ........... 139 65 109
2,4-Dimethylphenol............................. 14.54 ........... 122 107 121
2,4-Dichlorophenol............................. 15.12 ........... 162 164 98
4-Chloro-3-methylphenol........................ 16.83 ........... 142 107 144
2,4,6-Trichlorophenol.......................... 18.80 ........... 196 198 200
2,4-Dinitrophenol.............................. 21.51 ........... 184 63 154
4-Nitrophenol.................................. 21.77 ........... 65 139 109
2-Methyl-4,6-dinitrophenol..................... 22.83 ........... 198 182 77
Pentachlorophenol.............................. 25.52 ........... 266 264 268
----------------------------------------------------------------------------------------------------------------
\1\ The data presented in this table were obtained under the following conditions:
Column--30 5 meters x 0.25 .02 mm i.d., 94% methyl, 5% phenyl, 1%
vinyl silicone bonded phase fused silica capillary column (DB-5).
Temperature program--Five minutes at 30 [deg]C; 30-280 [deg]C at 8 [deg]C per minute; isothermal at 280 [deg]C
until benzo(ghi)perylene elutes.
Gas velocity--30 5 cm/sec at 30 [deg]C
\2\ Retention times are from EPA Method 1625, Revision C, using a capillary column, and are intended to be
consistent for all analytes in Tables 3 and 4 of this attachment.
\3\ Analysis of this pollutant is approved only for the Centralized Waste Treatment and Landfills industries.
Table 5--QC Acceptance Criteria
----------------------------------------------------------------------------------------------------------------
Test Limits for
conclusion s Range for X Range for
Analyte ([micro]g/ ([micro]g/ ([micro]g/ P, Ps(%)
L) L) L)
---------------------------------------------------------------------------------------------------------------
acetophenone \1\.......................................... 100 51 23-254 61-144
alpha-terpineol........................................... 100 47 46-163 58-156
aniline \2\............................................... 100 71 15-278 46-134
carbazole \1\............................................. 100 17 79-111 73-131
o-cresol \1\.............................................. 100 23 30-146 55-126
p-cresol \2\.............................................. 100 22 11-617 76-107
n-decane \1\.............................................. 100 70 D-651 D-ns
2,3-dichloroaniline \1\................................... 100 13 40-160 68-134
n-octadecane \1\.......................................... 100 10 52-147 65-123
pyridine \2\.............................................. 100 ns 7-392 33-158
----------------------------------------------------------------------------------------------------------------
s = Standard deviation for four recovery measurements, in [micro]g/L (Section 8.2)
X = Average recovery for four recovery measurements in [micro]g/L (Section 8.2)
P,Ps = Percent recovery measured (Section 8.3, Section 8.4)
D = Detected; result must be greater than zero.
ns = no specification; limit is outside the range that can be measured reliably.
\1\ Analysis of this pollutant is approved only for the Centralized Waste Treatment industry.
\2\ Analysis of this pollutant is approved only for the Centralized Waste Treatment and Landfills industries.
Method 1613, Revision B
Tetra- Through Octa-Chlorinated Dioxins and Furans by Isotope Dilution
HRGC/HRMS
1.0 Scope and Application
1.1 This method is for determination of tetra- through octa-
chlorinated dibenzo-p-dioxins (CDDs) and dibenzofurans (CDFs) in water,
soil, sediment, sludge, tissue, and other sample matrices by high
resolution gas chromatography/high resolution mass spectrometry (HRGC/
HRMS). The method is for use in EPA's data gathering and monitoring
programs associated with the Clean Water Act, the Resource Conservation
and Recovery Act, the Comprehensive Environmental Response, Compensation
and Liability Act, and the Safe Drinking Water Act. The method is based
on a compilation of EPA, industry, commercial laboratory, and academic
methods (References 1-6).
1.2 The seventeen 2,3,7,8-substituted CDDs/CDFs listed in Table 1
may be determined by this method. Specifications are also provided for
separate determination of 2,3,7,8-tetrachloro-dibenzo-p-dioxin (2,3,7,8-
TCDD) and 2,3,7,8-tetrachloro-dibenzofuran (2,3,7,8-TCDF).
1.3 The detection limits and quantitation levels in this method are
usually dependent on the level of interferences rather than instrumental
limitations. The minimum levels (MLs) in Table 2 are the levels at which
the CDDs/CDFs can be determined with no interferences present. The
Method Detection
[[Page 239]]
Limit (MDL) for 2,3,7,8-TCDD has been determined as 4.4 pg/L (parts-per-
quadrillion) using this method.
1.4 The GC/MS portions of this method are for use only by analysts
experienced with HRGC/HRMS or under the close supervision of such
qualified persons. Each laboratory that uses this method must
demonstrate the ability to generate acceptable results using the
procedure in Section 9.2.
1.5 This method is ``performance-based''. The analyst is permitted
to modify the method to overcome interferences or lower the cost of
measurements, provided that all performance criteria in this method are
met. The requirements for establishing method equivalency are given in
Section 9.1.2.
1.6 Any modification of this method, beyond those expressly
permitted, shall be considered a major modification subject to
application and approval of alternate test procedures under 40 CFR 136.4
and 136.5.
2.0 Summary of Method
Flow charts that summarize procedures for sample preparation,
extraction, and analysis are given in Figure 1 for aqueous and solid
samples, Figure 2 for multi-phase samples, and Figure 3 for tissue
samples.
2.1 Extraction.
2.1.1 Aqueous samples (samples containing less than 1% solids)--
Stable isotopically labeled analogs of 15 of the 2,3,7,8-substituted
CDDs/CDFs are spiked into a 1 L sample, and the sample is extracted by
one of three procedures:
2.1.1.1 Samples containing no visible particles are extracted with
methylene chloride in a separatory funnel or by the solid-phase
extraction technique summarized in Section 2.1.1.3. The extract is
concentrated for cleanup.
2.1.1.2 Samples containing visible particles are vacuum filtered
through a glass-fiber filter. The filter is extracted in a Soxhlet/Dean-
Stark (SDS) extractor (Reference 7), and the filtrate is extracted with
methylene chloride in a separatory funnel. The methylene chloride
extract is concentrated and combined with the SDS extract prior to
cleanup.
2.1.1.3 The sample is vacuum filtered through a glass-fiber filter
on top of a solid-phase extraction (SPE) disk. The filter and disk are
extracted in an SDS extractor, and the extract is concentrated for
cleanup.
2.1.2 Solid, semi-solid, and multi-phase samples (but not tissue)--
The labeled compounds are spiked into a sample containing 10 g (dry
weight) of solids. Samples containing multiple phases are pressure
filtered and any aqueous liquid is discarded. Coarse solids are ground
or homogenized. Any non-aqueous liquid from multi-phase samples is
combined with the solids and extracted in an SDS extractor. The extract
is concentrated for cleanup.
2.1.3 Fish and other tissue--The sample is extracted by one of two
procedures:
2.1.3.1 Soxhlet or SDS extraction--A 20 g aliquot of sample is
homogenized, and a 10 g aliquot is spiked with the labeled compounds.
The sample is mixed with sodium sulfate, allowed to dry for 12-24 hours,
and extracted for 18-24 hours using methylene chloride:hexane (1:1) in a
Soxhlet extractor. The extract is evaporated to dryness, and the lipid
content is determined.
2.1.3.2 HCl digestion--A 20 g aliquot is homogenized, and a 10 g
aliquot is placed in a bottle and spiked with the labeled compounds.
After equilibration, 200 mL of hydrochloric acid and 200 mL of methylene
chloride:hexane (1:1) are added, and the bottle is agitated for 12-24
hours. The extract is evaporated to dryness, and the lipid content is
determined.
2.2 After extraction, 37Cl4-labeled 2,3,7,8-
TCDD is added to each extract to measure the efficiency of the cleanup
process. Sample cleanups may include back-extraction with acid and/or
base, and gel permeation, alumina, silica gel, Florisil and activated
carbon chromatography. High-performance liquid chromatography (HPLC) can
be used for further isolation of the 2,3,7,8-isomers or other specific
isomers or congeners. Prior to the cleanup procedures cited above,
tissue extracts are cleaned up using an anthropogenic isolation column,
a batch silica gel adsorption, or sulfuric acid and base back-
extraction, depending on the tissue extraction procedure used.
2.3 After cleanup, the extract is concentrated to near dryness.
Immediately prior to injection, internal standards are added to each
extract, and an aliquot of the extract is injected into the gas
chromatograph. The analytes are separated by the GC and detected by a
high-resolution (=10,000) mass spectrometer. Two exact m/z's
are monitored for each analyte.
2.4 An individual CDD/CDF is identified by comparing the GC
retention time and ion-abundance ratio of two exact m/z's with the
corresponding retention time of an authentic standard and the
theoretical or acquired ion-abundance ratio of the two exact m/z's. The
non-2,3,7,8 substituted isomers and congeners are identified when
retention times and ion-abundance ratios agree within predefined limits.
Isomer specificity for 2,3,7,8-TCDD and 2,3,7,8-TCDF is achieved using
GC columns that resolve these isomers from the other tetra-isomers.
2.5 Quantitative analysis is performed using selected ion current
profile (SICP) areas, in one of three ways:
2.5.1 For the 15 2,3,7,8-substituted CDDs/CDFs with labeled analogs
(see Table 1), the GC/MS system is calibrated, and the concentration of
each compound is determined using the isotope dilution technique.
[[Page 240]]
2.5.2 For 1,2,3,7,8,9-HxCDD, OCDF, and the labeled compounds, the
GC/MS system is calibrated and the concentration of each compound is
determined using the internal standard technique.
2.5.3 For non-2,3,7,8-substituted isomers and for all isomers at a
given level of chlorination (i.e., total TCDD), concentrations are
determined using response factors from calibration of the CDDs/CDFs at
the same level of chlorination.
2.6 The quality of the analysis is assured through reproducible
calibration and testing of the extraction, cleanup, and GC/MS systems.
3.0 Definitions
Definitions are given in the glossary at the end of this method.
4.0 Contamination and Interferences
4.1 Solvents, reagents, glassware, and other sample processing
hardware may yield artifacts and/or elevated baselines causing
misinterpretation of chromatograms (References 8-9). Specific selection
of reagents and purification of solvents by distillation in all-glass
systems may be required. Where possible, reagents are cleaned by
extraction or solvent rinse.
4.2 Proper cleaning of glassware is extremely important, because
glassware may not only contaminate the samples but may also remove the
analytes of interest by adsorption on the glass surface.
4.2.1 Glassware should be rinsed with solvent and washed with a
detergent solution as soon after use as is practical. Sonication of
glassware containing a detergent solution for approximately 30 seconds
may aid in cleaning. Glassware with removable parts, particularly
separatory funnels with fluoropolymer stopcocks, must be disassembled
prior to detergent washing.
4.2.2 After detergent washing, glassware should be rinsed
immediately, first with methanol, then with hot tap water. The tap water
rinse is followed by another methanol rinse, then acetone, and then
methylene chloride.
4.2.3 Do not bake reusable glassware in an oven as a routine part of
cleaning. Baking may be warranted after particularly dirty samples are
encountered but should be minimized, as repeated baking of glassware may
cause active sites on the glass surface that will irreversibly adsorb
CDDs/CDFs.
4.2.4 Immediately prior to use, the Soxhlet apparatus should be pre-
extracted with toluene for approximately three hours (see Sections
12.3.1 through 12.3.3). Separatory funnels should be shaken with
methylene chloride/toluene (80/20 mixture) for two minutes, drained, and
then shaken with pure methylene chloride for two minutes.
4.3 All materials used in the analysis shall be demonstrated to be
free from interferences by running reference matrix method blanks
initially and with each sample batch (samples started through the
extraction process on a given 12-hour shift, to a maximum of 20
samples).
4.3.1 The reference matrix must simulate, as closely as possible,
the sample matrix under test. Ideally, the reference matrix should not
contain the CDDs/CDFs in detectable amounts, but should contain
potential interferents in the concentrations expected to be found in the
samples to be analyzed. For example, a reference sample of human adipose
tissue containing pentachloronaphthalene can be used to exercise the
cleanup systems when samples containing pentachloronaphthalene are
expected.
4.3.2 When a reference matrix that simulates the sample matrix under
test is not available, reagent water (Section 7.6.1) can be used to
simulate water samples; playground sand (Section 7.6.2) or white quartz
sand (Section 7.3.2) can be used to simulate soils; filter paper
(Section 7.6.3) can be used to simulate papers and similar materials;
and corn oil (Section 7.6.4) can be used to simulate tissues.
4.4 Interferences coextracted from samples will vary considerably
from source to source, depending on the diversity of the site being
sampled. Interfering compounds may be present at concentrations several
orders of magnitude higher than the CDDs/CDFs. The most frequently
encountered interferences are chlorinated biphenyls, methoxy biphenyls,
hydroxydiphenyl ethers, benzylphenyl ethers, polynuclear aromatics, and
pesticides. Because very low levels of CDDs/CDFs are measured by this
method, the elimination of interferences is essential. The cleanup steps
given in Section 13 can be used to reduce or eliminate these
interferences and thereby permit reliable determination of the CDDs/CDFs
at the levels shown in Table 2.
4.5 Each piece of reusable glassware should be numbered to associate
that glassware with the processing of a particular sample. This will
assist the laboratory in tracking possible sources of contamination for
individual samples, identifying glassware associated with highly
contaminated samples that may require extra cleaning, and determining
when glassware should be discarded.
4.6 Cleanup of tissue--The natural lipid content of tissue can
interfere in the analysis of tissue samples for the CDDs/CDFs. The lipid
contents of different species and portions of tissue can vary widely.
Lipids are soluble to varying degrees in various organic solvents and
may be present in sufficient quantity to overwhelm the column
chromatographic cleanup procedures used for cleanup of sample extracts.
Lipids must
[[Page 241]]
be removed by the lipid removal procedures in Section 13.7, followed by
alumina (Section 13.4) or Florisil (Section 13.8), and carbon (Section
13.5) as minimum additional cleanup steps. If chlorodiphenyl ethers are
detected, as indicated by the presence of peaks at the exact m/z's
monitored for these interferents, alumina and/or Florisil cleanup must
be employed to eliminate these interferences.
5.0 Safety
5.1 The toxicity or carcinogenicity of each compound or reagent used
in this method has not been precisely determined; however, each chemical
compound should be treated as a potential health hazard. Exposure to
these compounds should be reduced to the lowest possible level.
5.1.1 The 2,3,7,8-TCDD isomer has been found to be acnegenic,
carcinogenic, and teratogenic in laboratory animal studies. It is
soluble in water to approximately 200 ppt and in organic solvents to
0.14%. On the basis of the available toxicological and physical
properties of 2,3,7,8-TCDD, all of the CDDs/CDFs should be handled only
by highly trained personnel thoroughly familiar with handling and
cautionary procedures and the associated risks.
5.1.2 It is recommended that the laboratory purchase dilute standard
solutions of the analytes in this method. However, if primary solutions
are prepared, they shall be prepared in a hood, and a NIOSH/MESA
approved toxic gas respirator shall be worn when high concentrations are
handled.
5.2 The laboratory is responsible for maintaining a current
awareness file of OSHA regulations regarding the safe handling of the
chemicals specified in this method. A reference file of material safety
data sheets (MSDSs) should also be made available to all personnel
involved in these analyses. It is also suggested that the laboratory
perform personal hygiene monitoring of each analyst who uses this method
and that the results of this monitoring be made available to the
analyst. Additional information on laboratory safety can be found in
References 10-13. The references and bibliography at the end of
Reference 13 are particularly comprehensive in dealing with the general
subject of laboratory safety.
5.3 The CDDs/CDFs and samples suspected to contain these compounds
are handled using essentially the same techniques employed in handling
radioactive or infectious materials. Well-ventilated, controlled access
laboratories are required. Assistance in evaluating the health hazards
of particular laboratory conditions may be obtained from certain
consulting laboratories and from State Departments of Health or Labor,
many of which have an industrial health service. The CDDs/CDFs are
extremely toxic to laboratory animals. Each laboratory must develop a
strict safety program for handling these compounds. The practices in
References 2 and 14 are highly recommended.
5.3.1 Facility--When finely divided samples (dusts, soils, dry
chemicals) are handled, all operations (including removal of samples
from sample containers, weighing, transferring, and mixing) should be
performed in a glove box demonstrated to be leak tight or in a fume hood
demonstrated to have adequate air flow. Gross losses to the laboratory
ventilation system must not be allowed. Handling of the dilute solutions
normally used in analytical and animal work presents no inhalation
hazards except in the case of an accident.
5.3.2 Protective equipment--Disposable plastic gloves, apron or lab
coat, safety glasses or mask, and a glove box or fume hood adequate for
radioactive work should be used. During analytical operations that may
give rise to aerosols or dusts, personnel should wear respirators
equipped with activated carbon filters. Eye protection equipment
(preferably full face shields) must be worn while working with exposed
samples or pure analytical standards. Latex gloves are commonly used to
reduce exposure of the hands. When handling samples suspected or known
to contain high concentrations of the CDDs/CDFs, an additional set of
gloves can also be worn beneath the latex gloves.
5.3.3 Training--Workers must be trained in the proper method of
removing contaminated gloves and clothing without contacting the
exterior surfaces.
5.3.4 Personal hygiene--Hands and forearms should be washed
thoroughly after each manipulation and before breaks (coffee, lunch, and
shift).
5.3.5 Confinement--Isolated work areas posted with signs, segregated
glassware and tools, and plastic absorbent paper on bench tops will aid
in confining contamination.
5.3.6 Effluent vapors--The effluents of sample splitters from the
gas chromatograph (GC) and from roughing pumps on the mass spectrometer
(MS) should pass through either a column of activated charcoal or be
bubbled through a trap containing oil or high-boiling alcohols to
condense CDD/CDF vapors.
5.3.7 Waste Handling--Good technique includes minimizing
contaminated waste. Plastic bag liners should be used in waste cans.
Janitors and other personnel must be trained in the safe handling of
waste.
5.3.8 Decontamination
5.3.8.1 Decontamination of personnel--Use any mild soap with plenty
of scrubbing action.
5.3.8.2 Glassware, tools, and surfaces--Chlorothene NU Solvent is
the least toxic solvent shown to be effective. Satisfactory cleaning may
be accomplished by rinsing with Chlorothene, then washing with any
detergent and water. If glassware is first rinsed
[[Page 242]]
with solvent, then the dish water may be disposed of in the sewer. Given
the cost of disposal, it is prudent to minimize solvent wastes.
5.3.9 Laundry--Clothing known to be contaminated should be collected
in plastic bags. Persons who convey the bags and launder the clothing
should be advised of the hazard and trained in proper handling. The
clothing may be put into a washer without contact if the launderer knows
of the potential problem. The washer should be run through a cycle
before being used again for other clothing.
5.3.10 Wipe tests--A useful method of determining cleanliness of
work surfaces and tools is to wipe the surface with a piece of filter
paper. Extraction and analysis by GC with an electron capture detector
(ECD) can achieve a limit of detection of 0.1 [micro]g per wipe;
analysis using this method can achieve an even lower detection limit.
Less than 0.1 [micro]g per wipe indicates acceptable cleanliness;
anything higher warrants further cleaning. More than 10 [micro]g on a
wipe constitutes an acute hazard and requires prompt cleaning before
further use of the equipment or work space, and indicates that
unacceptable work practices have been employed.
5.3.11 Table or wrist-action shaker--The use of a table or wrist-
action shaker for extraction of tissues presents the possibility of
breakage of the extraction bottle and spillage of acid and flammable
organic solvent. A secondary containment system around the shaker is
suggested to prevent the spread of acid and solvents in the event of
such a breakage. The speed and intensity of shaking action should also
be adjusted to minimize the possibility of breakage.
6.0 Apparatus and Materials
Note: Brand names, suppliers, and part numbers are for illustration
purposes only and no endorsement is implied. Equivalent performance may
be achieved using apparatus and materials other than those specified
here. Meeting the performance requirements of this method is the
responsibility of the laboratory.
6.1 Sampling Equipment for Discrete or Composite Sampling
6.1.1 Sample bottles and caps
6.1.1.1 Liquid samples (waters, sludges and similar materials
containing 5% solids or less)--Sample bottle, amber glass, 1.1 L
minimum, with screw cap.
6.1.1.2 Solid samples (soils, sediments, sludges, paper pulps,
filter cake, compost, and similar materials that contain more than 5%
solids)--Sample bottle, wide mouth, amber glass, 500 mL minimum.
6.1.1.3 If amber bottles are not available, samples shall be
protected from light.
6.1.1.4 Bottle caps--Threaded to fit sample bottles. Caps shall be
lined with fluoropolymer.
6.1.1.5 Cleaning
6.1.1.5.1 Bottles are detergent water washed, then solvent rinsed
before use.
6.1.1.5.2 Liners are detergent water washed, rinsed with reagent
water (Section 7.6.1) followed by solvent, and baked at approximately
200 [deg]C for a minimum of 1 hour prior to use.
6.1.2 Compositing equipment--Automatic or manual compositing system
incorporating glass containers cleaned per bottle cleaning procedure
above. Only glass or fluoropolymer tubing shall be used. If the sampler
uses a peristaltic pump, a minimum length of compressible silicone
rubber tubing may be used in the pump only. Before use, the tubing shall
be thoroughly rinsed with methanol, followed by repeated rinsing with
reagent water to minimize sample contamination. An integrating flow
meter is used to collect proportional composite samples.
6.2 Equipment for Glassware Cleaning--Laboratory sink with overhead
fume hood.
6.3 Equipment for Sample Preparation
6.3.1 Laboratory fume hood of sufficient size to contain the sample
preparation equipment listed below.
6.3.2 Glove box (optional).
6.3.3 Tissue homogenizer--VirTis Model 45 Macro homogenizer
(American Scientific Products H-3515, or equivalent) with stainless
steel Macro-shaft and Turbo-shear blade.
6.3.4 Meat grinder--Hobart, or equivalent, with 3-5 mm holes in
inner plate.
6.3.5 Equipment for determining percent moisture
6.3.5.1 Oven--Capable of maintaining a temperature of 110 5 [deg]C.
6.3.5.2 Dessicator.
6.3.6 Balances
6.3.6.1 Analytical--Capable of weighing 0.1 mg.
6.3.6.2 Top loading--Capable of weighing 10 mg.
6.4 Extraction Apparatus
6.4.1 Water samples
6.4.1.1 pH meter, with combination glass electrode.
6.4.1.2 pH paper, wide range (Hydrion Papers, or equivalent).
6.4.1.3 Graduated cylinder, 1 L capacity.
6.4.1.4 Liquid/liquid extraction--Separatory funnels, 250 mL, 500
mL, and 2000 mL, with fluoropolymer stopcocks.
6.4.1.5 Solid-phase extraction
6.4.1.5.1 One liter filtration apparatus, including glass funnel,
glass frit support, clamp, adapter, stopper, filtration flask, and
vacuum tubing (Figure 4). For wastewater samples, the apparatus should
accept 90 or 144 mm disks. For drinking water or other samples
containing low solids, smaller disks may be used.
[[Page 243]]
6.4.1.5.2 Vacuum source capable of maintaining 25 in. Hg, equipped
with shutoff valve and vacuum gauge.
6.4.1.5.3 Glass-fiber filter--Whatman GMF 150 (or equivalent), 1
micron pore size, to fit filtration apparatus in Section 6.4.1.5.1.
6.4.1.5.4 Solid-phase extraction disk containing octadecyl
(C18) bonded silica uniformly enmeshed in an inert matrix--
Fisher Scientific 14-378F (or equivalent), to fit filtration apparatus
in Section 6.4.1.5.1.
6.4.2 Soxhlet/Dean-Stark (SDS) extractor (Figure 5)--For filters and
solid/sludge samples.
6.4.2.1 Soxhlet--50 mm ID, 200 mL capacity with 500 mL flask (Cal-
Glass LG-6900, or equivalent, except substitute 500 mL round-bottom
flask for 300 mL flat-bottom flask).
6.4.2.2 Thimble--43 x 123 to fit Soxhlet (Cal-Glass LG-6901-122, or
equivalent).
6.4.2.3 Moisture trap--Dean Stark or Barret with fluoropolymer
stopcock, to fit Soxhlet.
6.4.2.4 Heating mantle--Hemispherical, to fit 500 mL round-bottom
flask (Cal-Glass LG-8801-112, or equivalent).
6.4.2.5 Variable transformer--Powerstat (or equivalent), 110 volt,
10 amp.
6.4.3 Apparatus for extraction of tissue.
6.4.3.1 Bottle for extraction (if digestion/extraction using HCl is
used)'' 500-600 mL wide-mouth clear glass, with fluoropolymer-lined cap.
6.4.3.2 Bottle for back-extraction--100-200 mL narrow-mouth clear
glass with fluoropolymer-lined cap.
6.4.3.3 Mechanical shaker--Wrist-action or platform-type rotary
shaker that produces vigorous agitation (Sybron Thermolyne Model LE
``Big Bill'' rotator/shaker, or equivalent).
6.4.3.4 Rack attached to shaker table to permit agitation of four to
nine samples simultaneously.
6.4.4 Beakers--400-500 mL.
6.4.5 Spatulas--Stainless steel.
6.5 Filtration Apparatus.
6.5.1 Pyrex glass wool--Solvent-extracted by SDS for three hours
minimum.
Note: Baking glass wool may cause active sites that will
irreversibly adsorb CDDs/CDFs.
6.5.2 Glass funnel--125-250 mL.
6.5.3 Glass-fiber filter paper--Whatman GF/D (or equivalent), to fit
glass funnel in Section 6.5.2.
6.5.4 Drying column--15-20 mm ID Pyrex chromatographic column
equipped with coarse-glass frit or glass-wool plug.
6.5.5 Buchner funnel--15 cm.
6.5.6 Glass-fiber filter paper--to fit Buchner funnel in Section
6.5.5.
6.5.7 Filtration flasks--1.5-2.0 L, with side arm.
6.5.8 Pressure filtration apparatus--Millipore YT30 142 HW, or
equivalent.
6.6 Centrifuge Apparatus.
6.6.1 Centrifuge--Capable of rotating 500 mL centrifuge bottles or
15 mL centrifuge tubes at 5,000 rpm minimum.
6.6.2 Centrifuge bottles--500 mL, with screw-caps, to fit
centrifuge.
6.6.3 Centrifuge tubes--12-15 mL, with screw-caps, to fit
centrifuge.
6.7 Cleanup Apparatus.
6.7.1 Automated gel permeation chromatograph (Analytical Biochemical
Labs, Inc, Columbia, MO, Model GPC Autoprep 1002, or equivalent).
6.7.1.1 Column--600-700 mm long x 25 mm ID, packed with 70 g of
SX-3 Bio-beads (Bio-Rad Laboratories, Richmond, CA, or equivalent).
6.7.1.2 Syringe--10 mL, with Luer fitting.
6.7.1.3 Syringe filter holder--stainless steel, and glass-fiber or
fluoropolymer filters (Gelman 4310, or equivalent).
6.7.1.4 UV detectors--254 nm, preparative or semi-preparative flow
cell (Isco, Inc., Type 6; Schmadzu, 5 mm path length; Beckman-Altex
152W, 8 [micro]L micro-prep flow cell, 2 mm path; Pharmacia UV-1, 3 mm
flow cell; LDC Milton-Roy UV-3, monitor 1203; or equivalent).
6.7.2 Reverse-phase high-performance liquid chromatograph.
6.7.2.1 Column oven and detector--Perkin-Elmer Model LC-65T (or
equivalent) operated at 0.02 AUFS at 235 nm.
6.7.2.2 Injector--Rheodyne 7120 (or equivalent) with 50 [micro]L
sample loop.
6.7.2.3 Column--Two 6.2 mm x 250 mm Zorbax-ODS columns in series
(DuPont Instruments Division, Wilmington, DE, or equivalent), operated
at 50 [deg]C with 2.0 mL/min methanol isocratic effluent.
6.7.2.4 Pump--Altex 110A (or equivalent).
6.7.3 Pipets.
6.7.3.1 Disposable, pasteur--150 mm long x 5-mm ID (Fisher
Scientific 13-678-6A, or equivalent).
6.7.3.2 Disposable, serological--10 mL (6 mm ID).
6.7.4 Glass chromatographic columns.
6.7.4.1 150 mm long x 8-mm ID, (Kontes K-420155, or equivalent) with
coarse-glass frit or glass-wool plug and 250 mL reservoir.
6.7.4.2 200 mm long x 15 mm ID, with coarse-glass frit or glass-wool
plug and 250 mL reservoir.
6.7.4.3 300 mm long x 25 mm ID, with 300 mL reservoir and glass or
fluoropolymer stopcock.
6.7.5 Stirring apparatus for batch silica cleanup of tissue
extracts.
6.7.5.1 Mechanical stirrer--Corning Model 320, or equivalent.
6.7.5.2 Bottle--500-600 mL wide-mouth clear glass.
6.7.6 Oven--For baking and storage of adsorbents, capable of
maintaining a constant temperature (5 [deg]C) in
the range of 105-250 [deg]C.
6.8 Concentration Apparatus.
[[Page 244]]
6.8.1 Rotary evaporator--Buchi/Brinkman-American Scientific No.
E5045-10 or equivalent, equipped with a variable temperature water bath.
6.8.1.1 Vacuum source for rotary evaporator equipped with shutoff
valve at the evaporator and vacuum gauge.
6.8.1.2 A recirculating water pump and chiller are recommended, as
use of tap water for cooling the evaporator wastes large volumes of
water and can lead to inconsistent performance as water temperatures and
pressures vary.
6.8.1.3 Round-bottom flask--100 mL and 500 mL or larger, with
ground-glass fitting compatible with the rotary evaporator.
6.8.2 Kuderna-Danish (K-D) Concentrator.
6.8.2.1 Concentrator tube--10 mL, graduated (Kontes K-570050-1025,
or equivalent) with calibration verified. Ground-glass stopper (size 19/
22 joint) is used to prevent evaporation of extracts.
6.8.2.2 Evaporation flask--500 mL (Kontes K-570001-0500, or
equivalent), attached to concentrator tube with springs (Kontes K-
662750-0012 or equivalent).
6.8.2.3 Snyder column--Three-ball macro (Kontes K-503000-0232, or
equivalent).
6.8.2.4 Boiling chips.
6.8.2.4.1 Glass or silicon carbide--Approximately 10/40 mesh,
extracted with methylene chloride and baked at 450 [deg]C for one hour
minimum.
6.8.2.4.2 Fluoropolymer (optional)--Extracted with methylene
chloride.
6.8.2.5 Water bath--Heated, with concentric ring cover, capable of
maintaining a temperature within 2 [deg]C,
installed in a fume hood.
6.8.3 Nitrogen blowdown apparatus--Equipped with water bath
controlled in the range of 30-60 [deg]C (N-Evap, Organomation
Associates, Inc., South Berlin, MA, or equivalent), installed in a fume
hood.
6.8.4 Sample vials.
6.8.4.1 Amber glass--2-5 mL with fluoropolymer-lined screw-cap.
6.8.4.2 Glass--0.3 mL, conical, with fluoropolymer-lined screw or
crimp cap.
6.9 Gas Chromatograph--Shall have splitless or on-column injection
port for capillary column, temperature program with isothermal hold, and
shall meet all of the performance specifications in Section 10.
6.9.1 GC column for CDDs/CDFs and for isomer specificity for
2,3,7,8-TCDD--605 m long x 0.320.02 mm ID; 0.25 [micro]m 5% phenyl, 94% methyl, 1%
vinyl silicone bonded-phase fused-silica capillary column (J&W DB-5, or
equivalent).
6.9.2 GC column for isomer specificity for 2,3,7,8-TCDF--305 m long x 0.320.02 mm ID; 0.25
[micro]m bonded-phase fused-silica capillary column (J&W DB-225, or
equivalent).
6.10 Mass Spectrometer--28-40 eV electron impact ionization, shall
be capable of repetitively selectively monitoring 12 exact m/z's minimum
at high resolution (=10,000) during a period of approximately
one second, and shall meet all of the performance specifications in
Section 10.
6.11 GC/MS Interface--The mass spectrometer (MS) shall be interfaced
to the GC such that the end of the capillary column terminates within 1
cm of the ion source but does not intercept the electron or ion beams.
6.12 Data System--Capable of collecting, recording, and storing MS
data.
7.0 Reagents and Standards
7.1 pH Adjustment and Back-Extraction.
7.1.1 Potassium hydroxide--Dissolve 20 g reagent grade KOH in 100 mL
reagent water.
7.1.2 Sulfuric acid--Reagent grade (specific gravity 1.84).
7.1.3 Hydrochloric acid--Reagent grade, 6N.
7.1.4 Sodium chloride--Reagent grade, prepare at 5% (w/v) solution
in reagent water.
7.2 Solution Drying and Evaporation.
7.2.1 Solution drying--Sodium sulfate, reagent grade, granular,
anhydrous (Baker 3375, or equivalent), rinsed with methylene chloride
(20 mL/g), baked at 400 [deg]C for one hour minimum, cooled in a
dessicator, and stored in a pre-cleaned glass bottle with screw-cap that
prevents moisture from entering. If, after heating, the sodium sulfate
develops a noticeable grayish cast (due to the presence of carbon in the
crystal matrix), that batch of reagent is not suitable for use and
should be discarded. Extraction with methylene chloride (as opposed to
simple rinsing) and baking at a lower temperature may produce sodium
sulfate that is suitable for use.
7.2.2 Tissue drying--Sodium sulfate, reagent grade, powdered,
treated and stored as above.
7.2.3 Prepurified nitrogen.
7.3 Extraction.
7.3.1 Solvents--Acetone, toluene, cyclohexane, hexane, methanol,
methylene chloride, and nonane; distilled in glass, pesticide quality,
lot-certified to be free of interferences.
7.3.2 White quartz sand, 60/70 mesh--For Soxhlet/Dean-Stark
extraction (Aldrich Chemical, Cat. No. 27-437-9, or equivalent). Bake at
450 [deg]C for four hours minimum.
7.4 GPC Calibration Solution--Prepare a solution containing 300 mg/
mL corn oil, 15 mg/mL bis(2-ethylhexyl) phthalate, 1.4 mg/mL
pentachlorophenol, 0.1 mg/mL perylene, and 0.5 mg/mL sulfur.
7.5 Adsorbents for Sample Cleanup.
7.5.1 Silica gel.
7.5.1.1 Activated silica gel--100-200 mesh, Supelco 1-3651 (or
equivalent), rinsed with methylene chloride, baked at 180 [deg]C for a
minimum of one hour, cooled in a dessicator, and stored in a precleaned
glass bottle with
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screw-cap that prevents moisture from entering.
7.5.1.2 Acid silica gel (30% w/w)--Thoroughly mix 44.0 g of
concentrated sulfuric acid with 100.0 g of activated silica gel in a
clean container. Break up aggregates with a stirring rod until a uniform
mixture is obtained. Store in a bottle with a fluoropolymer-lined screw-
cap.
7.5.1.3 Basic silica gel--Thoroughly mix 30 g of 1N sodium hydroxide
with 100 g of activated silica gel in a clean container. Break up
aggregates with a stirring rod until a uniform mixture is obtained.
Store in a bottle with a fluoropolymer-lined screw-cap.
7.5.1.4 Potassium silicate.
7.5.1.4.1 Dissolve 56 g of high purity potassium hydroxide (Aldrich,
or equivalent) in 300 mL of methanol in a 750-1000 mL flat-bottom flask.
7.5.1.4.2 Add 100 g of silica gel and a stirring bar, and stir on a
hot plate at 60-70 [deg]C for one to two hours.
7.5.1.4.3 Decant the liquid and rinse the potassium silicate twice
with 100 mL portions of methanol, followed by a single rinse with 100 mL
of methylene chloride.
7.5.1.4.4 Spread the potassium silicate on solvent-rinsed aluminum
foil and dry for two to four hours in a hood.
7.5.1.4.5 Activate overnight at 200-250 [deg]C.
7.5.2 Alumina--Either one of two types of alumina, acid or basic,
may be used in the cleanup of sample extracts, provided that the
laboratory can meet the performance specifications for the recovery of
labeled compounds described in Section 9.3. The same type of alumina
must be used for all samples, including those used to demonstrate
initial precision and recovery (Section 9.2) and ongoing precision and
recovery (Section 15.5).
7.5.2.1 Acid alumina--Supelco 19996-6C (or equivalent). Activate by
heating to 130 [deg]C for a minimum of 12 hours.
7.5.2.2 Basic alumina--Supelco 19944-6C (or equivalent). Activate by
heating to 600 [deg]C for a minimum of 24 hours. Alternatively, activate
by heating in a tube furnace at 650-700 [deg]C under an air flow rate of
approximately 400 cc/minute. Do not heat over 700 [deg]C, as this can
lead to reduced capacity for retaining the analytes. Store at 130 [deg]C
in a covered flask. Use within five days of baking.
7.5.3 Carbon.
7.5.3.1 Carbopak C--(Supelco 1-0258, or equivalent).
7.5.3.2 Celite 545--(Supelco 2-0199, or equivalent).
7.5.3.3 Thoroughly mix 9.0 g Carbopak C and 41.0 g Celite 545 to
produce an 18% w/w mixture. Activate the mixture at 130 [deg]C for a
minimum of six hours. Store in a dessicator.
7.5.4 Anthropogenic isolation column--Pack the column in Section
6.7.4.3 from bottom to top with the following:
7.5.4.1 2 g silica gel (Section 7.5.1.1).
7.5.4.2 2 g potassium silicate (Section 7.5.1.4).
7.5.4.3 2 g granular anhydrous sodium sulfate (Section 7.2.1).
7.5.4.4 10 g acid silica gel (Section 7.5.1.2).
7.5.4.5 2 g granular anhydrous sodium sulfate.
7.5.5 Florisil column.
7.5.5.1 Florisil--60-100 mesh, Floridin Corp (or equivalent).
Soxhlet extract in 500 g portions for 24 hours.
7.5.5.2 Insert a glass wool plug into the tapered end of a graduated
serological pipet (Section 6.7.3.2). Pack with 1.5 g (approx 2 mL) of
Florisil topped with approx 1 mL of sodium sulfate (Section 7.2.1) and a
glass wool plug.
7.5.5.3 Activate in an oven at 130-150 [deg]C for a minimum of 24
hours and cool for 30 minutes. Use within 90 minutes of cooling.
7.6 Reference Matrices--Matrices in which the CDDs/CDFs and
interfering compounds are not detected by this method.
7.6.1 Reagent water--Bottled water purchased locally, or prepared by
passage through activated carbon.
7.6.2 High-solids reference matrix--Playground sand or similar
material. Prepared by extraction with methylene chloride and/or baking
at 450 [deg]C for a minimum of four hours.
7.6.3 Paper reference matrix--Glass-fiber filter, Gelman Type A, or
equivalent. Cut paper to simulate the surface area of the paper sample
being tested.
7.6.4 Tissue reference matrix--Corn or other vegetable oil. May be
prepared by extraction with methylene chloride.
7.6.5 Other matrices--This method may be verified on any reference
matrix by performing the tests given in Section 9.2. Ideally, the matrix
should be free of the CDDs/CDFs, but in no case shall the background
level of the CDDs/CDFs in the reference matrix exceed three times the
minimum levels in Table 2. If low background levels of the CDDs/CDFs are
present in the reference matrix, the spike level of the analytes used in
Section 9.2 should be increased to provide a spike-to-background ratio
in the range of 1:1 to 5:1 (Reference 15).
7.7 Standard Solutions--Purchased as solutions or mixtures with
certification to their purity, concentration, and authenticity, or
prepared from materials of known purity and composition. If the chemical
purity is 98% or greater, the weight may be used without correction to
compute the concentration of the standard. When not being used,
standards are stored in the dark at room temperature in screw-capped
vials with fluoropolymer-lined caps. A mark is placed on the vial at the
level of the solution so that solvent loss by evaporation can be
detected. If solvent loss has occurred, the solution should be replaced.
7.8 Stock Solutions.
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7.8.1 Preparation--Prepare in nonane per the steps below or purchase
as dilute solutions (Cambridge Isotope Laboratories (CIL), Woburn, MA,
or equivalent). Observe the safety precautions in Section 5, and the
recommendation in Section 5.1.2.
7.8.2 Dissolve an appropriate amount of assayed reference material
in solvent. For example, weigh 1-2 mg of 2,3,7,8-TCDD to three
significant figures in a 10 mL ground-glass-stoppered volumetric flask
and fill to the mark with nonane. After the TCDD is completely
dissolved, transfer the solution to a clean 15 mL vial with
fluoropolymer-lined cap.
7.8.3 Stock standard solutions should be checked for signs of
degradation prior to the preparation of calibration or performance test
standards. Reference standards that can be used to determine the
accuracy of calibration standards are available from CIL and may be
available from other vendors.
7.9 PAR Stock Solution
7.9.1 All CDDs/CDFs--Using the solutions in Section 7.8, prepare the
PAR stock solution to contain the CDDs/CDFs at the concentrations shown
in Table 3. When diluted, the solution will become the PAR (Section
7.14).
7.9.2 If only 2,3,7,8-TCDD and 2,3,7,8-TCDF are to be determined,
prepare the PAR stock solution to contain these compounds only.
7.10 Labeled-Compound Spiking Solution.
7.10.1 All CDDs/CDFs--From stock solutions, or from purchased
mixtures, prepare this solution to contain the labeled compounds in
nonane at the concentrations shown in Table 3. This solution is diluted
with acetone prior to use (Section 7.10.3).
7.10.2 If only 2,3,7,8-TCDD and 2,3,7,8-TCDF are to be determined,
prepare the labeled-compound solution to contain these compounds only.
This solution is diluted with acetone prior to use (Section 7.10.3).
7.10.3 Dilute a sufficient volume of the labeled compound solution
(Section 7.10.1 or 7.10.2) by a factor of 50 with acetone to prepare a
diluted spiking solution. Each sample requires 1.0 mL of the diluted
solution, but no more solution should be prepared than can be used in
one day.
7.11 Cleanup Standard--Prepare 37Cl4-2,3,7,8-
TCDD in nonane at the concentration shown in Table 3. The cleanup
standard is added to all extracts prior to cleanup to measure the
efficiency of the cleanup process.
7.12 Internal Standard(s).
7.12.1 All CDDs/CDFs--Prepare the internal standard solution to
contain 13C12-1,2,3,4-TCDD and
13C2-1,2,3,7,8,9-HxCDD in nonane at the
concentration shown in Table 3.
7.12.2 If only 2,3,7,8-TCDD and 2,3,7,8-TCDF are to be determined,
prepare the internal standard solution to contain
13C12-1,2,3,4-TCDD only.
7.13 Calibration Standards (CS1 through CS5)--Combine the solutions
in Sections 7.9 through 7.12 to produce the five calibration solutions
shown in Table 4 in nonane. These solutions permit the relative response
(labeled to native) and response factor to be measured as a function of
concentration. The CS3 standard is used for calibration verification
(VER). If only 2,3,7,8-TCDD and 2,3,7,8-TCDF are to be determined,
combine the solutions appropriate to these compounds.
7.14 Precision and Recovery (PAR) Standard--Used for determination
of initial (Section 9.2) and ongoing (Section 15.5) precision and
recovery. Dilute 10 [micro]L of the precision and recovery standard
(Section 7.9.1 or 7.9.2) to 2.0 mL with acetone for each sample matrix
for each sample batch. One mL each are required for the blank and OPR
with each matrix in each batch.
7.15 GC Retention Time Window Defining Solution and Isomer
Specificity Test Standard--Used to define the beginning and ending
retention times for the dioxin and furan isomers and to demonstrate
isomer specificity of the GC columns employed for determination of
2,3,7,8-TCDD and 2,3,7,8-TCDF. The standard must contain the compounds
listed in Table 5 (CIL EDF--4006, or equivalent), at a minimum. It is
not necessary to monitor the window-defining compounds if only 2,3,7,8-
TCDD and 2,3,7,8-TCDF are to be determined. In this case, an isomer-
specificity test standard containing the most closely eluted isomers
listed in Table 5 (CIL EDF-4033, or equivalent) may be used.
7.16 QC Check Sample--A QC Check Sample should be obtained from a
source independent of the calibration standards. Ideally, this check
sample would be a certified reference material containing the CDDs/CDFs
in known concentrations in a sample matrix similar to the matrix under
test.
7.17 Stability of Solutions--Standard solutions used for
quantitative purposes (Sections 7.9 through 7.15) should be analyzed
periodically, and should be assayed against reference standards (Section
7.8.3) before further use.
8.0 Sample Collection, Preservation, Storage, and Holding Times
8.1 Collect samples in amber glass containers following conventional
sampling practices (Reference 16). Aqueous samples that flow freely are
collected in refrigerated bottles using automatic sampling equipment.
Solid samples are collected as grab samples using wide-mouth jars.
8.2 Maintain aqueous samples in the dark at 0-4 [deg]C from the time
of collection until receipt at the laboratory. If residual chlorine is
present in aqueous samples, add 80 mg sodium thiosulfate per liter of
water. EPA
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Methods 330.4 and 330.5 may be used to measure residual chlorine
(Reference 17). If sample pH is greater than 9, adjust to pH 7-9 with
sulfuric acid.
Maintain solid, semi-solid, oily, and mixed-phase samples in the
dark at <4 [deg]C from the time of collection until receipt at the
laboratory.
Store aqueous samples in the dark at 0-4 [deg]C. Store solid, semi-
solid, oily, mixed-phase, and tissue samples in the dark at <-10 [deg]C.
8.3 Fish and Tissue Samples.
8.3.1 Fish may be cleaned, filleted, or processed in other ways in
the field, such that the laboratory may expect to receive whole fish,
fish fillets, or other tissues for analysis.
8.3.2 Fish collected in the field should be wrapped in aluminum
foil, and must be maintained at a temperature less than 4 [deg]C from
the time of collection until receipt at the laboratory.
8.3.3 Samples must be frozen upon receipt at the laboratory and
maintained in the dark at <-10 [deg]C until prepared. Maintain unused
sample in the dark at <-10 [deg]C.
8.4 Holding Times.
8.4.1 There are no demonstrated maximum holding times associated
with CDDs/CDFs in aqueous, solid, semi-solid, tissues, or other sample
matrices. If stored in the dark at 0-4 [deg]C and preserved as given
above (if required), aqueous samples may be stored for up to one year.
Similarly, if stored in the dark at <-10 [deg]C, solid, semi-solid,
multi-phase, and tissue samples may be stored for up to one year.
8.4.2 Store sample extracts in the dark at <-10 [deg]C until
analyzed. If stored in the dark at <-10 [deg]C, sample extracts may be
stored for up to one year.
9.0 Quality Assurance/Quality Control
9.1 Each laboratory that uses this method is required to operate a
formal quality assurance program (Reference 18). The minimum
requirements of this program consist of an initial demonstration of
laboratory capability, analysis of samples spiked with labeled compounds
to evaluate and document data quality, and analysis of standards and
blanks as tests of continued performance. Laboratory performance is
compared to established performance criteria to determine if the results
of analyses meet the performance characteristics of the method.
If the method is to be applied to sample matrix other than water
(e.g., soils, filter cake, compost, tissue) the most appropriate
alternate matrix (Sections 7.6.2 through 7.6.5) is substituted for the
reagent water matrix (Section 7.6.1) in all performance tests.
9.1.1 The analyst shall make an initial demonstration of the ability
to generate acceptable accuracy and precision with this method. This
ability is established as described in Section 9.2.
9.1.2 In recognition of advances that are occurring in analytical
technology, and to allow the analyst to overcome sample matrix
interferences, the analyst is permitted certain options to improve
separations or lower the costs of measurements. These options include
alternate extraction, concentration, cleanup procedures, and changes in
columns and detectors. Alternate determinative techniques, such as the
substitution of spectroscopic or immuno-assay techniques, and changes
that degrade method performance, are not allowed. If an analytical
technique other than the techniques specified in this method is used,
that technique must have a specificity equal to or better than the
specificity of the techniques in this method for the analytes of
interest.
9.1.2.1 Each time a modification is made to this method, the analyst
is required to repeat the procedure in Section 9.2. If the detection
limit of the method will be affected by the change, the laboratory is
required to demonstrate that the MDL (40 CFR Part 136, Appendix B) is
lower than one-third the regulatory compliance level or one-third the ML
in this method, whichever is higher. If calibration will be affected by
the change, the analyst must recalibrate the instrument per Section 10.
9.1.2.2 The laboratory is required to maintain records of
modifications made to this method. These records include the following,
at a minimum:
9.1.2.2.1 The names, titles, addresses, and telephone numbers of the
analyst(s) who performed the analyses and modification, and of the
quality control officer who witnessed and will verify the analyses and
modifications.
9.1.2.2.2 A listing of pollutant(s) measured, by name and CAS
Registry number.
9.1.2.2.3 A narrative stating reason(s) for the modifications.
9.1.2.2.4 Results from all quality control (QC) tests comparing the
modified method to this method, including:
(a) Calibration (Section 10.5 through 10.7).
(b) Calibration verification (Section 15.3).
(c) Initial precision and recovery (Section 9.2).
(d) Labeled compound recovery (Section 9.3).
(e) Analysis of blanks (Section 9.5).
(f) Accuracy assessment (Section 9.4).
9.1.2.2.5 Data that will allow an independent reviewer to validate
each determination by tracing the instrument output (peak height, area,
or other signal) to the final result. These data are to include:
(a) Sample numbers and other identifiers.
(b) Extraction dates.
(c) Analysis dates and times.
(d) Analysis sequence/run chronology.
(e) Sample weight or volume (Section 11).
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(f) Extract volume prior to each cleanup step (Section 13).
(g) Extract volume after each cleanup step (Section 13).
(h) Final extract volume prior to injection (Section 14).
(i) Injection volume (Section 14.3).
(j) Dilution data, differentiating between dilution of a sample or
extract (Section 17.5).
(k) Instrument and operating conditions.
(l) Column (dimensions, liquid phase, solid support, film thickness,
etc).
(m) Operating conditions (temperatures, temperature program, flow
rates).
(n) Detector (type, operating conditions, etc).
(o) Chromatograms, printer tapes, and other recordings of raw data.
(p) Quantitation reports, data system outputs, and other data to
link the raw data to the results reported.
9.1.3 Analyses of method blanks are required to demonstrate freedom
from contamination (Section 4.3). The procedures and criteria for
analysis of a method blank are described in Sections 9.5 and 15.6.
9.1.4 The laboratory shall spike all samples with labeled compounds
to monitor method performance. This test is described in Section 9.3.
When results of these spikes indicate atypical method performance for
samples, the samples are diluted to bring method performance within
acceptable limits. Procedures for dilution are given in Section 17.5.
9.1.5 The laboratory shall, on an ongoing basis, demonstrate through
calibration verification and the analysis of the ongoing precision and
recovery aliquot that the analytical system is in control. These
procedures are described in Sections 15.1 through 15.5.
9.1.6 The laboratory shall maintain records to define the quality of
data that is generated. Development of accuracy statements is described
in Section 9.4.
9.2 Initial Precision and Recovery (IPR)--To establish the ability
to generate acceptable precision and recovery, the analyst shall perform
the following operations.
9.2.1 For low solids (aqueous) samples, extract, concentrate, and
analyze four 1 L aliquots of reagent water spiked with the diluted
labeled compound spiking solution (Section 7.10.3) and the precision and
recovery standard (Section 7.14) according to the procedures in Sections
11 through 18. For an alternative sample matrix, four aliquots of the
alternative reference matrix (Section 7.6) are used. All sample
processing steps that are to be used for processing samples, including
preparation (Section 11), extraction (Section 12), and cleanup (Section
13), shall be included in this test.
9.2.2 Using results of the set of four analyses, compute the average
concentration (X) of the extracts in ng/mL and the standard deviation of
the concentration (s) in ng/mL for each compound, by isotope dilution
for CDDs/CDFs with a labeled analog, and by internal standard for
1,2,3,7,8,9-HxCDD, OCDF, and the labeled compounds.
9.2.3 For each CDD/CDF and labeled compound, compare s and X with
the corresponding limits for initial precision and recovery in Table 6.
If only 2,3,7,8-TCDD and 2,3,7,8-TCDF are to be determined, compare s
and X with the corresponding limits for initial precision and recovery
in Table 6a. If s and X for all compounds meet the acceptance criteria,
system performance is acceptable and analysis of blanks and samples may
begin. If, however, any individual s exceeds the precision limit or any
individual X falls outside the range for accuracy, system performance is
unacceptable for that compound. Correct the problem and repeat the test
(Section 9.2).
9.3 The laboratory shall spike all samples with the diluted labeled
compound spiking solution (Section 7.10.3) to assess method performance
on the sample matrix.
9.3.1 Analyze each sample according to the procedures in Sections 11
through 18.
9.3.2 Compute the percent recovery of the labeled compounds and the
cleanup standard using the internal standard method (Section 17.2).
9.3.3 The recovery of each labeled compound must be within the
limits in Table 7 when all 2,3,7,8-substituted CDDs/CDFs are determined,
and within the limits in Table 7a when only 2,3,7,8-TCDD and 2,3,7,8-
TCDF are determined. If the recovery of any compound falls outside of
these limits, method performance is unacceptable for that compound in
that sample. To overcome such difficulties, water samples are diluted
and smaller amounts of soils, sludges, sediments, and other matrices are
reanalyzed per Section 18.4.
9.4 Recovery of labeled compounds from samples should be assessed
and records should be maintained.
9.4.1 After the analysis of five samples of a given matrix type
(water, soil, sludge, pulp, etc.) for which the labeled compounds pass
the tests in Section 9.3, compute the average percent recovery (R) and
the standard deviation of the percent recovery (SR) for the labeled
compounds only. Express the assessment as a percent recovery interval
from R-2SR to R=2SR for each matrix. For example,
if R = 90% and SR = 10% for five analyses of pulp, the
recovery interval is expressed as 70-110%.
9.4.2 Update the accuracy assessment for each labeled compound in
each matrix on a regular basis (e.g., after each 5-10 new measurements).
9.5 Method Blanks--Reference matrix method blanks are analyzed to
demonstrate freedom from contamination (Section 4.3).
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9.5.1 Prepare, extract, clean up, and concentrate a method blank
with each sample batch (samples of the same matrix started through the
extraction process on the same 12-hour shift, to a maximum of 20
samples). The matrix for the method blank shall be similar to sample
matrix for the batch, e.g., a 1 L reagent water blank (Section 7.6.1),
high-solids reference matrix blank (Section 7.6.2), paper matrix blank
(Section 7.6.3); tissue blank (Section 7.6.4) or alternative reference
matrix blank (Section 7.6.5). Analyze the blank immediately after
analysis of the OPR (Section 15.5) to demonstrate freedom from
contamination.
9.5.2 If any 2,3,7,8-substituted CDD/CDF (Table 1) is found in the
blank at greater than the minimum level (Table 2) or one-third the
regulatory compliance level, whichever is greater; or if any potentially
interfering compound is found in the blank at the minimum level for each
level of chlorination given in Table 2 (assuming a response factor of 1
relative to the 13C12-1,2,3,4-TCDD internal
standard for compounds not listed in Table 1), analysis of samples is
halted until the blank associated with the sample batch shows no
evidence of contamination at this level. All samples must be associated
with an uncontaminated method blank before the results for those samples
may be reported for regulatory compliance purposes.
9.6 QC Check Sample--Analyze the QC Check Sample (Section 7.16)
periodically to assure the accuracy of calibration standards and the
overall reliability of the analytical process. It is suggested that the
QC Check Sample be analyzed at least quarterly.
9.7 The specifications contained in this method can be met if the
apparatus used is calibrated properly and then maintained in a
calibrated state. The standards used for calibration (Section 10),
calibration verification (Section 15.3), and for initial (Section 9.2)
and ongoing (Section 15.5) precision and recovery should be identical,
so that the most precise results will be obtained. A GC/MS instrument
will provide the most reproducible results if dedicated to the settings
and conditions required for the analyses of CDDs/CDFs by this method.
9.8 Depending on specific program requirements, field replicates may
be collected to determine the precision of the sampling technique, and
spiked samples may be required to determine the accuracy of the analysis
when the internal standard method is used.
10.0 Calibration
10.1 Establish the operating conditions necessary to meet the
minimum retention times for the internal standards in Section 10.2.4 and
the relative retention times for the CDDs/CDFs in Table 2.
10.1.1 Suggested GC operating conditions:
Injector temperature: 270 [deg]C
Interface temperature: 290 [deg]C
Initial temperature: 200 [deg]C
Initial time: Two minutes
Temperature program:
200-220 [deg]C, at 5 [deg]C/minute
220 [deg]C for 16 minutes
220-235 [deg]C, at 5 [deg]C/minute
235 [deg]C for seven minutes
235-330 [deg]C, at 5 [deg]C/minute
Note: All portions of the column that connect the GC to the ion
source shall remain at or above the interface temperature specified
above during analysis to preclude condensation of less volatile
compounds.
Optimize GC conditions for compound separation and sensitivity. Once
optimized, the same GC conditions must be used for the analysis of all
standards, blanks, IPR and OPR aliquots, and samples.
10.1.2 Mass spectrometer (MS) resolution--Obtain a selected ion
current profile (SICP) of each analyte in Table 3 at the two exact m/z's
specified in Table 8 and at =10,000 resolving power by
injecting an authentic standard of the CDDs/CDFs either singly or as
part of a mixture in which there is no interference between closely
eluted components.
10.1.2.1 The analysis time for CDDs/CDFs may exceed the long-term
mass stability of the mass spectrometer. Because the instrument is
operated in the high-resolution mode, mass drifts of a few ppm (e.g., 5
ppm in mass) can have serious adverse effects on instrument performance.
Therefore, a mass-drift correction is mandatory and a lock-mass m/z from
PFK is used for drift correction. The lock-mass m/z is dependent on the
exact m/z's monitored within each descriptor, as shown in Table 8. The
level of PFK metered into the HRMS during analyses should be adjusted so
that the amplitude of the most intense selected lock-mass m/z signal
(regardless of the descriptor number) does not exceed 10% of the full-
scale deflection for a given set of detector parameters. Under those
conditions, sensitivity changes that might occur during the analysis can
be more effectively monitored.
Note: Excessive PFK (or any other reference substance) may cause
noise problems and contamination of the ion source necessitating
increased frequency of source cleaning.
10.1.2.2 If the HRMS has the capability to monitor resolution during
the analysis, it is acceptable to terminate the analysis when the
resolution falls below 10,000 to save reanalysis time.
10.1.2.3 Using a PFK molecular leak, tune the instrument to meet the
minimum required resolving power of 10,000 (10% valley) at m/z 304.9824
(PFK) or any other reference signal close to m/z 304 (from TCDF). For
each
[[Page 250]]
descriptor (Table 8), monitor and record the resolution and exact m/z's
of three to five reference peaks covering the mass range of the
descriptor. The resolution must be greater than or equal to 10,000, and
the deviation between the exact m/z and the theoretical m/z (Table 8)
for each exact m/z monitored must be less than 5 ppm.
10.2 Ion Abundance Ratios, Minimum Levels, Signal-to-Noise Ratios,
and Absolute Retention Times--Choose an injection volume of either 1
[micro]L or 2 [micro]L, consistent with the capability of the HRGC/HRMS
instrument. Inject a 1 [micro]L or 2 [micro]L aliquot of the CS1
calibration solution (Table 4) using the GC conditions from Section
10.1.1. If only 2,3,7,8-TCDD and 2,3,7,8-TCDF are to be determined, the
operating conditions and specifications below apply to analysis of those
compounds only.
10.2.1 Measure the SICP areas for each analyte, and compute the ion
abundance ratios at the exact m/z's specified in Table 8. Compare the
computed ratio to the theoretical ratio given in Table 9.
10.2.1.1 The exact m/z's to be monitored in each descriptor are
shown in Table 8. Each group or descriptor shall be monitored in
succession as a function of GC retention time to ensure that all CDDs/
CDFs are detected. Additional m/z's may be monitored in each descriptor,
and the m/z's may be divided among more than the five descriptors listed
in Table 8, provided that the laboratory is able to monitor the m/z's of
all the CDDs/CDFs that may elute from the GC in a given retention-time
window. If only 2,3,7,8-TCDD and 2,3,7,8-TCDF are to be determined, the
descriptors may be modified to include only the exact m/z's for the
tetra-and penta-isomers, the diphenyl ethers, and the lock m/z's.
10.2.1.2 The mass spectrometer shall be operated in a mass-drift
correction mode, using perfluorokerosene (PFK) to provide lock m/z's.
The lock-mass for each group of m/z's is shown in Table 8. Each lock
mass shall be monitored and shall not vary by more than 20% throughout its respective retention time window.
Variations of the lock mass by more than 20% indicate the presence of
coeluting interferences that may significantly reduce the sensitivity of
the mass spectrometer. Reinjection of another aliquot of the sample
extract will not resolve the problem. Additional cleanup of the extract
may be required to remove the interferences.
10.2.2 All CDDs/CDFs and labeled compounds in the CS1 standard shall
be within the QC limits in Table 9 for their respective ion abundance
ratios; otherwise, the mass spectrometer shall be adjusted and this test
repeated until the m/z ratios fall within the limits specified. If the
adjustment alters the resolution of the mass spectrometer, resolution
shall be verified (Section 10.1.2) prior to repeat of the test.
10.2.3 Verify that the HRGC/HRMS instrument meets the minimum levels
in Table 2. The peaks representing the CDDs/CDFs and labeled compounds
in the CS1 calibration standard must have signal-to-noise ratios (S/N)
greater than or equal to 10.0. Otherwise, the mass spectrometer shall be
adjusted and this test repeated until the minimum levels in Table 2 are
met.
10.2.4 The absolute retention time of 13C12-
1,2,3,4-TCDD (Section 7.12) shall exceed 25.0 minutes on the DB-5
column, and the retention time of 13C12-1,2,3,4-
TCDD shall exceed 15.0 minutes on the DB-225 column; otherwise, the GC
temperature program shall be adjusted and this test repeated until the
above-stated minimum retention time criteria are met.
2010.3 Retention-Time Windows--Analyze the window defining mixtures
(Section 7.15) using the optimized temperature program in Section 10.1.
Table 5 gives the elution order (first/last) of the window-defining
compounds. If 2,3,7,8-TCDD and 2,3,7,8-TCDF only are to be analyzed,
this test is not required.
10.4 Isomer Specificity.
10.4.1 Analyze the isomer specificity test standards (Section 7.15)
using the procedure in Section 14 and the optimized conditions for
sample analysis (Section 10.1.1).
10.4.2 Compute the percent valley between the GC peaks that elute
most closely to the 2,3,7,8-TCDD and TCDF isomers, on their respective
columns, per Figures 6 and 7.
10.4.3 Verify that the height of the valley between the most closely
eluted isomers and the 2,3,7,8-substituted isomers is less than 25%
(computed as 100 x/y in Figures 6 and 7). If the valley exceeds 25%,
adjust the analytical conditions and repeat the test or replace the GC
column and recalibrate (Sections 10.1.2 through 10.7).
10.5 Calibration by Isotope Dilution--Isotope dilution calibration
is used for the 15 2,3,7,8-substituted CDDs/CDFs for which labeled
compounds are added to samples prior to extraction. The reference
compound for each CDD/CDF compound is shown in Table 2.
10.5.1 A calibration curve encompassing the concentration range is
prepared for each compound to be determined. The relative response (RR)
(labeled to native) vs. concentration in standard solutions is plotted
or computed using a linear regression. Relative response is determined
according to the procedures described below. Five calibration points are
employed.
10.5.2 The response of each CDD/CDF relative to its labeled analog
is determined using the area responses of both the primary and secondary
exact m/z's specified in Table 8, for each calibration standard, as
follows:
[[Page 251]]
[GRAPHIC] [TIFF OMITTED] TR15SE97.002
where:
A1n and A2n = The areas of the primary and
secondary m/z's for the CDD/CDF.
A1l and A2l = The areas of the primary and
secondary m/z's for the labeled compound.
Cl = The concentration of the labeled compound in the
calibration standard (Table 4).
Cn = The concentration of the native compound in the
calibration standard (Table 4).
10.5.3 To calibrate the analytical system by isotope dilution,
inject a volume of calibration standards CS1 through CS5 (Section 7.13
and Table 4) identical to the volume chosen in Section 10.2, using the
procedure in Section 14 and the conditions in Section 10.1.1 and Table
2. Compute the relative response (RR) at each concentration.
10.5.4 Linearity--If the relative response for any compound is
constant (less than 20% coefficient of variation) over the five-point
calibration range, an averaged relative response may be used for that
compound; otherwise, the complete calibration curve for that compound
shall be used over the five-point calibration range.
10.6 Calibration by Internal Standard--The internal standard method
is applied to determination of 1,2,3,7,8,9-HxCDD (Section 17.1.2), OCDF
(Section 17.1.1), the non 2,3,7,8-substituted compounds, and to the
determination of labeled compounds for intralaboratory statistics
(Sections 9.4 and 15.5.4).
10.6.1 Response factors--Calibration requires the determination of
response factors (RF) defined by the following equation:
[GRAPHIC] [TIFF OMITTED] TR15SE97.003
where:
A1s and A2s = The areas of the primary and
secondary m/z's for the CDD/CDF.
A1is and A2is = The areas of the primary and
secondary m/z's for the internal standard.
Cis = The concentration of the internal standard (Table 4).
Cs = The concentration of the compound in the calibration
standard (Table 4).
Note: There is only one m/z for 37Cl4-2,3,7,8-
TCDD. See Table 8.
10.6.2 To calibrate the analytical system by internal standard,
inject 1.0 [micro]L or 2.0 [micro]L of calibration standards CS1 through
CS5 (Section 7.13 and Table 4) using the procedure in Section 14 and the
conditions in Section 10.1.1 and Table 2. Compute the response factor
(RF) at each concentration.
10.6.3 Linearity--If the response factor (RF) for any compound is
constant (less than 35% coefficient of variation) over the five-point
calibration range, an averaged response factor may be used for that
compound; otherwise, the complete calibration curve for that compound
shall be used over the five-point range.
10.7 Combined Calibration--By using calibration solutions (Section
7.13 and Table 4) containing the CDDs/CDFs and labeled compounds and the
internal standards, a single set of analyses can be used to produce
calibration curves for the isotope dilution and internal standard
methods. These curves are verified each shift (Section 15.3) by
analyzing the calibration verification standard (VER, Table 4).
Recalibration is required if any of the calibration verification
criteria (Section 15.3) cannot be met.
10.8 Data Storage--MS data shall be collected, recorded, and stored.
10.8.1 Data acquisition--The signal at each exact m/z shall be
collected repetitively throughout the monitoring period and stored on a
mass storage device.
10.8.2 Response factors and multipoint calibrations--The data system
shall be used to record and maintain lists of response factors (response
ratios for isotope dilution) and multipoint calibration curves.
Computations of relative standard deviation (coefficient of variation)
shall be used to test calibration linearity. Statistics on initial
performance (Section 9.2) and ongoing performance (Section 15.5) should
be computed and maintained, either on the instrument data system, or on
a separate computer system.
11.0 Sample Preparation
11.1 Sample preparation involves modifying the physical form of the
sample so that the CDDs/CDFs can be extracted efficiently. In general,
the samples must be in a liquid form or in the form of finely divided
solids in order for efficient extraction to take place. Table 10 lists
the phases and suggested quantities for extraction of various sample
matrices.
For samples known or expected to contain high levels of the CDDs/
CDFs, the smallest sample size representative of the entire sample
should be used (see Section 17.5).
For all samples, the blank and IPR/OPR aliquots must be processed
through the same steps as the sample to check for contamination and
losses in the preparation processes.
11.1.1 For samples that contain particles, percent solids and
particle size are determined using the procedures in Sections 11.2 and
11.3, respectively.
11.1.2 Aqueous samples--Because CDDs/CDFs may be bound to suspended
particles, the preparation of aqueous samples is dependent on the solids
content of the sample.
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11.1.2.1 Aqueous samples visibly absent particles are prepared per
Section 11.4 and extracted directly using the separatory funnel or SPE
techniques in Sections 12.1 or 12.2, respectively.
11.1.2.2 Aqueous samples containing visible particles and containing
one percent suspended solids or less are prepared using the procedure in
Section 11.4. After preparation, the sample is extracted directly using
the SPE technique in 12.2 or filtered per Section 11.4.3. After
filtration, the particles and filter are extracted using the SDS
procedure in Section 12.3 and the filtrate is extracted using the
separatory funnel procedure in Section 12.1.
11.1.2.3 For aqueous samples containing greater than one percent
solids, a sample aliquot sufficient to provide 10 g of dry solids is
used, as described in Section 11.5.
11.1.3 Solid samples are prepared using the procedure described in
Section 11.5 followed by extraction via the SDS procedure in Section
12.3.
11.1.4 Multiphase samples--The phase(s) containing the CDDs/CDFs is
separated from the non-CDD/CDF phase using pressure filtration and
centrifugation, as described in Section 11.6. The CDDs/CDFs will be in
the organic phase in a multiphase sample in which an organic phase
exists.
11.1.5 Procedures for grinding, homogenization, and blending of
various sample phases are given in Section 11.7.
11.1.6 Tissue samples--Preparation procedures for fish and other
tissues are given in Section 11.8.
11.2 Determination of Percent Suspended Solids.
Note: This aliquot is used for determining the solids content of the
sample, not for determination of CDDs/CDFs.
11.2.1 Aqueous liquids and multi-phase samples consisting of mainly
an aqueous phase.
11.2.1.1 Dessicate and weigh a GF/D filter (Section 6.5.3) to three
significant figures.
11.2.1.2 Filter 10.00.02 mL of well-mixed
sample through the filter.
11.2.1.3 Dry the filter a minimum of 12 hours at 1105 [deg]C and cool in a dessicator.
11.2.1.4 Calculate percent solids as follows:
[GRAPHIC] [TIFF OMITTED] TR15SE97.004
11.2.2 Non-aqueous liquids, solids, semi-solid samples, and multi-
phase samples in which the main phase is not aqueous; but not tissues.
11.2.2.1 Weigh 5-10 g of sample to three significant figures in a
tared beaker.
11.2.2.2 Dry a minimum of 12 hours at 1105
[deg]C, and cool in a dessicator.
11.2.2.3 Calculate percent solids as follows:
[GRAPHIC] [TIFF OMITTED] TR15SE97.005
11.3 Determination of Particle Size.
11.3.1 Spread the dried sample from Section 11.2.2.2 on a piece of
filter paper or aluminum foil in a fume hood or glove box.
11.3.2 Estimate the size of the particles in the sample. If the size
of the largest particles is greater than 1 mm, the particle size must be
reduced to 1 mm or less prior to extraction using the procedures in
Section 11.7.
11.4 Preparation of Aqueous Samples Containing 1% Suspended Solids
or Less.
11.4.1 Aqueous samples visibly absent particles are prepared per the
procedure below and extracted directly using the separatory funnel or
SPE techniques in Sections 12.1 or 12.2, respectively. Aqueous samples
containing visible particles and one percent suspended solids or less
are prepared using the procedure below and extracted using either the
SPE technique in Section 12.2 or further prepared using the filtration
procedure in Section 11.4.3. The filtration procedure is followed by SDS
extraction of the filter and particles (Section 12.3) and separatory
funnel extraction of the filtrate (Section 12.1). The SPE procedure is
followed by SDS extraction of the filter and disk.
11.4.2 Preparation of sample and QC aliquots.
11.4.2.1 Mark the original level of the sample on the sample bottle
for reference. Weigh the sample plus bottle to 1.
[[Page 253]]
11.4.2.2 Spike 1.0 mL of the diluted labeled-compound spiking
solution (Section 7.10.3) into the sample bottle. Cap the bottle and mix
the sample by careful shaking. Allow the sample to equilibrate for one
to two hours, with occasional shaking.
11.4.2.3 For each sample or sample batch (to a maximum of 20
samples) to be extracted during the same 12-hour shift, place two 1.0 L
aliquots of reagent water in clean sample bottles or flasks.
11.4.2.4 Spike 1.0 mL of the diluted labeled-compound spiking
solution (Section 7.10.3) into both reagent water aliquots. One of these
aliquots will serve as the method blank.
11.4.2.5 Spike 1.0 mL of the PAR standard (Section 7.14) into the
remaining reagent water aliquot. This aliquot will serve as the OPR
(Section 15.5).
11.4.2.6 If SPE is to be used, add 5 mL of methanol to the sample,
cap and shake the sample to mix thoroughly, and proceed to Section 12.2
for extraction. If SPE is not to be used, and the sample is visibly
absent particles, proceed to Section 12.1 for extraction. If SPE is not
to be used and the sample contains visible particles, proceed to the
following section for filtration of particles.
11.4.3 Filtration of particles.
11.4.3.1 Assemble a Buchner funnel (Section 6.5.5) on top of a clean
filtration flask. Apply vacuum to the flask, and pour the entire
contents of the sample bottle through a glass-fiber filter (Section
6.5.6) in the Buchner funnel, swirling the sample remaining in the
bottle to suspend any particles.
11.4.3.2 Rinse the sample bottle twice with approximately 5 mL
portions of reagent water to transfer any remaining particles onto the
filter.
11.4.3.3 Rinse any particles off the sides of the Buchner funnel
with small quantities of reagent water.
11.4.3.4 Weigh the empty sample bottle to 1 g.
Determine the weight of the sample by difference. Save the bottle for
further use.
11.4.3.5 Extract the filtrate using the separatory funnel procedure
in Section 12.1.
11.4.3.6 Extract the filter containing the particles using the SDS
procedure in Section 12.3.
11.5 Preparation of Samples Containing Greater Than 1% Solids.
11.5.1 Weigh a well-mixed aliquot of each sample (of the same matrix
type) sufficient to provide 10 g of dry solids (based on the solids
determination in Section 11.2) into a clean beaker or glass jar.
11.5.2 Spike 1.0 mL of the diluted labeled compound spiking solution
(Section 7.10.3) into the sample.
11.5.3 For each sample or sample batch (to a maximum of 20 samples)
to be extracted during the same 12-hour shift, weigh two 10 g aliquots
of the appropriate reference matrix (Section 7.6) into clean beakers or
glass jars.
11.5.4 Spike 1.0 mL of the diluted labeled compound spiking solution
(Section 7.10.3) into each reference matrix aliquot. One aliquot will
serve as the method blank. Spike 1.0 mL of the PAR standard (Section
7.14) into the other reference matrix aliquot. This aliquot will serve
as the OPR (Section 15.5).
11.5.5 Stir or tumble and equilibrate the aliquots for one to two
hours.
11.5.6 Decant excess water. If necessary to remove water, filter the
sample through a glass-fiber filter and discard the aqueous liquid.
11.5.7 If particles 1mm are present in the sample (as
determined in Section 11.3.2), spread the sample on clean aluminum foil
in a hood. After the sample is dry, grind to reduce the particle size
(Section 11.7).
11.5.8 Extract the sample and QC aliquots using the SDS procedure in
Section 12.3.
11.6 Multiphase Samples.
11.6.1 Using the percent solids determined in Section 11.2.1 or
11.2.2, determine the volume of sample that will provide 10 g of solids,
up to 1 L of sample.
11.6.2 Pressure filter the amount of sample determined in Section
11.6.1 through Whatman GF/D glass-fiber filter paper (Section 6.5.3).
Pressure filter the blank and OPR aliquots through GF/D papers also. If
necessary to separate the phases and/or settle the solids, centrifuge
these aliquots prior to filtration.
11.6.3 Discard any aqueous phase (if present). Remove any non-
aqueous liquid present and reserve the maximum amount filtered from the
sample (Section 11.6.1) or 10 g, whichever is less, for combination with
the solid phase (Section 12.3.5).
11.6.4 If particles 1mm are present in the sample (as
determined in Section 11.3.2) and the sample is capable of being dried,
spread the sample and QC aliquots on clean aluminum foil in a hood.
After the aliquots are dry or if the sample cannot be dried, reduce the
particle size using the procedures in Section 11.7 and extract the
reduced particles using the SDS procedure in Section 12.3. If particles
1mm are not present, extract the particles and filter in the
sample and QC aliquots directly using the SDS procedure in Section 12.3.
11.7 Sample grinding, homogenization, or blending--Samples with
particle sizes greater than 1 mm (as determined in Section 11.3.2) are
subjected to grinding, homogenization, or blending. The method of
reducing particle size to less than 1 mm is matrix-dependent. In
general, hard particles can be reduced by grinding with a mortar and
pestle. Softer particles can be reduced by grinding in a Wiley mill or
meat grinder, by homogenization, or in a blender.
11.7.1 Each size-reducing preparation procedure on each matrix shall
be verified by running the tests in Section 9.2 before the procedure is
employed routinely.
[[Page 254]]
11.7.2 The grinding, homogenization, or blending procedures shall be
carried out in a glove box or fume hood to prevent particles from
contaminating the work environment.
11.7.3 Grinding--Certain papers and pulps, slurries, and amorphous
solids can be ground in a Wiley mill or heavy duty meat grinder. In some
cases, reducing the temperature of the sample to freezing or to dry ice
or liquid nitrogen temperatures can aid in the grinding process. Grind
the sample aliquots from Section 11.5.7 or 11.6.4 in a clean grinder. Do
not allow the sample temperature to exceed 50 [deg]C. Grind the blank
and reference matrix aliquots using a clean grinder.
11.7.4 Homogenization or blending--Particles that are not ground
effectively, or particles greater than 1 mm in size after grinding, can
often be reduced in size by high speed homogenization or blending.
Homogenize and/or blend the particles or filter from Section 11.5.7 or
11.6.4 for the sample, blank, and OPR aliquots.
11.7.5 Extract the aliquots using the SDS procedure in Section 12.3.
11.8 Fish and Other Tissues--Prior to processing tissue samples, the
laboratory must determine the exact tissue to be analyzed. Common
requests for analysis of fish tissue include whole fish--skin on, whole
fish--skin removed, edible fish fillets (filleted in the field or by the
laboratory), specific organs, and other portions. Once the appropriate
tissue has been determined, the sample must be homogenized.
11.8.1 Homogenization.
11.8.1.1 Samples are homogenized while still frozen, where
practical. If the laboratory must dissect the whole fish to obtain the
appropriate tissue for analysis, the unused tissues may be rapidly
refrozen and stored in a clean glass jar for subsequent use.
11.8.1.2 Each analysis requires 10 g of tissue (wet weight).
Therefore, the laboratory should homogenize at least 20 g of tissue to
allow for re-extraction of a second aliquot of the same homogenized
sample, if re-analysis is required. When whole fish analysis is
necessary, the entire fish is homogenized.
11.8.1.3 Homogenize the sample in a tissue homogenizer (Section
6.3.3) or grind in a meat grinder (Section 6.3.4). Cut tissue too large
to feed into the grinder into smaller pieces. To assure homogeneity,
grind three times.
11.8.1.4 Transfer approximately 10 g (wet weight) of homogenized
tissue to a clean, tared, 400-500 mL beaker. For the alternate HCl
digestion/extraction, transfer the tissue to a clean, tared 500-600 mL
wide-mouth bottle. Record the weight to the nearest 10 mg.
11.8.1.5 Transfer the remaining homogenized tissue to a clean jar
with a fluoropolymer-lined lid. Seal the jar and store the tissue at <-
10 [deg]C. Return any tissue that was not homogenized to its original
container and store at <-10 [deg]C.
11.8.2 QC aliquots.
11.8.2.1 Prepare a method blank by adding approximately 10 g of the
oily liquid reference matrix (Section 7.6.4) to a 400-500 mL beaker. For
the alternate HCl digestion/extraction, add the reference matrix to a
500-600 mL wide-mouth bottle. Record the weight to the nearest 10 mg.
11.8.2.2 Prepare a precision and recovery aliquot by adding
approximately 10 g of the oily liquid reference matrix (Section 7.6.4)
to a separate 400-500 mL beaker or wide-mouth bottle, depending on the
extraction procedure to be used. Record the weight to the nearest 10 mg.
If the initial precision and recovery test is to be performed, use four
aliquots; if the ongoing precision and recovery test is to be performed,
use a single aliquot.
11.8.3 Spiking
11.8.3.1 Spike 1.0 mL of the labeled compound spiking solution
(Section 7.10.3) into the sample, blank, and OPR aliquot.
11.8.3.2 Spike 1.0 mL of the PAR standard (Section 7.14) into the
OPR aliquot.
11.8.4 Extract the aliquots using the procedures in Section 12.4.
12.0 Extraction and Concentration
Extraction procedures include separatory funnel (Section 12.1) and
solid phase (Section 12.2) for aqueous liquids; Soxhlet/Dean-Stark
(Section 12.3) for solids, filters, and SPE disks; and Soxhlet
extraction (Section 12.4.1) and HCl digestion (Section 12.4.2) for
tissues. Acid/base back-extraction (Section 12.5) is used for initial
cleanup of extracts.
Macro-concentration procedures include rotary evaporation (Section
12.6.1), heating mantle (Section 12.6.2), and Kuderna-Danish (K-D)
evaporation (Section 12.6.3). Micro-concentration uses nitrogen blowdown
(Section 12.7).
12.1 Separatory funnel extraction of filtrates and of aqueous
samples visibly absent particles.
12.1.1 Pour the spiked sample (Section 11.4.2.2) or filtrate
(Section 11.4.3.5) into a 2 L separatory funnel. Rinse the bottle or
flask twice with 5 mL of reagent water and add these rinses to the
separatory funnel.
12.1.2 Add 60 mL methylene chloride to the empty sample bottle
(Section 12.1.1), seal, and shake 60 seconds to rinse the inner surface.
Transfer the solvent to the separatory funnel, and extract the sample by
shaking the funnel for two minutes with periodic venting. Allow the
organic layer to separate from the aqueous phase for a minimum of 10
minutes. If an emulsion forms and is more than one-third the volume of
the solvent layer, employ mechanical techniques to complete the phase
separation (see note below). Drain the methylene chloride extract
[[Page 255]]
through a solvent-rinsed glass funnel approximately one-half full of
granular anhydrous sodium sulfate (Section 7.2.1) supported on clean
glass-fiber paper into a solvent-rinsed concentration device (Section
12.6).
Note: If an emulsion forms, the analyst must employ mechanical
techniques to complete the phase separation. The optimum technique
depends upon the sample, but may include stirring, filtration through
glass wool, use of phase separation paper, centrifugation, use of an
ultrasonic bath with ice, addition of NaCl, or other physical methods.
Alternatively, solid-phase or other extraction techniques may be used to
prevent emulsion formation. Any alternative technique is acceptable so
long as the requirements in Section 9 are met.
Experience with aqueous samples high in dissolved organic materials
(e.g., paper mill effluents) has shown that acidification of the sample
prior to extraction may reduce the formation of emulsions. Paper
industry methods suggest that the addition of up to 400 mL of ethanol to
a 1 L effluent sample may also reduce emulsion formation. However,
studies by EPA suggest that the effect may be a result of sample
dilution, and that the addition of reagent water may serve the same
function. Mechanical techniques may still be necessary to complete the
phase separation. If either acidification or addition of ethanol is
utilized, the laboratory must perform the startup tests described in
Section 9.2 using the same techniques.
12.1.3 Extract the water sample two more times with 60 mL portions
of methylene chloride. Drain each portion through the sodium sulfate
into the concentrator. After the third extraction, rinse the separatory
funnel with at least 20 mL of methylene chloride, and drain this rinse
through the sodium sulfate into the concentrator. Repeat this rinse at
least twice. Set aside the funnel with sodium sulfate if the extract is
to be combined with the extract from the particles.
12.1.4 Concentrate the extract using one of the macro-concentration
procedures in Section 12.6.
12.1.4.1 If the extract is from a sample visibly absent particles
(Section 11.1.2.1), adjust the final volume of the concentrated extract
to approximately 10 mL with hexane, transfer to a 250 mL separatory
funnel, and back-extract using the procedure in Section 12.5.
12.1.4.2 If the extract is from the aqueous filtrate (Section
11.4.3.5), set aside the concentration apparatus for addition of the SDS
extract from the particles (Section 12.3.9.1.2).
12.2 SPE of Samples Containing Less Than 1% Solids (References 19-
20).
12.2.1 Disk preparation.
12.2.1.1 Place an SPE disk on the base of the filter holder (Figure
4) and wet with toluene. While holding a GMF 150 filter above the SPE
disk with tweezers, wet the filter with toluene and lay the filter on
the SPE disk, making sure that air is not trapped between the filter and
disk. Clamp the filter and SPE disk between the 1 L glass reservoir and
the vacuum filtration flask.
12.2.1.2 Rinse the sides of the filtration flask with approx 15 mL
of toluene using a squeeze bottle or syringe. Apply vacuum momentarily
until a few drops appear at the drip tip. Release the vacuum and allow
the filter/disk to soak for approx one minute. Apply vacuum and draw all
of the toluene through the filter/disk. Repeat the wash step with approx
15 mL of acetone and allow the filter/disk to air dry.
12.2.1.3 Re-wet the filter/disk with approximately 15 mL of
methanol, allowing the filter/disk to soak for approximately one minute.
Pull the methanol through the filter/disk using the vacuum, but retain a
layer of methanol approximately 1 mm thick on the filter. Do not allow
the disk to go dry from this point until the end of the extraction.
12.2.1.4 Rinse the filter/disk with two 50-mL portions of reagent
water by adding the water to the reservoir and pulling most through,
leaving a layer of water on the surface of the filter.
12.2.2 Extraction.
12.2.2.1 Pour the spiked sample (Section 11.4.2.2), blank (Section
11.4.2.4), or IPR/OPR aliquot (Section 11.4.2.5) into the reservoir and
turn on the vacuum to begin the extraction. Adjust the vacuum to
complete the extraction in no less than 10 minutes. For samples
containing a high concentration of particles (suspended solids),
filtration times may be eight hours or longer.
12.2.2.2 Before all of the sample has been pulled through the
filter/disk, rinse the sample bottle with approximately 50 mL of reagent
water to remove any solids, and pour into the reservoir. Pull through
the filter/disk. Use additional reagent water rinses until all visible
solids are removed.
12.2.2.3 Before all of the sample and rinses have been pulled
through the filter/disk, rinse the sides of the reservoir with small
portions of reagent water.
12.2.2.4 Allow the filter/disk to dry, then remove the filter and
disk and place in a glass Petri dish. Extract the filter and disk per
Section 12.3.
12.3 SDS Extraction of Samples Containing Particles, and of Filters
and/or Disks.
12.3.1 Charge a clean extraction thimble (Section 6.4.2.2) with 5.0
g of 100/200 mesh silica (Section 7.5.1.1) topped with 100 g of quartz
sand (Section 7.3.2).
Note: Do not disturb the silica layer throughout the extraction
process.
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12.3.2 Place the thimble in a clean extractor. Place 30-40 mL of
toluene in the receiver and 200-250 mL of toluene in the flask.
12.3.3 Pre-extract the glassware by heating the flask until the
toluene is boiling. When properly adjusted, one to two drops of toluene
will fall per second from the condenser tip into the receiver. Extract
the apparatus for a minimum of three hours.
12.3.4 After pre-extraction, cool and disassemble the apparatus.
Rinse the thimble with toluene and allow to air dry.
12.3.5 Load the wet sample, filter, and/or disk from Section
11.4.3.6, 11.5.8, 11.6.4, 11.7.3, 11.7.4, or 12.2.2.4 and any nonaqueous
liquid from Section 11.6.3 into the thimble and manually mix into the
sand layer with a clean metal spatula, carefully breaking up any large
lumps of sample.
12.3.6 Reassemble the pre-extracted SDS apparatus, and add a fresh
charge of toluene to the receiver and reflux flask. Apply power to the
heating mantle to begin refluxing. Adjust the reflux rate to match the
rate of percolation through the sand and silica beds until water removal
lessens the restriction to toluene flow. Frequently check the apparatus
for foaming during the first two hours of extraction. If foaming occurs,
reduce the reflux rate until foaming subsides.
12.3.7 Drain the water from the receiver at one to two hours and
eight to nine hours, or sooner if the receiver fills with water. Reflux
the sample for a total of 16-24 hours. Cool and disassemble the
apparatus. Record the total volume of water collected.
12.3.8 Remove the distilling flask. Drain the water from the Dean-
Stark receiver and add any toluene in the receiver to the extract in the
flask.
12.3.9 Concentrate the extract using one of the macro-concentration
procedures in Section 12.6 per the following:
12.3.9.1 Extracts from the particles in an aqueous sample containing
less than 1% solids (Section 11.4.3.6).
12.3.9.1.1 Concentrate the extract to approximately 5 mL using the
rotary evaporator or heating mantle procedures in Section 12.6.1 or
12.6.2.
12.3.9.1.2 Quantitatively transfer the extract through the sodium
sulfate (Section 12.1.3) into the apparatus that was set aside (Section
12.1.4.2) and reconcentrate to the level of the toluene.
12.3.9.1.3 Adjust to approximately 10 mL with hexane, transfer to a
250 mL separatory funnel, and proceed with back-extraction (Section
12.5).
12.3.9.2 Extracts from particles (Sections 11.5 through 11.6) or
from the SPE filter and disk (Section 12.2.2.4)--Concentrate to
approximately 10 mL using the rotary evaporator or heating mantle
(Section 12.6.1 or 12.6.2), transfer to a 250 mL separatory funnel, and
proceed with back-extraction (Section 12.5).
12.4 Extraction of Tissue--Two procedures are provided for tissue
extraction.
12.4.1 Soxhlet extraction (Reference 21).
12.4.1.1 Add 30-40 g of powdered anhydrous sodium sulfate to each of
the beakers (Section 11.8.4) and mix thoroughly. Cover the beakers with
aluminum foil and allow to equilibrate for 12-24 hours. Remix prior to
extraction to prevent clumping.
12.4.1.2 Assemble and pre-extract the Soxhlet apparatus per Sections
12.3.1 through 12.3.4, except use the methylene chloride:hexane (1:1)
mixture for the pre-extraction and rinsing and omit the quartz sand. The
Dean-Stark moisture trap may also be omitted, if desired.
12.4.1.3 Reassemble the pre-extracted Soxhlet apparatus and add a
fresh charge of methylene chloride:hexane to the reflux flask.
12.4.1.4 Transfer the sample/sodium sulfate mixture (Section
12.4.1.1) to the Soxhlet thimble, and install the thimble in the Soxhlet
apparatus.
12.4.1.5 Rinse the beaker with several portions of solvent mixture
and add to the thimble. Fill the thimble/receiver with solvent. Extract
for 18-24 hours.
12.4.1.6 After extraction, cool and disassemble the apparatus.
12.4.1.7 Quantitatively transfer the extract to a macro-
concentration device (Section 12.6), and concentrate to near dryness.
Set aside the concentration apparatus for re-use.
12.4.1.8 Complete the removal of the solvent using the nitrogen
blowdown procedure (Section 12.7) and a water bath temperature of 60
[deg]C. Weigh the receiver, record the weight, and return the receiver
to the blowdown apparatus, concentrating the residue until a constant
weight is obtained.
12.4.1.9 Percent lipid determination--The lipid content is
determined by extraction of tissue with the same solvent system
(methylene chloride:hexane) that was used in EPA's National Dioxin Study
(Reference 22) so that lipid contents are consistent with that study.
12.4.1.9.1 Redissolve the residue in the receiver in hexane and
spike 1.0 mL of the cleanup standard (Section 7.11) into the solution.
12.4.1.9.2 Transfer the residue/hexane to the anthropogenic
isolation column (Section 13.7.1) or bottle for the acidified silica gel
batch cleanup (Section 13.7.2), retaining the boiling chips in the
concentration apparatus. Use several rinses to assure that all material
is transferred. If necessary, sonicate or heat the receiver slightly to
assure that all material is re-dissolved. Allow the receiver to dry.
Weigh the receiver and boiling chips.
12.4.1.9.3 Calculate the lipid content to the nearest three
significant figures as follows:
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[GRAPHIC] [TIFF OMITTED] TR15SE97.006
12.4.1.9.4 It is not necessary to determine the lipid content of the
blank, IPR, or OPR aliquots.
12.4.2 HCl digestion/extraction and concentration (References 23-
26).
12.4.2.1 Add 200 mL of 6 N HCl and 200 mL of methylene
chloride:hexane (1:1) to the sample and QC aliquots (Section 11.8.4).
12.4.2.2 Cap and shake each bottle one to three times. Loosen the
cap in a hood to vent excess pressure. Shake each bottle for 10-30
seconds and vent.
12.4.2.3 Tightly cap and place on shaker. Adjust the shaker action
and speed so that the acid, solvent, and tissue are in constant motion.
However, take care to avoid such violent action that the bottle may be
dislodged from the shaker. Shake for 12-24 hours.
12.4.2.4 After digestion, remove the bottles from the shaker. Allow
the bottles to stand so that the solvent and acid layers separate.
12.4.2.5 Decant the solvent through a glass funnel with glass-fiber
filter (Sections 6.5.2 through 6.5.3) containing approximately 10 g of
granular anhydrous sodium sulfate (Section 7.2.1) into a macro-
concentration apparatus (Section 12.6). Rinse the contents of the bottle
with two 25 mL portions of hexane and pour through the sodium sulfate
into the apparatus.
12.4.2.6 Concentrate the solvent to near dryness using a macro-
concentration procedure (Section 12.6).
12.4.2.7 Complete the removal of the solvent using the nitrogen
blowdown apparatus (Section 12.7) and a water bath temperature of 60
[deg]C. Weigh the receiver, record the weight, and return the receiver
to the blowdown apparatus, concentrating the residue until a constant
weight is obtained.
12.4.2.8 Percent lipid determination--The lipid content is
determined in the same solvent system [methylene chloride:hexane (1:1)]
that was used in EPA's National Dioxin Study (Reference 22) so that
lipid contents are consistent with that study.
12.4.2.8.1 Redissolve the residue in the receiver in hexane and
spike 1.0 mL of the cleanup standard (Section 7.11) into the solution.
12.4.2.8.2 Transfer the residue/hexane to the narrow-mouth 100-200
mL bottle retaining the boiling chips in the receiver. Use several
rinses to assure that all material is transferred, to a maximum hexane
volume of approximately 70 mL. Allow the receiver to dry. Weigh the
receiver and boiling chips.
12.4.2.8.3 Calculate the percent lipid per Section 12.4.1.9.3. It is
not necessary to determine the lipid content of the blank, IPR, or OPR
aliquots.
12.4.2.9 Clean up the extract per Section 13.7.3.
12.5 Back-Extraction with Base and Acid.
12.5.1 Spike 1.0 mL of the cleanup standard (Section 7.11) into the
separatory funnels containing the sample and QC extracts from Section
12.1.4.1, 12.3.9.1.3, or 12.3.9.2.
12.5.2 Partition the extract against 50 mL of potassium hydroxide
solution (Section 7.1.1). Shake for two minutes with periodic venting
into a hood. Remove and discard the aqueous layer. Repeat the base
washing until no color is visible in the aqueous layer, to a maximum of
four washings. Minimize contact time between the extract and the base to
prevent degradation of the CDDs/CDFs. Stronger potassium hydroxide
solutions may be employed for back-extraction, provided that the
laboratory meets the specifications for labeled compound recovery and
demonstrates acceptable performance using the procedure in Section 9.2.
12.5.3 Partition the extract against 50 mL of sodium chloride
solution (Section 7.1.4) in the same way as with base. Discard the
aqueous layer.
12.5.4 Partition the extract against 50 mL of sulfuric acid (Section
7.1.2) in the same way as with base. Repeat the acid washing until no
color is visible in the aqueous layer, to a maximum of four washings.
12.5.5 Repeat the partitioning against sodium chloride solution and
discard the aqueous layer.
12.5.6 Pour each extract through a drying column containing 7-10 cm
of granular anhydrous sodium sulfate (Section 7.2.1). Rinse the
separatory funnel with 30-50 mL of solvent, and pour through the drying
column. Collect each extract in a round-bottom flask. Re-concentrate the
sample and QC aliquots per Sections 12.6 through 12.7, and clean up the
samples and QC aliquots per Section 13.
12.6 Macro-Concentration--Extracts in toluene are concentrated using
a rotary evaporator or a heating mantle; extracts in methylene chloride
or hexane are concentrated using a rotary evaporator, heating mantle, or
Kuderna-Danish apparatus.
12.6.1 Rotary evaporation--Concentrate the extracts in separate
round-bottom flasks.
12.6.1.1 Assemble the rotary evaporator according to manufacturer's
instructions, and warm the water bath to 45 [deg]C. On a daily basis,
preclean the rotary evaporator by concentrating 100 mL of clean
extraction solvent through the system. Archive both the concentrated
solvent and the solvent in the catch flask for a contamination check if
necessary. Between samples, three 2-3 mL aliquots of solvent should be
rinsed down the feed tube into a waste beaker.
12.6.1.2 Attach the round-bottom flask containing the sample extract
to the rotary evaporator. Slowly apply vacuum to the system, and begin
rotating the sample flask.
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12.6.1.3 Lower the flask into the water bath, and adjust the speed
of rotation and the temperature as required to complete concentration in
15-20 minutes. At the proper rate of concentration, the flow of solvent
into the receiving flask will be steady, but no bumping or visible
boiling of the extract will occur.
Note: If the rate of concentration is too fast, analyte loss may
occur.
12.6.1.4 When the liquid in the concentration flask has reached an
apparent volume of approximately 2 mL, remove the flask from the water
bath and stop the rotation. Slowly and carefully admit air into the
system. Be sure not to open the valve so quickly that the sample is
blown out of the flask. Rinse the feed tube with approximately 2 mL of
solvent.
12.6.1.5 Proceed to Section 12.6.4 for preparation for back-
extraction or micro-concentration and solvent exchange.
12.6.2 Heating mantle--Concentrate the extracts in separate round-
bottom flasks.
12.6.2.1 Add one or two clean boiling chips to the round-bottom
flask, and attach a three-ball macro Snyder column. Prewet the column by
adding approximately 1 mL of solvent through the top. Place the round-
bottom flask in a heating mantle, and apply heat as required to complete
the concentration in 15-20 minutes. At the proper rate of distillation,
the balls of the column will actively chatter, but the chambers will not
flood.
12.6.2.2 When the liquid has reached an apparent volume of
approximately 10 mL, remove the round-bottom flask from the heating
mantle and allow the solvent to drain and cool for at least 10 minutes.
Remove the Snyder column and rinse the glass joint into the receiver
with small portions of solvent.
12.6.2.3 Proceed to Section 12.6.4 for preparation for back-
extraction or micro-concentration and solvent exchange.
12.6.3 Kuderna-Danish (K-D)--Concentrate the extracts in separate
500 mL K-D flasks equipped with 10 mL concentrator tubes. The K-D
technique is used for solvents such as methylene chloride and hexane.
Toluene is difficult to concentrate using the K-D technique unless a
water bath fed by a steam generator is used.
12.6.3.1 Add one to two clean boiling chips to the receiver. Attach
a three-ball macro Snyder column. Prewet the column by adding
approximately 1 mL of solvent through the top. Place the K-D apparatus
in a hot water bath so that the entire lower rounded surface of the
flask is bathed with steam.
12.6.3.2 Adjust the vertical position of the apparatus and the water
temperature as required to complete the concentration in 15-20 minutes.
At the proper rate of distillation, the balls of the column will
actively chatter but the chambers will not flood.
12.6.3.3 When the liquid has reached an apparent volume of 1 mL,
remove the K-D apparatus from the bath and allow the solvent to drain
and cool for at least 10 minutes. Remove the Snyder column and rinse the
flask and its lower joint into the concentrator tube with 1-2 mL of
solvent. A 5 mL syringe is recommended for this operation.
12.6.3.4 Remove the three-ball Snyder column, add a fresh boiling
chip, and attach a two-ball micro Snyder column to the concentrator
tube. Prewet the column by adding approximately 0.5 mL of solvent
through the top. Place the apparatus in the hot water bath.
12.6.3.5 Adjust the vertical position and the water temperature as
required to complete the concentration in 5-10 minutes. At the proper
rate of distillation, the balls of the column will actively chatter but
the chambers will not flood.
12.6.3.6 When the liquid reaches an apparent volume of 0.5 mL,
remove the apparatus from the water bath and allow to drain and cool for
at least 10 minutes.
12.6.3.7 Proceed to 12.6.4 for preparation for back-extraction or
micro-concentration and solvent exchange.
12.6.4 Preparation for back-extraction or micro-concentration and
solvent exchange.
12.6.4.1 For back-extraction (Section 12.5), transfer the extract to
a 250 mL separatory funnel. Rinse the concentration vessel with small
portions of hexane, adjust the hexane volume in the separatory funnel to
10-20 mL, and proceed to back-extraction (Section 12.5).
12.6.4.2 For determination of the weight of residue in the extract,
or for clean-up procedures other than back-extraction, transfer the
extract to a blowdown vial using two to three rinses of solvent. Proceed
with micro-concentration and solvent exchange (Section 12.7).
12.7 Micro-Concentration and Solvent Exchange.
12.7.1 Extracts to be subjected to GPC or HPLC cleanup are exchanged
into methylene chloride. Extracts to be cleaned up using silica gel,
alumina, carbon, and/or Florisil are exchanged into hexane.
12.7.2 Transfer the vial containing the sample extract to a nitrogen
blowdown device. Adjust the flow of nitrogen so that the surface of the
solvent is just visibly disturbed.
Note: A large vortex in the solvent may cause analyte loss.
12.7.3 Lower the vial into a 45 [deg]C water bath and continue
concentrating.
12.7.3.1 If the extract is to be concentrated to dryness for weight
determination (Sections 12.4.1.8, 12.4.2.7, and 13.7.1.4), blow dry
until a constant weight is obtained.
12.7.3.2 If the extract is to be concentrated for injection into the
GC/MS or the
[[Page 259]]
solvent is to be exchanged for extract cleanup, proceed as follows:
12.7.4 When the volume of the liquid is approximately 100 L, add 2-3
mL of the desired solvent (methylene chloride for GPC and HPLC, or
hexane for the other cleanups) and continue concentration to
approximately 100 [micro]L. Repeat the addition of solvent and
concentrate once more.
12.7.5 If the extract is to be cleaned up by GPC, adjust the volume
of the extract to 5.0 mL with methylene chloride. If the extract is to
be cleaned up by HPLC, further concentrate the extract to 30 [micro]L.
Proceed with GPC or HPLC cleanup (Section 13.2 or 13.6, respectively).
12.7.6 If the extract is to be cleaned up by column chromatography
(alumina, silica gel, Carbopak/Celite, or Florisil), bring the final
volume to 1.0 mL with hexane. Proceed with column cleanups (Sections
13.3 through 13.5 and 13.8).
12.7.7 If the extract is to be concentrated for injection into the
GC/MS (Section 14), quantitatively transfer the extract to a 0.3 mL
conical vial for final concentration, rinsing the larger vial with
hexane and adding the rinse to the conical vial. Reduce the volume to
approximately 100 [micro]L. Add 10 [micro]L of nonane to the vial, and
evaporate the solvent to the level of the nonane. Seal the vial and
label with the sample number. Store in the dark at room temperature
until ready for GC/MS analysis. If GC/MS analysis will not be performed
on the same day, store the vial at <-10 [deg]C.
13.0 Extract Cleanup
13.1 Cleanup may not be necessary for relatively clean samples
(e.g., treated effluents, groundwater, drinking water). If particular
circumstances require the use of a cleanup procedure, the analyst may
use any or all of the procedures below or any other appropriate
procedure. Before using a cleanup procedure, the analyst must
demonstrate that the requirements of Section 9.2 can be met using the
cleanup procedure. If only 2,3,7,8-TCDD and 2,3,7,8-TCDF are to be
determined, the cleanup procedures may be optimized for isolation of
these two compounds.
13.1.1 Gel permeation chromatography (Section 13.2) removes high
molecular weight interferences that cause GC column performance to
degrade. It should be used for all soil and sediment extracts and may be
used for water extracts that are expected to contain high molecular
weight organic compounds (e.g., polymeric materials, humic acids).
13.1.2 Acid, neutral, and basic silica gel (Section 13.3), alumina
(Section 13.4), and Florisil (Section 13.8) are used to remove nonpolar
and polar interferences. Alumina and Florisil are used to remove
chlorodiphenyl ethers.
13.1.3 Carbopak/Celite (Section 13.5) is used to remove nonpolar
interferences.
13.1.4 HPLC (Section 13.6) is used to provide specificity for the
2,3,7,8-substituted and other CDD and CDF isomers.
13.1.5 The anthropogenic isolation column (Section 13.7.1),
acidified silica gel batch adsorption procedure (Section 13.7.2), and
sulfuric acid and base back-extraction (Section 13.7.3) are used for
removal of lipids from tissue samples.
13.2 Gel Permeation Chromatography (GPC).
13.2.1 Column packing.
13.2.1.1 Place 70-75 g of SX-3 Bio-beads (Section 6.7.1.1) in a 400-
500 mL beaker.
13.2.1.2 Cover the beads with methylene chloride and allow to swell
overnight (a minimum of 12 hours).
13.2.1.3 Transfer the swelled beads to the column (Section 6.7.1.1)
and pump solvent through the column, from bottom to top, at 4.5-5.5 mL/
minute prior to connecting the column to the detector.
13.2.1.4 After purging the column with solvent for one to two hours,
adjust the column head pressure to 7-10 psig and purge for four to five
hours to remove air. Maintain a head pressure of 7-10 psig. Connect the
column to the detector (Section 6.7.1.4).
13.2.2 Column calibration.
13.2.2.1 Load 5 mL of the calibration solution (Section 7.4) into
the sample loop.
13.2.2.2 Inject the calibration solution and record the signal from
the detector. The elution pattern will be corn oil, bis(2-ethyl
hexyl)phthalate, pentachlorophenol, perylene, and sulfur.
13.2.2.3 Set the ``dump time'' to allow 85% removal of
the corn oil and 85% collection of the phthalate.
13.2.2.4 Set the ``collect time'' to the peak minimum between
perylene and sulfur.
13.2.2.5 Verify the calibration with the calibration solution after
every 20 extracts. Calibration is verified if the recovery of the
pentachlorophenol is greater than 85%. If calibration is not verified,
the system shall be recalibrated using the calibration solution, and the
previous 20 samples shall be re-extracted and cleaned up using the
calibrated GPC system.
13.2.3 Extract cleanup--GPC requires that the column not be
overloaded. The column specified in this method is designed to handle a
maximum of 0.5 g of high molecular weight material in a 5 mL extract. If
the extract is known or expected to contain more than 0.5 g, the extract
is split into aliquots for GPC, and the aliquots are combined after
elution from the column. The residue content of the extract may be
obtained gravimetrically by evaporating the solvent from a 50 [micro]L
aliquot.
13.2.3.1 Filter the extract or load through the filter holder
(Section 6.7.1.3) to remove the particles. Load the 5.0 mL extract onto
the column.
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13.2.3.2 Elute the extract using the calibration data determined in
Section 13.2.2. Collect the eluate in a clean 400-500 mL beaker.
13.2.3.3 Rinse the sample loading tube thoroughly with methylene
chloride between extracts to prepare for the next sample.
13.2.3.4 If a particularly dirty extract is encountered, a 5.0 mL
methylene chloride blank shall be run through the system to check for
carry-over.
13.2.3.5 Concentrate the eluate per Sections 12.6 and 12.7 for
further cleanup or injection into the GC/MS.
13.3 Silica Gel Cleanup.
13.3.1 Place a glass-wool plug in a 15 mm ID chromatography column
(Section 6.7.4.2). Pack the column bottom to top with: 1 g silica gel
(Section 7.5.1.1), 4 g basic silica gel (Section 7.5.1.3), 1 g silica
gel, 8 g acid silica gel (Section 7.5.1.2), 2 g silica gel, and 4 g
granular anhydrous sodium sulfate (Section 7.2.1). Tap the column to
settle the adsorbents.
13.3.2 Pre-elute the column with 50-100 mL of hexane. Close the
stopcock when the hexane is within 1 mm of the sodium sulfate. Discard
the eluate. Check the column for channeling. If channeling is present,
discard the column and prepare another.
13.3.3 Apply the concentrated extract to the column. Open the
stopcock until the extract is within 1 mm of the sodium sulfate.
13.3.4 Rinse the receiver twice with 1 mL portions of hexane, and
apply separately to the column. Elute the CDDs/CDFs with 100 mL hexane,
and collect the eluate.
13.3.5 Concentrate the eluate per Sections 12.6 and 12.7 for further
cleanup or injection into the HPLC or GC/MS.
13.3.6 For extracts of samples known to contain large quantities of
other organic compounds (such as paper mill effluents), it may be
advisable to increase the capacity of the silica gel column. This may be
accomplished by increasing the strengths of the acid and basic silica
gels. The acid silica gel (Section 7.5.1.2) may be increased in strength
to as much as 44% w/w (7.9 g sulfuric acid added to 10 g silica gel).
The basic silica gel (Section 7.5.1.3) may be increased in strength to
as much as 33% w/w (50 mL 1N NaOH added to 100 g silica gel), or the
potassium silicate (Section 7.5.1.4) may be used.
Note: The use of stronger acid silica gel (44% w/w) may lead to
charring of organic compounds in some extracts. The charred material may
retain some of the analytes and lead to lower recoveries of CDDs/CDFs.
Increasing the strengths of the acid and basic silica gel may also
require different volumes of hexane than those specified above to elute
the analytes off the column. Therefore, the performance of the method
after such modifications must be verified by the procedure in Section
9.2.
13.4 Alumina Cleanup.
13.4.1 Place a glass-wool plug in a 15 mm ID chromatography column
(Section 6.7.4.2).
13.4.2 If using acid alumina, pack the column by adding 6 g acid
alumina (Section 7.5.2.1). If using basic alumina, substitute 6 g basic
alumina (Section 7.5.2.2). Tap the column to settle the adsorbents.
13.4.3 Pre-elute the column with 50-100 mL of hexane. Close the
stopcock when the hexane is within 1 mm of the alumina.
13.4.4 Discard the eluate. Check the column for channeling. If
channeling is present, discard the column and prepare another.
13.4.5 Apply the concentrated extract to the column. Open the
stopcock until the extract is within 1 mm of the alumina.
13.4.6 Rinse the receiver twice with 1 mL portions of hexane and
apply separately to the column. Elute the interfering compounds with 100
mL hexane and discard the eluate.
13.4.7 The choice of eluting solvents will depend on the choice of
alumina (acid or basic) made in Section 13.4.2.
13.4.7.1 If using acid alumina, elute the CDDs/CDFs from the column
with 20 mL methylene chloride:hexane (20:80 v/v). Collect the eluate.
13.4.7.2 If using basic alumina, elute the CDDs/CDFs from the column
with 20 mL methylene chloride:hexane (50:50 v/v). Collect the eluate.
13.4.8 Concentrate the eluate per Sections 12.6 and 12.7 for further
cleanup or injection into the HPLC or GC/MS.
13.5 Carbon Column.
13.5.1 Cut both ends from a 10 mL disposable serological pipet
(Section 6.7.3.2) to produce a 10 cm column. Fire-polish both ends and
flare both ends if desired. Insert a glass-wool plug at one end, and
pack the column with 0.55 g of Carbopak/Celite (Section 7.5.3.3) to form
an adsorbent bed approximately 2 cm long. Insert a glass-wool plug on
top of the bed to hold the adsorbent in place.
13.5.2 Pre-elute the column with 5 mL of toluene followed by 2 mL of
methylene chloride: methanol:toluene (15:4:1 v/v), 1 mL of methylene
chloride:cyclohexane (1:1 v/v), and 5 mL of hexane. If the flow rate of
eluate exceeds 0.5 mL/minute, discard the column.
13.5.3 When the solvent is within 1 mm of the column packing, apply
the sample extract to the column. Rinse the sample container twice with
1 mL portions of hexane and apply separately to the column. Apply 2 mL
of hexane to complete the transfer.
13.5.4 Elute the interfering compounds with two 3 mL portions of
hexane, 2 mL of methylene chloride:cyclohexane (1:1 v/v), and 2 mL of
methylene chloride:methanol:toluene (15:4:1 v/v). Discard the eluate.
13.5.5 Invert the column, and elute the CDDs/CDFs with 20 mL of
toluene. If carbon particles are present in the eluate, filter through
glass-fiber filter paper.
[[Page 261]]
13.5.6 Concentrate the eluate per Sections 12.6 and 12.7 for further
cleanup or injection into the HPLC or GC/MS.
13.6 HPLC (Reference 6).
13.6.1 Column calibration.
13.6.1.1 Prepare a calibration standard containing the 2,3,7,8-
substituted isomers and/or other isomers of interest at a concentration
of approximately 500 pg/[micro]L in methylene chloride.
13.6.1.2 Inject 30 [micro]L of the calibration solution into the
HPLC and record the signal from the detector. Collect the eluant for
reuse. The elution order will be the tetra- through octa-isomers.
13.6.1.3 Establish the collection time for the tetra-isomers and for
the other isomers of interest. Following calibration, flush the
injection system with copious quantities of methylene chloride,
including a minimum of five 50 [micro]L injections while the detector is
monitored, to ensure that residual CDDs/CDFs are removed from the
system.
13.6.1.4 Verify the calibration with the calibration solution after
every 20 extracts. Calibration is verified if the recovery of the CDDs/
CDFs from the calibration standard (Section 13.6.1.1) is 75-125%
compared to the calibration (Section 13.6.1.2). If calibration is not
verified, the system shall be recalibrated using the calibration
solution, and the previous 20 samples shall be re-extracted and cleaned
up using the calibrated system.
13.6.2 Extract cleanup--HPLC requires that the column not be
overloaded. The column specified in this method is designed to handle a
maximum of 30 [micro]L of extract. If the extract cannot be concentrated
to less than 30 [micro]L, it is split into fractions and the fractions
are combined after elution from the column.
13.6.2.1 Rinse the sides of the vial twice with 30 [micro]L of
methylene chloride and reduce to 30 [micro]L with the evaporation
apparatus (Section 12.7).
13.6.2.2 Inject the 30 [micro]L extract into the HPLC.
13.6.2.3 Elute the extract using the calibration data determined in
Section 13.6.1. Collect the fraction(s) in a clean 20 mL concentrator
tube containing 5 mL of hexane:acetone (1:1 v/v).
13.6.2.4 If an extract containing greater than 100 ng/mL of total
CDD or CDF is encountered, a 30 [micro]L methylene chloride blank shall
be run through the system to check for carry-over.
13.6.2.5 Concentrate the eluate per Section 12.7 for injection into
the GC/MS.
13.7 Cleanup of Tissue Lipids--Lipids are removed from the Soxhlet
extract using either the anthropogenic isolation column (Section 13.7.1)
or acidified silica gel (Section 13.7.2), or are removed from the HCl
digested extract using sulfuric acid and base back-extraction (Section
13.7.3).
13.7.1 Anthropogenic isolation column (References 22 and 27)--Used
for removal of lipids from the Soxhlet/SDS extraction (Section 12.4.1).
13.7.1.1 Prepare the column as given in Section 7.5.4.
13.7.1.2 Pre-elute the column with 100 mL of hexane. Drain the
hexane layer to the top of the column, but do not expose the sodium
sulfate.
13.7.1.3 Load the sample and rinses (Section 12.4.1.9.2) onto the
column by draining each portion to the top of the bed. Elute the CDDs/
CDFs from the column into the apparatus used for concentration (Section
12.4.1.7) using 200 mL of hexane.
13.7.1.4 Concentrate the cleaned up extract (Sections 12.6 through
12.7) to constant weight per Section 12.7.3.1. If more than 500 mg of
material remains, repeat the cleanup using a fresh anthropogenic
isolation column.
13.7.1.5 Redissolve the extract in a solvent suitable for the
additional cleanups to be used (Sections 13.2 through 13.6 and 13.8).
13.7.1.6 Spike 1.0 mL of the cleanup standard (Section 7.11) into
the residue/solvent.
13.7.1.7 Clean up the extract using the procedures in Sections 13.2
through 13.6 and 13.8. Alumina (Section 13.4) or Florisil (Section 13.8)
and carbon (Section 13.5) are recommended as minimum additional cleanup
steps.
13.7.1.8 Following cleanup, concentrate the extract to 10 [micro]L
as described in Section 12.7 and proceed with the analysis in Section
14.
13.7.2 Acidified silica gel (Reference 28)--Procedure alternate to
the anthropogenic isolation column (Section 13.7.1) that is used for
removal of lipids from the Soxhlet/SDS extraction (Section 12.4.1).
13.7.2.1 Adjust the volume of hexane in the bottle (Section
12.4.1.9.2) to approximately 200 mL.
13.7.2.2 Spike 1.0 mL of the cleanup standard (Section 7.11) into
the residue/solvent.
13.7.2.3 Drop the stirring bar into the bottle, place the bottle on
the stirring plate, and begin stirring.
13.7.2.4 Add 30-100 g of acid silica gel (Section 7.5.1.2) to the
bottle while stirring, keeping the silica gel in motion. Stir for two to
three hours.
Note: 30 grams of silica gel should be adequate for most samples and
will minimize contamination from this source.
13.7.2.5 After stirring, pour the extract through approximately 10 g
of granular anhydrous sodium sulfate (Section 7.2.1) contained in a
funnel with glass-fiber filter into a macro contration device (Section
12.6). Rinse the bottle and sodium sulfate with hexane to complete the
transfer.
[[Page 262]]
13.7.2.6 Concentrate the extract per Sections 12.6 through 12.7 and
clean up the extract using the procedures in Sections 13.2 through 13.6
and 13.8. Alumina (Section 13.4) or Florisil (Section 13.8) and carbon
(Section 13.5) are recommended as minimum additional cleanup steps.
13.7.3 Sulfuric acid and base back-extraction. Used with HCl
digested extracts (Section 12.4.2).
13.7.3.1 Spike 1.0 mL of the cleanup standard (Section 7.11) into
the residue/solvent (Section 12.4.2.8.2).
13.7.3.2 Add 10 mL of concentrated sulfuric acid to the bottle.
Immediately cap and shake one to three times. Loosen cap in a hood to
vent excess pressure. Cap and shake the bottle so that the residue/
solvent is exposed to the acid for a total time of approximately 45
seconds.
13.7.3.3 Decant the hexane into a 250 mL separatory funnel making
sure that no acid is transferred. Complete the quantitative transfer
with several hexane rinses.
13.7.3.4 Back extract the solvent/residue with 50 mL of potassium
hydroxide solution per Section 12.5.2, followed by two reagent water
rinses.
13.7.3.5 Drain the extract through a filter funnel containing
approximately 10 g of granular anhydrous sodium sulfate in a glass-fiber
filter into a macro concentration device (Section 12.6).
13.7.3.6 Concentrate the cleaned up extract to a volume suitable for
the additional cleanups given in Sections 13.2 through 13.6 and 13.8.
Gel permeation chromatography (Section 13.2), alumina (Section 13.4) or
Florisil (Section 13.8), and Carbopak/Celite (Section 13.5) are
recommended as minimum additional cleanup steps.
13.7.3.7 Following cleanup, concentrate the extract to 10 L as
described in Section 12.7 and proceed with analysis per Section 14.
13.8 Florisil Cleanup (Reference 29).
13.8.1 Pre-elute the activated Florisil column (Section 7.5.3) with
10 mL of methylene chloride followed by 10 mL of hexane:methylene
chloride (98:2 v/v) and discard the solvents.
13.8.2 When the solvent is within 1 mm of the packing, apply the
sample extract (in hexane) to the column. Rinse the sample container
twice with 1 mL portions of hexane and apply to the column.
13.8.3 Elute the interfering compounds with 20 mL of
hexane:methylene chloride (98:2) and discard the eluate.
13.8.4 Elute the CDDs/CDFs with 35 mL of methylene chloride and
collect the eluate. Concentrate the eluate per Sections 12.6 through
12.7 for further cleanup or for injection into the HPLC or GC/MS.
14.0 HRGC/HRMS Analysis
14.1 Establish the operating conditions given in Section 10.1.
14.2 Add 10 uL of the appropriate internal standard solution
(Section 7.12) to the sample extract immediately prior to injection to
minimize the possibility of loss by evaporation, adsorption, or
reaction. If an extract is to be reanalyzed and evaporation has
occurred, do not add more instrument internal standard solution. Rather,
bring the extract back to its previous volume (e.g., 19 L) with pure
nonane only (18 L if 2 L injections are used).
14.3 Inject 1.0 [micro]L or 2.0 [micro]L of the concentrated extract
containing the internal standard solution, using on-column or splitless
injection. The volume injected must be identical to the volume used for
calibration (Section 10). Start the GC column initial isothermal hold
upon injection. Start MS data collection after the solvent peak elutes.
Stop data collection after the OCDD and OCDF have eluted. If only
2,3,7,8-TCDD and 2,3,7,8-TCDF are to be determined, stop data collection
after elution of these compounds. Return the column to the initial
temperature for analysis of the next extract or standard.
15.0 System and Laboratory Performance
15.1 At the beginning of each 12-hour shift during which analyses
are performed, GC/MS system performance and calibration are verified for
all CDDs/CDFs and labeled compounds. For these tests, analysis of the
CS3 calibration verification (VER) standard (Section 7.13 and Table 4)
and the isomer specificity test standards (Section 7.15 and Table 5)
shall be used to verify all performance criteria. Adjustment and/or
recalibration (Section 10) shall be performed until all performance
criteria are met. Only after all performance criteria are met may
samples, blanks, IPRs, and OPRs be analyzed.
15.2 MS Resolution--A static resolving power of at least 10,000 (10%
valley definition) must be demonstrated at the appropriate m/z before
any analysis is performed. Static resolving power checks must be
performed at the beginning and at the end of each 12-hour shift
according to procedures in Section 10.1.2. Corrective actions must be
implemented whenever the resolving power does not meet the requirement.
15.3 Calibration Verification.
15.3.1 Inject the VER standard using the procedure in Section 14.
15.3.2 The m/z abundance ratios for all CDDs/CDFs shall be within
the limits in Table 9; otherwise, the mass spectrometer shall be
adjusted until the m/z abundance ratios fall within the limits
specified, and the verification test shall be repeated. If the
adjustment alters the resolution of the mass spectrometer, resolution
shall be verified (Section 10.1.2) prior to repeat of the verification
test.
15.3.3 The peaks representing each CDD/CDF and labeled compound in
the VER
[[Page 263]]
standard must be present with S/N of at least 10; otherwise, the mass
spectrometer shall be adjusted and the verification test repeated.
15.3.4 Compute the concentration of each CDD/CDF compound by isotope
dilution (Section 10.5) for those compounds that have labeled analogs
(Table 1). Compute the concentration of the labeled compounds by the
internal standard method (Section 10.6). These concentrations are
computed based on the calibration data in Section 10.
15.3.5 For each compound, compare the concentration with the
calibration verification limit in Table 6. If only 2,3,7,8-TCDD and
2,3,7,8-TCDF are to be determined, compare the concentration to the
limit in Table 6a. If all compounds meet the acceptance criteria,
calibration has been verified and analysis of standards and sample
extracts may proceed. If, however, any compound fails its respective
limit, the measurement system is not performing properly for that
compound. In this event, prepare a fresh calibration standard or correct
the problem causing the failure and repeat the resolution (Section 15.2)
and verification (Section 15.3) tests, or recalibrate (Section 10).
15.4 Retention Times and GC Resolution.
15.4.1 Retention times.
15.4.1.1 Absolute--The absolute retention times of the
13C12-1,2,3,4-TCDD and
13C12-1,2,3,7,8,9-HxCDD GCMS internal standards in
the verification test (Section 15.3) shall be within 15 seconds of the retention times obtained during
calibration (Sections 10.2.1 and 10.2.4).
15.4.1.2 Relative--The relative retention times of CDDs/CDFs and
labeled compounds in the verification test (Section 15.3) shall be
within the limits given in Table 2.
15.4.2 GC resolution.
15.4.2.1 Inject the isomer specificity standards (Section 7.15) on
their respective columns.
15.4.2.2 The valley height between 2,3,7,8-TCDD and the other tetra-
dioxin isomers at m/z 319.8965, and between 2,3,7,8-TCDF and the other
tetra-furan isomers at m/z 303.9016 shall not exceed 25% on their
respective columns (Figures 6 and 7).
15.4.3 If the absolute retention time of any compound is not within
the limits specified or if the 2,3,7,8-isomers are not resolved, the GC
is not performing properly. In this event, adjust the GC and repeat the
verification test (Section 15.3) or recalibrate (Section 10), or replace
the GC column and either verify calibration or recalibrate.
15.5 Ongoing Precision and Recovery.
15.5.1 Analyze the extract of the ongoing precision and recovery
(OPR) aliquot (Section 11.4.2.5, 11.5.4, 11.6.2, 11.7.4, or 11.8.3.2)
prior to analysis of samples from the same batch.
15.5.2 Compute the concentration of each CDD/CDF by isotope dilution
for those compounds that have labeled analogs (Section 10.5). Compute
the concentration of 1,2,3,7,8,9-HxCDD, OCDF, and each labeled compound
by the internal standard method (Section 10.6).
15.5.3 For each CDD/CDF and labeled compound, compare the
concentration to the OPR limits given in Table 6. If only 2,3,7,8-TCDD
and 2,3,7,8-TCDF are to be determined, compare the concentration to the
limits in Table 6a. If all compounds meet the acceptance criteria,
system performance is acceptable and analysis of blanks and samples may
proceed. If, however, any individual concentration falls outside of the
range given, the extraction/concentration processes are not being
performed properly for that compound. In this event, correct the
problem, re-prepare, extract, and clean up the sample batch and repeat
the ongoing precision and recovery test (Section 15.5).
15.5.4 Add results that pass the specifications in Section 15.5.3 to
initial and previous ongoing data for each compound in each matrix.
Update QC charts to form a graphic representation of continued
laboratory performance. Develop a statement of laboratory accuracy for
each CDD/CDF in each matrix type by calculating the average percent
recovery (R) and the standard deviation of percent recovery
(SR). Express the accuracy as a recovery interval from R-
2SR to R=2SR. For example, if R=95% and
SR=5%, the accuracy is 85-105%.
15.6 Blank--Analyze the method blank extracted with each sample
batch immediately following analysis of the OPR aliquot to demonstrate
freedom from contamination and freedom from carryover from the OPR
analysis. The results of the analysis of the blank must meet the
specifications in Section 9.5.2 before sample analyses may proceed.
16.0 Qualitative Determination
A CDD, CDF, or labeled compound is identified in a standard, blank,
or sample when all of the criteria in Sections 16.1 through 16.4 are
met.
16.1 The signals for the two exact m/z's in Table 8 must be present
and must maximize within the same two seconds.
16.2 The signal-to-noise ratio (S/N) for the GC peak at each exact
m/z must be greater than or equal to 2.5 for each CDD or CDF detected in
a sample extract, and greater than or equal to 10 for all CDDs/CDFs in
the calibration standard (Sections 10.2.3 and 15.3.3).
16.3 The ratio of the integrated areas of the two exact m/z's
specified in Table 8 must be within the limit in Table 9, or within
10% of the ratio in the midpoint (CS3) calibration
or calibration verification (VER), whichever is most recent.
16.4 The relative retention time of the peak for a 2,3,7,8-
substituted CDD or CDF must be within the limit in Table 2. The
retention time of peaks representing non-
[[Page 264]]
2,3,7,8-substituted CDDs/CDFs must be within the retention time windows
established in Section 10.3.
16.5 Confirmatory Analysis--Isomer specificity for 2,3,7,8-TCDF
cannot be achieved on the DB-5 column. Therefore, any sample in which
2,3,7,8-TCDF is identified by analysis on a DB-5 column must have a
confirmatory analysis performed on a DB-225, SP-2330, or equivalent GC
column. The operating conditions in Section 10.1.1 may be adjusted to
optimize the analysis on the second GC column, but the GC/MS must meet
the mass resolution and calibration specifications in Section 10.
16.6 If the criteria for identification in Sections 16.1 through
16.5 are not met, the CDD or CDF has not been identified and the results
may not be reported for regulatory compliance purposes. If interferences
preclude identification, a new aliquot of sample must be extracted,
further cleaned up, and analyzed.
17.0 Quantitative Determination
17.1 Isotope Dilution Quantitation--By adding a known amount of a
labeled compound to every sample prior to extraction, correction for
recovery of the CDD/CDF can be made because the CDD/CDF and its labeled
analog exhibit similar effects upon extraction, concentration, and gas
chromatography. Relative response (RR) values are used in conjunction
with the initial calibration data described in Section 10.5 to determine
concentrations directly, so long as labeled compound spiking levels are
constant, using the following equation:
[GRAPHIC] [TIFF OMITTED] TR15SE97.007
where:
Cex = The concentration of the CDD/CDF in the extract, and
the other terms are as defined in Section 10.5.2.
17.1.1 Because of a potential interference, the labeled analog of
OCDF is not added to the sample. Therefore, OCDF is quantitated against
labeled OCDD. As a result, the concentration of OCDF is corrected for
the recovery of the labeled OCDD. In instances where OCDD and OCDF
behave differently during sample extraction, concentration, and cleanup
procedures, this may decrease the accuracy of the OCDF results. However,
given the low toxicity of this compound relative to the other dioxins
and furans, the potential decrease in accuracy is not considered
significant.
17.1.2 Because 13C12-1,2,3,7,8,9-HxCDD is used
as an instrument internal standard (i.e., not added before extraction of
the sample), it cannot be used to quantitate the 1,2,3,7,8,9-HxCDD by
strict isotope dilution procedures. Therefore, 1,2,3,7,8,9-HxCDD is
quantitated using the averaged response of the labeled analogs of the
other two 2,3,7,8-substituted HxCDD's: 1,2,3,4,7,8-HxCDD and
1,2,3,6,7,8-HxCDD. As a result, the concentration of 1,2,3,7,8,9-HxCDD
is corrected for the average recovery of the other two HxCDD's.
17.1.3 Any peaks representing non-2,3,7,8-substituted CDDs/CDFs are
quantitated using an average of the response factors from all of the
labeled 2,3,7,8-isomers at the same level of chlorination.
17.2 Internal Standard Quantitation and Labeled Compound Recovery.
17.2.1 Compute the concentrations of 1,2,3,7,8,9-HxCDD, OCDF, the
13C-labeled analogs and the 37C-labeled cleanup
standard in the extract using the response factors determined from the
initial calibration data (Section 10.6) and the following equation:
[GRAPHIC] [TIFF OMITTED] TR15SE97.008
where:
Cex = The concentration of the CDD/CDF in the extract, and
the other terms are as defined in Section 10.6.1.
Note: There is only one m/z for the 37Cl-labeled
standard.
17.2.2 Using the concentration in the extract determined above,
compute the percent recovery of the 13C-labeled compounds and
the 37C-labeled cleanup standard using the following
equation:
[GRAPHIC] [TIFF OMITTED] TR15SE97.009
17.3 The concentration of a CDD/CDF in the solid phase of the sample
is computed using the concentration of the compound in the extract and
the weight of the solids (Section 11.5.1), as follows:
[[Page 265]]
[GRAPHIC] [TIFF OMITTED] TR15SE97.010
where:
Cex = The concentration of the compound in the extract.
Vex = The extract volume in mL.
Ws = The sample weight (dry weight) in kg.
17.4 The concentration of a CDD/CDF in the aqueous phase of the
sample is computed using the concentration of the compound in the
extract and the volume of water extracted (Section 11.4 or 11.5), as
follows:
[GRAPHIC] [TIFF OMITTED] TR15SE97.011
where:
Cex = The concentration of the compound in the extract.
Vex = The extract volume in mL.
Vs = The sample volume in liters.
17.5 If the SICP area at either quantitation m/z for any compound
exceeds the calibration range of the system, a smaller sample aliquot is
extracted.
17.5.1 For aqueous samples containing 1% solids or less, dilute 100
mL, 10 mL, etc., of sample to 1 L with reagent water and re-prepare,
extract, clean up, and analyze per Sections 11 through 14.
17.5.2 For samples containing greater than 1% solids, extract an
amount of sample equal to 1/10, 1/100, etc., of
the amount used in Section 11.5.1. Re-prepare, extract, clean up, and
analyze per Sections 11 through 14.
17.5.3 If a smaller sample size will not be representative of the
entire sample, dilute the sample extract by a factor of 10, adjust the
concentration of the instrument internal standard to 100 pg/[micro]L in
the extract, and analyze an aliquot of this diluted extract by the
internal standard method.
17.6 Results are reported to three significant figures for the CDDs/
CDFs and labeled compounds found in all standards, blanks, and samples.
17.6.1 Reporting units and levels.
17.6.1.1 Aqueous samples--Report results in pg/L (parts-per-
quadrillion).
17.6.1.2 Samples containing greater than 1% solids (soils,
sediments, filter cake, compost)--Report results in ng/kg based on the
dry weight of the sample. Report the percent solids so that the result
may be corrected.
17.6.1.3 Tissues--Report results in ng/kg of wet tissue, not on the
basis of the lipid content of the sample. Report the percent lipid
content, so that the data user can calculate the concentration on a
lipid basis if desired.
17.6.1.4 Reporting level.
17.6.1.4.1 Standards (VER, IPR, OPR) and samples--Report results at
or above the minimum level (Table 2). Report results below the minimum
level as not detected or as required by the regulatory authority.
17.6.1.4.2 Blanks--Report results above one-third the ML.
17.6.2 Results for CDDs/CDFs in samples that have been diluted are
reported at the least dilute level at which the areas at the
quantitation m/z's are within the calibration range (Section 17.5).
17.6.3 For CDDs/CDFs having a labeled analog, results are reported
at the least dilute level at which the area at the quantitation m/z is
within the calibration range (Section 17.5) and the labeled compound
recovery is within the normal range for the method (Section 9.3 and
Tables 6, 6a, 7, and 7a).
17.6.4 Additionally, if requested, the total concentration of all
isomers in an individual level of chlorination (i.e., total TCDD, total
TCDF, total Paced, etc.) may be reported by summing the concentrations
of all isomers identified in that level of chlorination, including both
2,3,7,8-substituted and non-2,3,7,8-substituted isomers.
18.0 Analysis of Complex Samples
18.1 Some samples may contain high levels (10 ng/L;
1000 ng/kg) of the compounds of interest, interfering
compounds, and/or polymeric materials. Some extracts will not
concentrate to 10 [micro]L (Section 12.7); others may overload the GC
column and/or mass spectrometer.
18.2 Analyze a smaller aliquot of the sample (Section 17.5) when the
extract will not concentrate to 10 [micro]L after all cleanup procedures
have been exhausted.
18.3 Chlorodiphenyl Ethers--If chromatographic peaks are detected at
the retention time of any CDDs/CDFs in any of the m/z channels being
monitored for the
[[Page 266]]
chlorodiphenyl ethers (Table 8), cleanup procedures must be employed
until these interferences are removed. Alumina (Section 13.4) and
Florisil (Section 13.8) are recommended for removal of chlorodiphenyl
ethers.
18.4 Recovery of Labeled Compounds--In most samples, recoveries of
the labeled compounds will be similar to those from reagent water or
from the alternate matrix (Section 7.6).
18.4.1 If the recovery of any of the labeled compounds is outside of
the normal range (Table 7), a diluted sample shall be analyzed (Section
17.5).
18.4.2 If the recovery of any of the labeled compounds in the
diluted sample is outside of normal range, the calibration verification
standard (Section 7.13) shall be analyzed and calibration verified
(Section 15.3).
18.4.3 If the calibration cannot be verified, a new calibration must
be performed and the original sample extract reanalyzed.
18.4.4 If the calibration is verified and the diluted sample does
not meet the limits for labeled compound recovery, the method does not
apply to the sample being analyzed and the result may not be reported
for regulatory compliance purposes. In this case, alternate extraction
and cleanup procedures in this method must be employed to resolve the
interference. If all cleanup procedures in this method have been
employed and labeled compound recovery remains outside of the normal
range, extraction and/or cleanup procedures that are beyond this scope
of this method will be required to analyze these samples.
19.0 Pollution Prevention
19.1 The solvents used in this method pose little threat to the
environment when managed properly. The solvent evaporation techniques
used in this method are amenable to solvent recovery, and it is
recommended that the laboratory recover solvents wherever feasible.
19.2 Standards should be prepared in volumes consistent with
laboratory use to minimize disposal of standards.
20.0 Waste Management
20.1 It is the laboratory's responsibility to comply with all
federal, state, and local regulations governing waste management,
particularly the hazardous waste identification rules and land disposal
restrictions, and to protect the air, water, and land by minimizing and
controlling all releases from fume hoods and bench operations.
Compliance is also required with any sewage discharge permits and
regulations.
20.2 Samples containing HCl to pH <2 are hazardous and must be
neutralized before being poured down a drain or must be handled as
hazardous waste.
20.3 The CDDs/CDFs decompose above 800 [deg]C. Low-level waste such
as absorbent paper, tissues, animal remains, and plastic gloves may be
burned in an appropriate incinerator. Gross quantities (milligrams)
should be packaged securely and disposed of through commercial or
governmental channels that are capable of handling extremely toxic
wastes.
20.4 Liquid or soluble waste should be dissolved in methanol or
ethanol and irradiated with ultraviolet light with a wavelength shorter
than 290 nm for several days. Use F40 BL or equivalent lamps. Analyze
liquid wastes, and dispose of the solutions when the CDDs/CDFs can no
longer be detected.
20.5 For further information on waste management, consult ``The
Waste Management Manual for Laboratory Personnel'' and ``Less is
Better--Laboratory Chemical Management for Waste Reduction,'' available
from the American Chemical Society's Department of Government Relations
and Science Policy, 1155 16th Street N.W., Washington, D.C. 20036.
21.0 Method Performance
Method performance was validated and performance specifications were
developed using data from EPA's international interlaboratory validation
study (References 30-31) and the EPA/paper industry Long-Term
Variability Study of discharges from the pulp and paper industry (58 FR
66078).
22.0 References
1. Tondeur, Yves. ``Method 8290: Analytical Procedures and Quality
Assurance for Multimedia Analysis of Polychlorinated Dibenzo-p-dioxins
and Dibenzofurans by High Resolution Gas Chromatography/High Resolution
Mass Spectrometry,'' USEPA EMSL, Las Vegas, Nevada, June 1987.
2. ``Measurement of 2,3,7,8-Tetrachlorinated Dibenzo-p-dioxin (TCDD)
and 2,3,7,8-Tetrachlorinated Dibenzofuran (TCDF) in Pulp, Sludges,
Process Samples and Wastewaters from Pulp and Paper Mills,'' Wright
State University, Dayton, OH 45435, June 1988.
3. ``NCASI Procedures for the Preparation and Isomer Specific
Analysis of Pulp and Paper Industry Samples for 2,3,7,8-TCDD and
2,3,7,8-TCDF,'' National Council of the Paper Industry for Air and
Stream Improvement Inc., 260 Madison Avenue, New York, NY 10016,
Technical Bulletin No. 551, Pre-Release Copy, July 1988.
4. ``Analytical Procedures and Quality Assurance Plan for the
Determination of PCDD/PCDF in Fish,'' USEPA, Environmental Research
Laboratory, 6201 Congdon Boulevard, Duluth, MN 55804, April 1988.
5. Tondeur, Yves. ``Proposed GC/MS Methodology for the Analysis of
PCDDs and
[[Page 267]]
PCDFs in Special Analytical Services Samples,'' Triangle Laboratories,
Inc., 801-10 Capitola Dr, Research Triangle Park, NC 27713, January
1988; updated by personal communication September 1988.
6. Lamparski, L.L. and Nestrick, T.J. ``Determination of Tetra-,
Hexa-, Hepta-, and Octachlorodibenzo-p-dioxin Isomers in Particulate
Samples at Parts per Trillion Levels,'' Analytical Chemistry, 52: 2045-
2054, 1980.
7. Lamparski, L.L. and Nestrick, T.J. ``Novel Extraction Device for
the Determination of Chlorinated Dibenzo-p-dioxins (PCDDs) and
Dibenzofurans (PCDFs) in Matrices Containing Water,'' Chemosphere,
19:27-31, 1989.
8. Patterson, D.G., et. al. ``Control of Interferences in the
Analysis of Human Adipose Tissue for 2,3,7,8-Tetrachlorodibenzo-p-
dioxin,'' Environmental Toxicological Chemistry, 5:355-360, 1986.
9. Stanley, John S. and Sack, Thomas M. ``Protocol for the Analysis
of 2,3,7,8-Tetrachlorodibenzo-p-dioxin by High Resolution Gas
Chromatography/High Resolution Mass Spectrometry,'' USEPA EMSL, Las
Vegas, Nevada 89114, EPA 600/4-86-004, January 1986.
10. ``Working with Carcinogens,'' Department of Health, Education, &
Welfare, Public Health Service, Centers for Disease Control, NIOSH,
Publication 77-206, August 1977, NTIS PB-277256.
11. ``OSHA Safety and Health Standards, General Industry,'' OSHA
2206, 29 CFR 1910.
12. ``Safety in Academic Chemistry Laboratories,'' ACS Committee on
Chemical Safety, 1979.
13. ``Standard Methods for the Examination of Water and
Wastewater,'' 18th edition and later revisions, American Public Health
Association, 1015 15th St, N.W., Washington, DC 20005, 1-35: Section
1090 (Safety), 1992.
14. ``Method 613--2,3,7,8-Tetrachlorodibenzo-p-dioxin,'' 40 CFR 136
(49 FR 43234), October 26, 1984, Section 4.1.
15. Provost, L.P. and Elder, R.S. ``Interpretation of Percent
Recovery Data,'' American Laboratory, 15: 56-83, 1983.
16. ``Standard Practice for Sampling Water,'' ASTM Annual Book of
Standards, ASTM, 1916 Race Street, Philadelphia, PA 19103-1187, 1980.
17. ``Methods 330.4 and 330.5 for Total Residual Chlorine,'' USEPA,
EMSL, Cincinnati, OH 45268, EPA 600/4-79-020, March 1979.
18. ``Handbook of Analytical Quality Control in Water and Wastewater
Laboratories,'' USEPA EMSL, Cincinnati, OH 45268, EPA-600/4-79-019,
March 1979.
19. Williams, Rick. Letter to Bill Telliard, June 4, 1993, available
from the EPA Sample Control Center operated by DynCorp Viar, Inc., 300 N
Lee St, Alexandria, VA 22314, 703-519-1140.
20. Barkowski, Sarah. Fax to Sue Price, August 6, 1992, available
from the EPA Sample Control Center operated by DynCorp Viar, Inc., 300 N
Lee St, Alexandria VA 22314, 703-519-1140.
21. ``Analysis of Multi-media, Multi-concentration Samples for
Dioxins and Furans, PCDD/PCDF Analyses Data Package'', Narrative for
Episode 4419, MRI Project No. 3091-A, op.cit. February 12, 1993,
Available from the EPA Sample Control Center operated by DynCorp Viar
Inc, 300 N Lee St, Alexandria, VA 22314 (703-519-1140).
22. ``Analytical Procedures and Quality Assurance Plan for the
Determination of PCDD/PCDF in Fish'', U.S. Environmental Protection
Agency, Environmental Research Laboratory, Duluth, MN 55804, EPA/600/3-
90/022, March 1990.
23. Afghan, B.K., Carron, J., Goulden, P.D., Lawrence, J., Leger,
D., Onuska, F., Sherry, J., and Wilkenson, R.J., ``Recent Advances in
Ultratrace Analysis of Dioxins and Related Halogenated Hydrocarbons'',
Can J. Chem., 65: 1086-1097, 1987.
24. Sherry, J.P. and Tse, H. ``A Procedure for the Determination of
Polychlorinated Dibenzo-p-dioxins in Fish'', Chemosphere, 20: 865-872,
1990.
25. ``Preliminary Fish Tissue Study'', Results of Episode 4419,
available from the EPA Sample Control Center operated by DynCorp Viar,
Inc., 300 N Lee St, Alexandria, VA 22314, 703-519-1140.
26. Nestrick, Terry L. DOW Chemical Co., personal communication with
D.R. Rushneck, April 8, 1993. Details available from the U.S.
Environmental Protection Agency Sample Control Center operated by
DynCorp Viar Inc, 300 N Lee St, Alexandria, VA 22314, 703-519-1140.
27. Barnstadt, Michael. ``Big Fish Column'', Triangle Laboratories
of RTP, Inc., SOP 129-90, 27 March 27, 1992.
28. ``Determination of Polychlorinated Dibenzo-p-Dioxins (PCDD) and
Dibenzofurans (PCDF) in Environmental Samples Using EPA Method 1613'',
Chemical Sciences Department, Midwest Research Institute, 425 Volker
Boulevard, Kansas City, MO 44110-2299, Standard Operating Procedure No.
CS-153, January 15, 1992.
29. Ryan, John J. Raymonde Lizotte and William H. Newsome, J.
Chromatog. 303 (1984) 351-360.
30. Telliard, William A., McCarty, Harry B., and Riddick, Lynn S.
``Results of the Interlaboratory Validation Study of USEPA Method 1613
for the Analysis of Tetra-through Octachlorinated Dioxins and Furans by
Isotope Dilution GC/MS,'' Chemosphere, 27, 41-46 (1993).
31. ``Results of the International Interlaboratory Validation Study
of USEPA Method 1613'', October 1994, available from the EPA Sample
Control Center operated by DynCorp
[[Page 268]]
Viar, Inc., 300 N Lee St, Alexandria, VA 22314, 703-519-1140.
23.0 Tables and Figures
Table 1--Chlorinated Dibenzo-p-Dioxins and Furans Determined by Isotope Dilution and Internal Standard High
Resolution Gas Chromatography (HRGC)/High Resolution Mass Spectrometry (HRMS)
----------------------------------------------------------------------------------------------------------------
CDDs/CDFs \1\ CAS registry Labeled analog CAS registry
----------------------------------------------------------------------------------------------------------------
2,3,7,8-TCDD.................................. 1746-01-6 13C12-2,3,7,8-TCDD.............. 76523-40-5
37Cl4-2,3,7,8-TCDD.............. 85508-50-5
Total TCDD.................................... 41903-57-5
2,3,7,8-TCDF.................................. 51207-31-9 13C12-2,3,7,8-TCDF.............. 89059-46-1
Total-TCDF.................................... 55722-27-5
1,2,3,7,8-PeCDD............................... 40321-76-4 13C12-1,2,3,7,8-PeCDD........... 109719-79-1
Total-PeCDD................................... 36088-22-9
1,2,3,7,8-PeCDF............................... 57117-41-6 13C12-1,2,3,7,8-PeCDF........... 109719-77-9
2,3,4,7,8-PeCDF............................... 57117-31-4 13C12-2,3,4,7,8-PeCDF........... 116843-02-8
Total-PeCDF................................... 30402-15-4
1,2,3,4,7,8-HxCDD............................. 39227-28-6 13C12-1,2,3,4,7,8-HxCDD......... 109719-80-4
1,2,3,6,7,8-HxCDD............................. 57653-85-7 13C12-1,2,3,6,7,8-HxCDD......... 109719-81-5
1,2,3,7,8,9-HxCDD............................. 19408-74-3 13C12-1,2,3,7,8,9-HxCDD......... 109719-82-6
Total-HxCDD................................... 34465-46-8
1,2,3,4,7,8-HxCDF............................. 70648-26-9 13C12-1,2,3,4,7,8-HxCDF......... 114423-98-2
1,2,3,6,7,8-HxCDF............................. 57117-44-9 13C12-1,2,3,6,7,8-HxCDF......... 116843-03-9
1,2,3,7,8,9-HxCDF............................. 72918-21-9 13C12-1,2,3,7,8,9-HxCDF......... 116843-04-0
2,3,4,6,7,8-HxCDF............................. 60851-34-5 13C12-2,3,4,6,7,8-HxCDF......... 116843-05-1
Total-HxCDF................................... 55684-94-1
1,2,3,4,6,7,8-HpCDD........................... 35822-46-9 13C12-1,2,3,4,6,7,8-HpCDD....... 109719-83-7
Total-HpCDD................................... 37871-00-4
1,2,3,4,6,7,8-HpCDF........................... 67562-39-4 13C12-1,2,3,4,6,7,8-HpCDF....... 109719-84-8
1,2,3,4,7,8,9-HpCDF........................... 55673-89-7 13C12-1,2,3,4,7,8,9-HpCDF....... 109719-94-0
Total-HpCDF................................... 38998-75-3
OCDD.......................................... 3268-87-9 13C12-OCDD...................... 114423-97-1
OCDF.......................................... 39001-02-0 Not used........................
----------------------------------------------------------------------------------------------------------------
\1\ Chlorinated dibenzo-p-dioxins and chlorinated dibenzofurans.
TCDD = Tetrachlorodibenzo-p-dioxin.
TCDF = Tetrachlorodibenzofuran.
PeCDD = Pentachlorodibenzo-p-dioxin.
PeCDF = Pentachlorodibenzofuran.
HxCDD = Hexachlorodibenzo-p-dioxin.
HxCDF = Hexachlorodibenzofuran.
HpCDD = Heptachlorodibenzo-p-dioxin.
HpCDF = Heptachlorodibenzofuran.
OCDD = Octachlorodibenzo-p-dioxin.
OCDF = Octachlorodibenzofuran.
Table 2--Retention Time References, Quantitation References, Relative Retention Times, and Minimum Levels for
CDDS and DCFS
----------------------------------------------------------------------------------------------------------------
Minimum level \1\
--------------------------------
Retention time and Relative Extract
CDD/CDF quantitation reference retention time Water (pg/ Solid (ng/ (pg/
L; ppq) kg; ppt) [micro]L;
ppb)
----------------------------------------------------------------------------------------------------------------
Compounds using 13 C12-1,2,3,4-TCDD as the Injection Internal Standard
----------------------------------------------------------------------------------------------------------------
2,3,7,8-TCDF......................... 13 C12-2,3,7,8-TCDF..... 0.999-1.003 10 1 0.5
2,3,7,8-TCDD......................... 13 C12-2,3,7,8-TCDD..... 0.999-1.002 10 1 0.5
1,2,3,7,8-Pe......................... 13 C12-1,2,3,7,8-PeCDF.. 0.999-1.002 50 5 2.5
2,3,4,7,8-PeCDF...................... 13 C12-2,3,4,7,8-PeCDF.. 0.999-1.002 50 5 2.5
1,2,3,7,8-PeCDD...................... 13 C12-1,2,3,7,8-PeCDD.. 0.999-1.002 50 5 2.5
13 C12-2,3,7,8-TCDF.................. 13 C12-1,2,3,4-TCDD..... 0.923-1.103 ......... ......... .........
13 C12-2,3,7,8-TCDD.................. 13 C12-1,2,3,4-TCDD..... 0.976-1.043 ......... ......... .........
13 C12-2,3,7,8-TCDD.................. 13 C12-1,2,3,4-TCDD..... 0.989-1.052 ......... ......... .........
13 C12-1,2,3,7,8-PeCDF............... 13 C12-1,2,3,4-TCDD..... 1.000-1.425 ......... ......... .........
13 C12-2,3,4,7,8-PeCDF............... 13 C12-1,2,3,4-TCDD..... 1.001-1.526 ......... ......... .........
13 C12-1,2,3,7,8-PeCDF............... 13 C12-1,2,3,4-TCDD..... 1.000-1.567 ......... ......... .........
--------------------------------------
Compounds using 13 C12-1,2,3,7,8,9-HxCDD as the Injection Internal Standard
----------------------------------------------------------------------------------------------------------------
1,2,3,4,7,8-HxCDF.................... 13 C12-1,2,3,4,7,8-HxCDF 0.999-1.001 50 5 2.5
1,2,3,6,7,8-HxCDF.................... 13 C12-1,2,3,6,7,8-HxCDF 0.997-1.005 50 5 2.5
1,2,3,7,8,9-HxCDF.................... 13 C12-1,2,3,7,8,9-HxCDF 0.999-1.001 50 5 2.5
2,3,4,6,7,8-HxCDF.................... 13 C12-2,3,4,6,7,8-HxCDF 0.999-1.001 50 5 2.5
1,2,3,4,7,8-HxCDD.................... 13 C12-1,2,3,4,7,8-HxCDD 0.999-1.001 50 5 2.5
[[Page 269]]
1,2,3,6,7,8-HxCDD.................... 13 C12-1,2,3,6,7,8-HxCDD 0.998-1.004 50 5 2.5
1,2,3,7,8,9-HxCDD.................... (\2\)................... 1.000-1.019 50 5 2.5
1,2,3,4,6,7,8-HpCDF.................. 13 C12-1,2,3,4,6,7,8- 0.999-1.001 50 5 2.5
HpCDF.
1,2,3,4,7,8,9-HpCDF.................. 13 C12-1,2,3,4,7,8,9- 0.999-1.001 50 5 2.5
HpCDF.
1,2,3,4,6,7,8-HpCDD.................. 13 C12-1,2,3,4,6,7,8- 0.999-1.001 50 5 2.5
HpCDD.
OCDF................................. 13 C12-OCDD............. 0.999-1.001 100 10 5.0
OCDD................................. 13 C12-OCDD............. 0.999-1.001 100 10 5.0
1,2,3,4,6,7,8,-HxCDF................. 13 C12-1,2,3,7,8,9-HpCDD 0.949-0.975 ......... ......... .........
13 C121,2,3,7,8,9-HxCDF.............. 13 C12-1,2,3,7,8,9-HpCDD 0.977-1.047 ......... ......... .........
13 C122,3,4,6,7,8,-HxCDF............. 13 C12-1,2,3,7,8,9-HpCDD 0.959-1.021 ......... ......... .........
13 C121,2,3,4,7,8,-HxCDF............. 13 C12-1,2,3,7,8,9-HpCDD 0.977-1.000 ......... ......... .........
13 C121,2,3,6,7,8,-HxCDF............. 13 C12-1,2,3,7,8,9-HpCDD 0.981-1.003 ......... ......... .........
13 C121,2,3,4,6,7,8-HxCDF............ 13 C12-1,2,3,7,8,9-HpCDD 1.043-1.085 ......... ......... .........
13 C121,2,3,4,7,8,9-HxCDF............ 13 C12-1,2,3,7,8,9-HpCDD 1.057-1.151 ......... ......... .........
13 C121,2,3,4,6,7,8-HxCDF............ 13 C12-1,2,3,7,8,9-HpCDD 1.086-1.110 ......... ......... .........
13 C12OCDD........................... 13 C12-1,2,3,7,8,9-HpCDD 1.032-1.311 ......... ......... .........
----------------------------------------------------------------------------------------------------------------
\1\ The Minimum Level (ML) for each analyte is defined as the level at which the entire analytical system must
give a recognizable signal and acceptable calibration point. It is equivalent to the concentration of the
lowest calibration standard, assuming that all method-specified sample weights, volumes, and cleanup
procedures have been employed.
\2\ The retention time reference for 1,2,3,7,8,9-HxCDD is 13C12-1,2,3,6,7,8-HxCDD, and 1,2,3,7,8,9-HxCDD is
quantified using the averaged responses for 13C12-1,2,3,4,7,8-HxCDD and 13C12-1,2,3,6,7,8-HxCDD.
Table 3--Concentration of Stock and Spiking Solutions Containing CDDS/CDFS and Labeled Compounds
----------------------------------------------------------------------------------------------------------------
Labeled
Labeled compound
compound spiking PAR stock PAR spiking
CDD/CDF stock solution solution solution \4\
solution \1\ \2\ (ng/ \3\ (ng/mL) (ng/mL)
(ng/mL) mL)
----------------------------------------------------------------------------------------------------------------
2,3,7,8-TCDD.............................................. ............ ........... 40 0.8
2,3,7,8-TCDF.............................................. ............ ........... 40 0.8
1,2,3,7,8-PeCDD........................................... ............ ........... 200 4
1,2,3,7,8-PeCDF........................................... ............ ........... 200 4
2,3,4,7,8-PeCDF........................................... ............ ........... 200 4
1,2,3,4,7,8-HxCDD......................................... ............ ........... 200 4
1,2,3,6,7,8-HxCDD......................................... ............ ........... 200 4
1,2,3,7,8,9-HxCDD......................................... ............ ........... 200 4
1,2,3,4,7,8-HxCDF......................................... ............ ........... 200 4
1,2,3,6,7,8-HxCDF......................................... ............ ........... 200 4
1,2,3,7,8,9-HxCDF......................................... ............ ........... 200 4
2,3,4,6,7,8-HxCDF......................................... ............ ........... 200 4
1,2,3,4,6,7,8-HpCDD....................................... ............ ........... 200 4
1,2,3,4,6,7,8-HpCDF....................................... ............ ........... 200 4
1,2,3,4,7,8,9-HpCDF....................................... ............ ........... 200 4
OCDD...................................................... ............ ........... 400 8
OCDF...................................................... ............ ........... 400 8
13C12-2,3,7,8-TCDD........................................ 100 2 ........... ............
13C12-2,3,7,8-TCDF........................................ 100 2 ........... ............
13C12-1,2,3,7,8-PeCDD..................................... 100 2 ........... ............
13C12-1,2,3,7,8-PeCDF..................................... 100 2 ........... ............
13C12-2,3,4,7,8-PeCDF..................................... 100 2 ........... ............
13C12-1,2,3,4,7,8-HxCDD................................... 100 2 ........... ............
13C12-1,2,3,6,7,8-HxCDD................................... 100 2 ........... ............
13C12-1,2,3,4,7,8-HxCDF................................... 100 2 ........... ............
13C12-1,2,3,6,7,8-HxCDF................................... 100 2 ........... ............
13C12-1,2,3,7,8,9-HxCDF................................... 100 2 ........... ............
13C12-2,3,4,6,7,8-HxCDF................................... 100 2 ........... ............
13C12-1,2,3,4,6,7,8-HpCDD................................. 100 2 ........... ............
13C12-1,2,3,4,6,7,8-HpCDF................................. 100 2 ........... ............
13C12-1,2,3,4,7,8,9-HpCDF................................. 100 2 ........... ............
13C12-OCDD................................................ 200 4 ........... ............
Cleanup Standard \5\
37Cl4-2,3,7,8-TCDD.................................... 0.8 ........... ........... ............
Internal Standards \6\
13C12-1,2,3,4-TCDD.................................... 200 ........... ........... ............
[[Page 270]]
13C12-1,2,3,7,8,9-HxCDD............................... 200 ........... ........... ............
----------------------------------------------------------------------------------------------------------------
\1\ Section 7.10--prepared in nonane and diluted to prepare spiking solution.
\2\ Section 7.10.3--prepared in acetone from stock solution daily.
\3\ Section 7.9--prepared in nonane and diluted to prepare spiking solution.
\4\ Section 7.14--prepared in acetone from stock solution daily.
\5\ Section 7.11--prepared in nonane and added to extract prior to cleanup.
\6\ Section 7.12--prepared in nonane and added to the concentrated extract immediately prior to injection into
the GC (Section 14.2).
Table 4--Concentration of CDDS/CDFS in Calibration and Calibration Verification Solutions \1\ (Section 15.3)
----------------------------------------------------------------------------------------------------------------
CS2 (ng/ CS3 (ng/ CS4 (ng/ CS5 (ng/
CDD/CDF mL) mL) mL) mL)
----------------------------------------------------------------------------------------------------------------
2,3,7,8-TCDD.................................. 0.5 2 10 40 200
2,3,7,8-TCDF.................................. 0.5 2 10 40 200
1,2,3,7,8-PeCDD............................... 2.5 10 50 200 1000
1,2,3,7,8-PeCDF............................... 2.5 10 50 200 1000
2,3,4,7,8-PeCDF............................... 2.5 10 50 200 1000
1,2,3,4,7,8-HxCDD............................. 2.5 10 50 200 1000
1,2,3,6,7,8-HxCDD............................. 2.5 10 50 200 1000
1,2,3,7,8,9-HxCDD............................. 2.5 10 50 200 1000
1,2,3,4,7,8-HxCDF............................. 2.5 10 50 200 1000
1,2,3,6,7,8-HxCDF............................. 2.5 10 50 200 1000
1,2,3,7,8,9-HxCDF............................. 2.5 10 50 200 1000
2,3,4,6,7,8-HxCDF............................. 2.5 10 50 200 1000
1,2,3,4,6,7,8-HpCDD........................... 2.5 10 50 200 1000
1,2,3,4,6,7,8-HpCDF........................... 2.5 10 50 200 1000
1,2,3,4,7,8,9-HpCDF........................... 2.5 10 50 200 1000
OCDD.......................................... 5.0 20 100 400 2000
OCDF.......................................... 5.0 20 100 400 2000
13 C12-2,3,7,8-TCDD........................... 100 100 100 100 100
13 C12-2,3,7,8-TCDF........................... 100 100 100 100 100
13 C12-1,2,3,7,8-PeCDD........................ 100 100 100 100 100
13 C12-PeCDF.................................. 100 100 100 100 100
13 C12-2,3,4,7,8-PeCDF........................ 100 100 100 100 100
13 C12-1,2,3,4,7,8-HxCDD...................... 100 100 100 100 100
13 C12-1,2,3,6,7,8-HxCDD...................... 100 100 100 100 100
13 C12-1,2,3,4,7,8-HxCDF...................... 100 100 100 100 100
13 C12-1,2,3,6,7,8-HxCDF...................... 100 100 100 100 100
13 C12-1,2,3,7,8,9-HxCDF...................... 100 100 100 100 100
13 C12-1,2,3,4,6,7,8-HpCDD.................... 100 100 100 100 100
13 C12-1,2,3,4,6,7,8-HpCDF.................... 100 100 100 100 100
13 C12-1,2,3,4,7,8,9-Hp CDF................... 100 100 100 100 100
13 C12-OCDD................................... 200 200 200 200 200
Cleanup Standard:
37 C14-2,3,7,8-TCDD....................... 0.5 2 10 40 200
Internal Standards:
13 C12-1,2,3,4-TCDD........................... 100 100 100 100 100
13 C12-1,2,3,7,8,9-HxCDD...................... 100 100 100 100 100
----------------------------------------------------------------------------------------------------------------
Table 5--GC Retention Time Window Defining Solution and Isomer Specificity Test Standard (Section 7.15)
----------------------------------------------------------------------------------------------------------------
DB-5 column GC retention-time window defining solution
-----------------------------------------------------------------------------------------------------------------
CDD/CDF First eluted Last eluted
----------------------------------------------------------------------------------------------------------------
TCDF................................. 1,3,6,8-.................................. 1,2,8,9-
TCDD................................. 1,3,6,8-.................................. 1,2,8,9-
PeCDF................................ 1,3,4,6,8-................................ 1,2,3,8,9-
PeCDD................................ 1,2,4,7,9-................................ 1,2,3,8,9-
HxCDF................................ 1,2,3,4,6,8-.............................. 1,2,3,4,8,9-
HxCDD................................ 1,2,4,6,7,9-.............................. 1,2,3,4,6,7-
HpCDF................................ 1,2,3,4,6,7,8-............................ 1,2,3,4,7,8,9-
[[Page 271]]
HpCDD................................ 1,2,3,4,6,7,9-............................ 1,2,3,4,6,7,8-
----------------------------------------------------------------------------------------------------------------
DB-5 Column TCDD Specificity Test Standard
1,2,3,7=1,2,3,8-TCDD
2,3,7,8-TCDD
1,2,3,9-TCDD
DB-225 Column TCDF Isomer Specificity Test Standard
2,3,4,7-TCDF
2,3,7,8-TCDF
1,2,3,9-TCDF
Table 6--Acceptance Criteria for Performance Tests When All CDDS/CDFS Are Tested \1\
----------------------------------------------------------------------------------------------------------------
IPR 2 3
CDD/CDF Test conc. ---------------------------- OPR (ng/mL) VER (ng/mL)
(ng/mL) s (ng/mL) X (ng/mL)
----------------------------------------------------------------------------------------------------------------
2,3,7,8-TCDD............................... 10 2.8 8.3-12.9 6.7-15.8 7.8-12.9
2,3,7,8-TCDF............................... 10 2.0 8.7-13.7 7.5-15.8 8.4-12.0
1,2,3,7,8-PeCDD............................ 50 7.5 38-66 35-71 39-65
1,2,3,7,8-PeCDF............................ 50 7.5 43-62 40-67 41-60
2,3,4,7,8-PeCDF............................ 50 8.6 36-75 34-80 41-61
1,2,3,4,7,8-HxCDD.......................... 50 9.4 39-76 35-82 39-64
1,2,3,6,7,8-HxCDD.......................... 50 7.7 42-62 38-67 39-64
1,2,3,7,8,9-HxCDD.......................... 50 11.1 37-71 32-81 41-61
1,2,3,4,7,8-HxCDF.......................... 50 8.7 41-59 36-67 45-56
1,2,3,6,7,8-HxCDF.......................... 50 6.7 46-60 42-65 44-57
1,2,3,7,8,9-HxCDF.......................... 50 6.4 42-61 39-65 45-56
2,3,4,6,7,8-HxCDF.......................... 50 7.4 37-74 35-78 44-57
1,2,3,4,6,7,8-HpCDD........................ 50 7.7 38-65 35-70 43-58
1,2,3,4,6,7,8-HpCDF........................ 50 6.3 45-56 41-61 45-55
1,2,3,4,7,8,9-HpCDF........................ 50 8.1 43-63 39-69 43-58
OCDD....................................... 100 19 89-127 78-144 79-126
OCDF....................................... 100 27 74-146 63-170 63-159
13C12-2,3,7,8-TCDD......................... 100 37 28-134 20-175 82-121
13C12-2,3,7,8-TCDF......................... 100 35 31-113 22-152 71-140
13C12-1,2,3,7,8-PeCDD...................... 100 39 27-184 21-227 62-160
13C12-1,2,3,7,8-PeCDF...................... 100 34 27-156 21-192 76-130
13C12-2,3,4,7,8-PeCDF...................... 100 38 16-279 13-328 77-130
13C12-1,2,3,4,7,8-HxCDD.................... 100 41 29-147 21-193 85-117
13C12-1,2,3,6,7,8-HxCDD.................... 100 38 34-122 25-163 85-118
13C12-1,2,3,4,7,8-HxCDF.................... 100 43 27-152 19-202 76-131
13C12-1,2,3,6,7,8-HxCDF.................... 100 35 30-122 21-159 70-143
13C12-1,2,3,7,8,9-HxCDF.................... 100 40 24-157 17-205 74-135
13C12-2,3,4,6,7,8,-HxCDF................... 100 37 29-136 22-176 73-137
13C12-1,2,3,4,6,7,8-HpCDD.................. 100 35 34-129 26-166 72-138
13C12-1,2,3,4,6,7,8-HpCDF.................. 100 41 32-110 21-158 78-129
13C12-1,2,3,4,7,8,9-HpCDF.................. 100 40 28-141 20-186 77-129
13C12-OCDD................................. 200 95 41-276 26-397 96-415
37Cl4-2,3,7,8-TCDD......................... 10 3.6 3.9-15.4 3.1-19.1 7.9-12.7
----------------------------------------------------------------------------------------------------------------
\1\ All specifications are given as concentration in the final extract, assuming a 20 [micro]L volume.
\2\ s = standard deviation of the concentration.
\3\ X = average concentration.
Table 6a--Acceptance Criteria for Performance Tests When Only Tetra Compounds are Tested 1
----------------------------------------------------------------------------------------------------------------
IPR 2 3
CDD/CDF Test Conc. --------------------------- OPR (ng/mL) VER (ng/mL)
(ng/mL) s (ng/mL) X (ng/mL)
----------------------------------------------------------------------------------------------------------------
2,3,7,8-TCDD................................ 10 2.7 8.7-12.4 7.314.6 8.2-12.3
2,3,7,8-TCDF................................ 10 2.0 9.1-13.1 8.0-14.7 8.6-11.6
13C12-2,3,7,8-TCDD.......................... 100 35 32-115 25-141 85-117
13C12-2,3,7,8-TCDF.......................... 100 34 35-99 26-126 76-131
[[Page 272]]
37Cl4-2,3,7,8-TCDD.......................... 10 3.4 4.5-13.4 3.7-15.8 8.3-12.1
----------------------------------------------------------------------------------------------------------------
1 All specifications are given as concentration in the final extract, assuming a 20 [micro]L volume.
2 s = standard deviation of the concentration.
3 X = average concentration.
Table 7--Labeled Compounds Recovery in Samples When all CDDS/CDFS are
Tested
------------------------------------------------------------------------
Labeled compound
Test conc. recovery
Compound (ng/mL) --------------------------
(ng/mL) 1 (%)
------------------------------------------------------------------------
13C12-2,3,7,8-TCDD.............. 100 25-164 25-164
13C12-2,3,7,8-TCDF.............. 100 24-169 24-169
13C12-1,2,3,7,8-PeCDD........... 100 25-181 25-181
13C12-1,2,3,7,8-PeCDF........... 100 24-185 24-185
13C12-2,3,4,7,8-PeCDF........... 100 21-178 21-178
13C12-1,2,3,4,7,8-HxCDD......... 100 32-141 32-141
13C12-1,2,3,6,7,8-HxCDD......... 100 28-130 28-130
13C12-1,2,3,4,7,8-HxCDF......... 100 26-152 26-152
13C12-1,2,3,6,7,8-HxCDF......... 100 26-123 26-123
13C12-1,2,3,7,8,9-HxCDF......... 100 29-147 29-147
13C12-2,3,4,6,7,8-HxCDF......... 100 28-136 28-136
13C12-1,2,3,4,6,7,8-HpCDD....... 100 23-140 23-140
13C12-1,2,3,4,6,7,8-HpCDF....... 100 28-143 28-143
13C12-1,2,3,4,7,8,9-HpCDF....... 100 26-138 26-138
13C12-OCDD...................... 200 34-313 17-157
37Cl4-2,3,7,8-TCDD.............. 10 3.5-19.7 35-197
------------------------------------------------------------------------
1 Specification given as concentration in the final extract, assuming a
20-[micro]L volume.
Table 7a--Labeled Compound Recovery in Samples When Only Tetra Compounds
are Tested
------------------------------------------------------------------------
Labeled compound
Test conc. recovery
Compound (ng/mL) --------------------------
(ng/mL) \1\ (%)
------------------------------------------------------------------------
13C12-2,3,7,8-TCDD.............. 100 31-137 31-137
13C12-2,3,7,8-TCDF.............. 100 29-140 29-140
37Cl4-2,3,7,8-TCDD.............. 10 4.2-16.4 42-164
------------------------------------------------------------------------
\1\ Specification given as concentration in the final extract, assuming
a 20 [micro]L volume.
Table 8--Descriptors, Exact M/Z's, M/Z Types, and Elemental Compositions of the CDDs and CDFs
----------------------------------------------------------------------------------------------------------------
Exact M/Z
Descriptor \1\ M/Z type Elemental composition Substance \2\
----------------------------------------------------------------------------------------------------------------
1........................ 292.9825 Lock C7F11.................... PFK
303.9016 M C12H435Cl4O.............. TCDF
305.8987 M=2 C12H435Cl337ClO.......... TCDF
315.9419 M 13C12H435Cl4O............ TCDF \3\
317.9389 M=2 13C12H435Cl337ClO........ TCDF \3\
319.8965 M C12H435Cl4O2............. TCDD
321.8936 M=2 C12H435Cl337ClO2......... TCDD
327.8847 M C12H437Cl4O2............. TCDD \4\
330.9792 QC C7F13.................... PFK
331.9368 M 13C12H435Cl4O2........... TCDD \3\
333.9339 M=2 13C12H435Cl337ClO2....... TCDD \3\
375.8364 M=2 C12H435Cl537ClO.......... HxCDPE
2........................ 339.8597 M=2 C12H335Cl437ClO.......... PeCDF
341.8567 M=4 C12H335Cl337Cl2O......... PeCDF
351.9000 M=2 13C12H335Cl437ClO........ PeCDF
353.8970 M=4 13C12H335Cl337Cl2O....... PeCDF \3\
354.9792 Lock C9F13.................... PFK
355.8546 M=2 C12H335Cl437ClO2......... PeCDD
357.8516 M=4 C12H335Cl337Cl2O2........ PeCDD
[[Page 273]]
367.8949 M=2 13C12H335Cl437ClO2....... PeCDD \3\
369.8919 M=4 13C12H335Cl337Cl2O2...... PeCDD \3\
409.7974 M=2 C12H335Cl637ClO.......... HpCDPE
3........................ 373.8208 M=2 C12H235Cl537ClO.......... HxCDF
375.8178 M=4 C12H235Cl437Cl2O......... HxCDF
383.8639 M 13C12H235Cl6O............ HxCDF \3\
385.8610 M=2 13C12H235Cl537ClO........ HxCDF \3\
389.8157 M=2 C12H235Cl537ClO2......... HxCDD
391.8127 M=4 C12H235Cl437Cl2O2........ HxCDD
392.9760 Lock C9F15.................... PFK
401.8559 M=2 13C12H235Cl537ClO2....... HxCDD \3\
403.8529 M=4 13C12H235Cl437Cl2O2...... HxCDD \3\
430.9729 QC C9F17.................... PFK
445.7555 M=4 C12H235Cl637Cl2O......... OCDPE
4........................ 407.7818 M=2 C12H35Cl637ClO........... HpCDF
409.7789 M=4 C12H35Cl537Cl2O.......... HpCDF
417.8253 M 13C12H35Cl7O............. HpCDF \3\
419.8220 M=2 13C12H35Cl637ClO......... HpCDF \3\
423.7766 M=2 C12H35Cl637ClO2.......... HpCDD
425.7737 M=4 C12H35Cl537Cl2O2......... HpCDD
430.9729 Lock C9F17.................... PFK
435.8169 M=2 13C12H35Cl637ClO2........ HpCDD \3\
437.8140 M=4 13C12H35Cl537Cl2O2....... HpCDD \3\
479.7165 M=4 C12H35Cl737Cl2O.......... NCDPE
5........................ 441.7428 M=2 C1235Cl737ClO............ OCDF
442.9728 Lock C10F17................... PFK
443.7399 M=4 C1235Cl637Cl2O........... OCDF
457.7377 M=2 C1235Cl737ClO2........... OCDD
459.7348 M=4 C1235Cl637Cl2O2.......... OCDD
469.7779 M=2 13C1235Cl737ClO2......... OCDD\3\
471.7750 M=4 13C1235Cl637Cl2O2........ OCDD\3\
513.6775 M=4 C1235Cl837Cl2O........... DCDPE
----------------------------------------------------------------------------------------------------------------
\1\ Nuclidic masses used:
H = 1.007825.
O = 15.994915.
C = 12.00000.
35Cl = 34.968853.
13C = 13.003355.
37Cl = 36.965903.
F = 18.9984.
\2\ TCDD = Tetrachlorodibenzo-p-dioxin.
PeCDD = Pentachlorodibenzo-p-dioxin.
HxCDD = Hexachlorodibenzo-p-dioxin.
HpCDD = Heptachlorodibenzo-p-dioxin.
OCDD = Octachlorodibenzo-p-dioxin.
HxCDPE = Hexachlorodiphenyl ether.
OCDPE = Octachlorodiphenyl ether.
DCDPE = Decachlorodiphenyl ether.
TCDF = Tetrachlorodibenzofuran.
PeCDF = Pentachlorodibenzofuran.
HxCDF = Hexachlorodibenzofuran.
HpCDF = Heptachlorodibenzofuran.
OCDF = Octachlorodibenzofuran.
HpCDPE = Heptachlorodiphenyl ether.
NCDPE = Nonachlorodiphenyl ether.
PFK = Perfluorokerosene.
\3\ Labeled compound.
\4\ There is only one m/z for 37Cl4-2,3,7,8,-TCDD (cleanup standard).
Table 9--Theoretical Ion Abundance Ratios and QC Limits
----------------------------------------------------------------------------------------------------------------
QC limit \1\
Number of chlorine atoms M/Z's forming ratio Theoretical -------------------------
ratio Lower Upper
----------------------------------------------------------------------------------------------------------------
4 \2\................................... M/(M=2)........................ 0.77 0.65 0.89
5....................................... (M=2)/(M=4).................... 1.55 1.32 1.78
6....................................... (M=2)/(M=4).................... 1.24 1.05 1.43
6 \3\................................... M/(M=2)........................ 0.51 0.43 0.59
7....................................... (M=2)/(M=4).................... 1.05 0.88 1.20
7 \4\................................... M/(M=2)........................ 0.44 0.37 0.51
8....................................... (M=2)/(M=4).................... 0.89 0.76 1.02
----------------------------------------------------------------------------------------------------------------
\1\ QC limits represent 15% windows around the theoretical ion abundance ratios.
[[Page 274]]
\2\ Does not apply to 37Cl4-2,3,7,8-TCDD (cleanup standard).
\3\ Used for 13C12-HxCDF only.
\4\ Used for 13C12-HpCDF only.
Table 10--Suggested Sample Quantities To Be Extracted for Various Matrices \1\
----------------------------------------------------------------------------------------------------------------
Quantity
Sample Matrix \2\ Example Percent solids Phase extracted
----------------------------------------------------------------------------------------------------------------
Single-phase:
Aqueous...................... Drinking water...... <1 (\3\)............... 1000 mL.
Groundwater .............. .................... .................
Treated wastewater .............. .................... .................
Solid........................ Dry soil............ 20 Solid............... 10 g.
Compost .............. .................... .................
Ash .............. .................... .................
Organic...................... Waste solvent....... <1 Organic............. 10 g.
Waste oil .............. .................... .................
Organic polymer .............. .................... .................
Tissue....................... Fish................ .............. Organic............. 10 g.
Human adipose .............. .................... .................
Multi-phase:
Liquid/Solid:
Aqueous/Solid............ Wet soil............ 1-30 Solid............... 10 g.
Untreated effluent..
Digested municipal
sludge.
Filter cake.........
Paper pulp..........
Organic/solid............ Industrial sludge... 1-100 Both................ 10 g.
Oily waste .............. .................... .................
Liquid/Liquid:
Aqueous/organic.......... In-process effluent. <1 Organic............. 10 g.
Untreated effluent .............. .................... .................
Drum waste .............. .................... .................
Aqueous/organic/solid.... Untreated effluent.. 1 Organic and solid... 10 g.
Drum waste .............. .................... .................
----------------------------------------------------------------------------------------------------------------
\1\ The quantity of sample to be extracted is adjusted to provide 10 g of solids (dry weight). One liter of
aqueous samples containing 1% solids will contain 10 g of solids. For aqueous samples containing greater than
1% solids, a lesser volume is used so that 10 g of solids (dry weight) will be extracted.
\2\ The sample matrix may be amorphous for some samples. In general, when the CDDs/CDFs are in contact with a
multiphase system in which one of the phases is water, they will be preferentially dispersed in or adsorbed on
the alternate phase because of their low solubility in water.
\3\ Aqueous samples are filtered after spiking with the labeled compounds. The filtrate and the materials
trapped on the filter are extracted separately, and the extracts are combined for cleanup and analysis.
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24.0 Glossary of Definitions and Purposes
These definitions and purposes are specific to this method but have
been conformed to common usage as much as possible.
24.1 Units of weight and Measure and Their Abbreviations.
24.1.1 Symbols:
[deg]C--degrees Celsius
[micro]L--microliter
[micro]m--micrometer
<--less than
--greater than
%--percent
24.1.2 Alphabetical abbreviations:
amp--ampere
cm--centimeter
g--gram
h--hour
D--inside diameter
in.--inch
L--liter
M--Molecular ion
m--meter
mg--milligram
min--minute
mL--milliliter
mm--millimeter
m/z--mass-to-charge ratio
[[Page 282]]
N--normal; gram molecular weight of solute divided by hydrogen
equivalent of solute, per liter of solution
OD--outside diameter
pg--picogram
ppb--part-per-billion
ppm--part-per-million
ppq--part-per-quadrillion
ppt--part-per-trillion
psig--pounds-per-square inch gauge
v/v--volume per unit volume
w/v--weight per unit volume
24.2 Definitions and Acronyms (in Alphabetical Order).
Analyte--A CDD or CDF tested for by this method. The analytes are
listed in Table 1.
Calibration Standard (CAL)--A solution prepared from a secondary
standard and/or stock solutions and used to calibrate the response of
the instrument with respect to analyte concentration.
Calibration Verification Standard (VER)--The mid-point calibration
standard (CS3) that is used in to verify calibration. See Table 4.
CDD--Chlorinated Dibenzo-p-ioxin--The isomers and congeners of
tetra-through octa-chlorodibenzo-p-dioxin.
CDF--Chlorinated Dibenzofuran--The isomers and congeners of tetra-
through octa-chlorodibenzofuran.
CS1, CS2, CS3, CS4, CS5--See Calibration standards and Table 4.
Field Blank--An aliquot of reagent water or other reference matrix
that is placed in a sample container in the laboratory or the field, and
treated as a sample in all respects, including exposure to sampling site
conditions, storage, preservation, and all analytical procedures. The
purpose of the field blank is to determine if the field or sample
transporting procedures and environments have contaminated the sample.
GC--Gas chromatograph or gas chromatography.
GPC--Gel permeation chromatograph or gel permeation chromatography.
HPLC--High performance liquid chromatograph or high performance
liquid chromatography.
HRGC--High resolution GC.
HRMS--High resolution MS.
IPR--Initial precision and recovery; four aliquots of the diluted
PAR standard analyzed to establish the ability to generate acceptable
precision and accuracy. An IPR is performed prior to the first time this
method is used and any time the method or instrumentation is modified.
K-D--Kuderna-Danish concentrator; a device used to concentrate the
analytes in a solvent.
Laboratory Blank--See method blank.
Laboratory Control sample (LCS)--See ongoing precision and recovery
standard (OPR).
Laboratory Reagent Blank--See method blank.
May--This action, activity, or procedural step is neither required
nor prohibited.
May Not--This action, activity, or procedural step is prohibited.
Method Blank--An aliquot of reagent water that is treated exactly as
a sample including exposure to all glassware, equipment, solvents,
reagents, internal standards, and surrogates that are used with samples.
The method blank is used to determine if analytes or interferences are
present in the laboratory environment, the reagents, or the apparatus.
Minimum Level (ML)--The level at which the entire analytical system
must give a recognizable signal and acceptable calibration point for the
analyte. It is equivalent to the concentration of the lowest calibration
standard, assuming that all method-specified sample weights, volumes,
and cleanup procedures have been employed.
MS--Mass spectrometer or mass spectrometry.
Must--This action, activity, or procedural step is required.
OPR--Ongoing precision and recovery standard (OPR); a laboratory
blank spiked with known quantities of analytes. The OPR is analyzed
exactly like a sample. Its purpose is to assure that the results
produced by the laboratory remain within the limits specified in this
method for precision and recovery.
PAR--Precision and recovery standard; secondary standard that is
diluted and spiked to form the IPR and OPR.
PFK--Perfluorokerosene; the mixture of compounds used to calibrate
the exact m/z scale in the HRMS.
Preparation Blank--See method blank.
Primary Dilution Standard--A solution containing the specified
analytes that is purchased or prepared from stock solutions and diluted
as needed to prepare calibration solutions and other solutions.
Quality Control Check Sample (QCS)--A sample containing all or a
subset of the analytes at known concentrations. The QCS is obtained from
a source external to the laboratory or is prepared from a source of
standards different from the source of calibration standards. It is used
to check laboratory performance with test materials prepared external to
the normal preparation process.
Reagent Water--Water demonstrated to be free from the analytes of
interest and potentially interfering substances at the method detection
limit for the analyte.
Relative Standard Deviation (RSD)--The standard deviation times 100
divided by the mean. Also termed ``coefficient of variation.''
RF--Response factor. See Section 10.6.1.
RR--Relative response. See Section 10.5.2.
RSD--See relative standard deviation.
[[Page 283]]
SDS--Soxhlet/Dean-Stark extractor; an extraction device applied to
the extraction of solid and semi-solid materials (Reference 7).
Should--This action, activity, or procedural step is suggested but
not required.
SICP--Selected ion current profile; the line described by the signal
at an exact m/z.
SPE--Solid-phase extraction; an extraction technique in which an
analyte is extracted from an aqueous sample by passage over or through a
material capable of reversibly adsorbing the analyte. Also termed
liquid-solid extraction.
Stock Solution--A solution containing an analyte that is prepared
using a reference material traceable to EPA, the National Institute of
Science and Technology (NIST), or a source that will attest to the
purity and authenticity of the reference material.
TCDD--Tetrachlorodibenzo-p-dioxin.
TCDF--Tetrachlorodibenzofuran.
VER--See calibration verification standard.
Method 1624 Revision B--Volatile Organic Compounds by Isotope Dilution
GC/MS
1. Scope and Application
1.1 This method is designed to determine the volatile toxic organic
pollutants associated with the 1976 Consent Decree and additional
compounds amenable to purge and trap gas chromatography-mass
spectrometry (GC/MS).
1.2 The chemical compounds listed in table 1 may be determined in
municipal and industrial discharges by this method. The methmd is
designed to meet the survey requirements of Effluent Guidelines Division
(EGD) and the National Pollutants Discharge Elimination System (NPDES)
under 40 CFR 136.1 and 136.5. Any modifications of this method, beyond
those expressly permitted, shall be considered as major modifications
subject to application and approval of alternate test procedures under
40 CFR 136.4 and 136.5.
1.3 The detection limit of this method is usually dependent on the
level of interfer ences rather than instrumental limitations. The limits
in table 2 represent the minimum quantity that can be detected with no
interferences present.
1.4 The GC/MS portions of this method are for use only by analysts
experienced with GC/MS or under the close supervision of such qualified
persons. Laboratories unfamiliar with the analyses of environmental
samples by GC/MS should run the performance tests in reference 1 before
beginning.
2. Summary of Method
2.1 Stable isotopically labeled analogs of the compounds of interest
are added to a 5 mL water sample. The sample is purged at 20-25 [deg]C
with an inert gas in a specially designed chamber. The volatile organic
compounds are transferred from the aqueous phase into the gaseous phase
where they are passed into a sorbent column and trapped. After purging
is completed, the trap is backflushed and heated rapidly to desorb the
compounds into a gas chromatograph (GC). The compounds are separated by
the GC and detected by a mass spectrometer (MS) (references 2 and 3).
The labeled compounds serve to correct the variability of the analytical
technique.
2.2 Identification of a compound (qualitative analysis) is performed
by comparing the GC retention time and the background corrected
characteristic spectral masses with those of authentic standards.
2.3 Quantitative analysis is performed by GC/MS using extracted ion
current profile (EICP) areas. Isotope dilution is used when labeled
compounds are available; otherwise, an internal standard method is used.
2.4 Quality is assured through reproducible calibration and testing
of the purge and trap and GC/MS systems.
3. Contamination and Interferences
3.1 Impurities in the purge gas, organic compounds out-gassing from
the plumbing upstream of the trap, and solvent vapors in the laboratory
account for the majority of contamination problems. The analytical
system is demonstrated to be free from interferences under conditions of
the analysis by analyzing blanks initially and with each sample lot
(samples analyzed on the same 8 hr shift), as described in Section 8.5.
3.2 Samples can be contaminated by diffusion of volatile organic
compounds (particularly methylene chloride) through the bottle seal
during shipment and storage. A field blank prepared from reagent water
and carried through the sampling and handling protocol serves as a check
on such contamination.
3.3 Contamination by carry-over can occur when high level and low
level samples are analyzed sequentially. To reduce carry-over, the
purging device and sample syringe are rinsed between samples with
reagent water. When an unusually concentrated sample is encountered, it
is followed by analysis of a reagent water blank to check for carry-
over. For samples containing large amounts of water soluble materials,
suspended solids, high boiling compounds, or high levels or purgeable
compounds, the purge device is washed with soap solution, rinsed with
tap and distilled water, and dried in an oven at 100-125 [deg]C. The
trap and other parts of the system are also subject to contamination;
therefore, frequent bakeout and purging of the entire system may be
required.
3.4 Interferences resulting from samples will vary considerably from
source to source, depending on the diversity of the industrial complex
or municipality being sampled.
[[Page 284]]
4. Safety
4.1 The toxicity or carcinogenicity of each com pound or reagent
used in this method has not been precisely determined; how ever, each
chemical compound should be treated as a potential health hazard.
Exposure to these compounds should be reduced to the lowest possible
level. The laboratory is responsible for maintaining a current awareness
file of OSHA regulations regarding the safe handling of the chemicals
specified in this method. A reference file of data handling sheets
should also be made available to all personnel involved in these
analyses. Additional information on laboratory safety can be found in
references 4-6.
4.2 The following compounds covered by this method have been
tentatively classified as known or suspected human or mammalian
carcinogens: benzene, carbon tetrachloride, chloroform, and vinyl
chloride. Primary standards of these toxic compounds should be prepared
in a hood, and a NIOSH/MESA approved toxic gas respirator should be worn
when high concentrations are handled.
5. Apparatus and Materials
5.1 Sample bottles for discrete sampling.
5.1.1 Bottle--25 to 40 mL with screw cap (Pierce 13075, or
equivalent). Detergent wash, rinse with tap and distilled water, and dry
at 105 [deg]C for one hr minimum before use.
5.1.2 Septum--Teflon-faced silicone (Pierce 12722, or equivalent),
cleaned as above and baked at 100-200 [deg]C, for one hour mini mum.
5.2 Purge and trap device--consists of purging device, trap, and
desorber. Complete devices are commercially available.
5.2.1 Purging device--designed to accept 5 mL samples with water
column at least 3 cm deep. The volume of the gaseous head space between
the water and trap shall be less than 15 mL. The purge gas shall be
introduced less than 5 mm from the base of the water column and shall
pass through the water as bubbles with a diameter less than 3 mm. The
purging device shown in Figure 1 meets these criteria.
5.2.2 Trap--25 to 30 cm x 2.5 mm i.d. minimum, containing the
following:
5.2.2.1 Methyl silicone packing--one 0.2 cm, 3
percent OV-1 on 60/80 mesh Chromosorb W, or equivalent.
5.2.2.2 Porous polymer--15 1.0 cm, Tenax GC
(2,6-diphenylene oxide polymer), 60/80 mesh, chromatographic grade, or
equivalent.
5.2.2.3 Silica gel--8 1.0 cm, Davison
Chemical, 35/60 mesh, grade 15, or equivalent. The trap shown in Figure
2 meets these specifications.
5.2.3 Desorber--shall heat the trap to 175 5
[deg]C in 45 seconds or less. The polymer section of the trap shall not
exceed 180 [deg]C, and the remaining sections shall not exceed 220
[deg]C. The desorber shown in Figure 2 meets these specifications.
5.2.4 The purge and trap device may be a separate unit or coupled to
a GC as shown in Figures 3 and 4.
5.3 Gas chromatograph--shall be linearly temperature programmable
with initial and final holds, shall contain a glass jet separator as the
MS interface, and shall produce results which meet the calibration
(Section 7), quality assurance (Section 8), and performance tests
(Section 11) of this method.
5.3.1 Column--2.8 0.4 m x 2 0.5 mm i. d. glass, packekd with one percent SP-1000 on
Carbopak B, 60/80 mesh, or equivalent.
5.4 Mass spectrometer--70 eV electron impact ionization; shall
repetitively scan from 20 to 250 amu every 2-3 seconds, and produce a
unit resolution (valleys between m/z 174-176 less than 10 percent of the
height of the m/z 175 peak), background corrected mass spectrum from 50
ng 4-bromo-fluorobenzene (BFB) injected into the GC. The BFB spectrum
shall meet the mass-intensity criteria in Table 3. All portions of the
GC column, transfer lines, and separator which connect the GC column to
the ion source shall remain at or above the column temperature during
analysis to preclude condensation of less volatile compounds.
5.5 Data system--shall collect and record MS data, store mass
intensity data in spectral libraries, process GC/MS data and generate
reports, and shall calculate and record response factors.
5.5.1 Data acquisition--mass spectra shall be collected continuously
throughout the analysis and stored on a mass storage device.
5.5.2 Mass spectral libraries--user created libraries containing
mass spectra obtained from analysis of authentic standards shall be
employed to reverse search GC/MS runs for the compounds of interest
(Section 7.2).
5.5.3 Data processing--the data system shall be used to search,
locate, identify, and quantify the compounds of interest in each GC/MS
analysis. Software routines shall be employed to compute retention times
and EICP areas. Displays of spectra, mass chromatograms, and library
comparisons are required to verify results.
5.5.4 Response factors and multipoint calibrations--the data system
shall be used to record and maintain lists of response factors (response
ratios for isotope dilution) and generate multi-point calibration curves
(Section 7). Computations of relative standard deviation (coefficient of
variation) are useful for testing calibration linearity. Statistics on
initial and on-going performance shall be maintained (Sections 8 and
11).
5.6 Syringes--5 mL glass hypodermic, with Luer-lok tips.
5.7 Micro syringes--10, 25, and 100 uL.
5.8 Syringe valves--2-way, with Luer ends (Telfon or Kel-F).
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5.9 Syringe--5 mL, gas-tight, with shut-off valve.
5.10 Bottles--15 mL., screw-cap with Telfon liner.
5.11 Balance--analytical, capable of weighing 0.1 mg.
6. Reagents and Standards
6.1 Reagent water--water in which the compounds of interest and
interfering compounds are not detected by this method (Section 11.7). It
may be generated by any of the following methods:
6.1.1 Activated carbon--pass tap water through a carbon bed (Calgon
Filtrasorb-300, or equivalent).
6.1.2 Water purifier--pass tap water through a purifier (Millipore
Super Q, or equivalent).
6.1.3 Boil and purge--heat tap water to 90-100 [deg]C and bubble
contaminant free inert gas through it for approx one hour. While still
hot, transfer the water to screw-cap bottles and seal with a Teflon-
lined cap.
6.2 Sodium thiosulfate--ACS granular.
6.3 Methanol--pesticide quality or equivalent.
6.4 Standard solutions--purchased as solution or mixtures with
certification to their purity, concentration, and authenticity, or
prepared from materials of known purity and composition. If compound
purity is 96 percent or greater, the weight may be used without
correction to calculate the concentration of the standard.
6.5 Preparation of stock solutions--prepare in methanol using liquid
or gaseous standards per the steps below. Observe the safety precautions
given in Section 4.
6.5.1 Place approx 9.8 mL of methanol in a 10 mL ground glass
stoppered volumetric flask. Allow the flask to stand unstoppered for
approximately 10 minutes or until all methanol wetted surfaces have
dried. In each case, weigh the flask, immediately add the compound, then
immediately reweigh to prevent evaporation losses from affecting the
measurement.
6.5.1.1 Liquids--using a 100 [micro]L syringe, permit 2 drops of
liquid to fall into the methanol without contacting the leck of the
flask. Alternatively, inject a known volume of the compound into the
methanol in the flask using a micro-syringe.
6.5.1.2 Gases (chloromethane, bromome thane, chloro ethane, vinyl
chloride)--fill a valved 5 mL gas-tight syringe with the compound. Lower
the needle to approximately 5 mm above the methanol meniscus. Slowly
introduce the compound above the surface of the meniscus. The gas will
dissolve rapidly in the methanol.
6.5.2 Fill the flask to volume, stopper, then mix by inverting
several times. Calculate the concentration in mg/mL ([micro]g/[micro]L )
from the weight gain (or density if a known volume was injected).
6.5.3 Transfer the stock solution to a Teflon sealed screw-cap-
bottle. Store, with minimal headspace, in the dark at -10 to -20 [deg]C.
6.5.4 Prepare fresh standards weekly for the gases and 2-
chloroethylvinyl ether. All other standards are replaced after one
month, or sooner if comparison with check standards indicate a change in
concentration. Quality control check standards that can be used to
determine the accuracy of calibration standards are available from the
US Environmental Protection Agency, Environmental Monitoring and Support
Laboratory, Cincinnati, Ohio.
6.6 Labeled compound spiking solution--from stock standard solutions
prepared as above, or from mixtures, prepare the spiking solution to
contain a concentration such that a 5-10 [micro]L spike into each 5 mL
sample, blank, or aqueous standard analyzed will result in a
concentration of 20 [micro]g/L of each labeled compound. For the gases
and for the water soluble compounds (acrolein, acrylonitrile, acetone,
diethyl ether, and MEK), a concentration of 100 [micro]g/L may be used.
Include the internal standards (Section 7.5) in this solution so that a
concentration of 20 [micro]g/L in each sample, blank, or aqueous
standard will be produced.
6.7 Secondary standards--using stock solutions, prepare a secondary
standard in methanol to contain each pollutant at a concentration of 500
[micro]g/mL For the gases and water soluble compounds (Section 6.6), a
concentration of 2.5 mg/mL may be used.
6.7.1 Aqueous calibration standards--using a 25 [micro]L syringe,
add 20 [micro]L of the secondary standard (Section 6.7) to 50, 100, 200,
500, and 1000 mL of reagent water to produce concentrations of 200, 100,
50, 20, and 10 [micro]g/L, respectively. If the higher concentration
standard for the gases and water soluble compounds was chosen (Section
6.6), these compounds will be at concentrations of 1000, 500, 250, 100,
and 50 [micro]g/L in the aqueous calibration standards.
6.7.2 Aqueous performance standard--an aqueous standard containing
all pollutants, internal standards, labeled compounds, and BFB is
prepared daily, and analyzed each shift to demonstrate performance
(Section 11). This standard shall contain either 20 or 100 [micro]g/L of
the labeled and pollutant gases and water soluble compounds, 10
[micro]g/L BFB, and 20 [micro]g/L of all other pollutants, labeled
compounds, and internal standards. It may be the nominal 20 [micro]g/L
aqueous calibration standard (Section 6.7.1).
6.7.3 A methanolic standard containing all pollutants and internal
standards is prepared to demonstrate recovery of these compounds when
syringe injection and purge and trap analyses are compared. This
standard shall contain either 100 [micro]g/mL or 500 [micro]g/mL of the
gases and water soluble compounds, and 100 [micro]g/mL of the remaining
pollutants
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and internal standards (consistent with the amounts in the aqueous
performance standard in 6.7.2).
6.7.4 Other standards which may be needed are those for test of BFB
performance (Section 7.1) and for collection of mass spectra for storage
in spectral libraries (Section 7.2).
7. Calibration
7.1 Assemble the gas chromatographic apparatus and establish
operating conditions given in table 2. By injecting standards into the
GC, demonstrate that the analytical system meets the detection limits in
table 2 and the mass-intensity criteria in table 3 for 50 ng BFB.
7.2 Mass spectral libraries--detection and identification of the
compound of interest are dependent upon the spectra stored in user
created libraries.
7.2.1 Obtain a mass spectrum of each pollutant and labeled compound
and each internal standard by analyzing an authentic standard either
singly or as part of a mixture in which there is no interference between
closely eluted components. That only a single compound is present is
determined by examination of the spectrum. Fragments not attributable to
the compound under study indicate the presence of an interfering
compound. Adjust the analytical conditions and scan rate (for this test
only) to produce an undistorted spectrum at the GC peak maximum. An
undistorted spectrum will usually be obtained if five complete spectra
are collected across the upper half of the GC peak. Software algorithms
designed to ``enhance'' the spectrum may eliminate distortion, but may
also eliminate authentic m/z's or introduce other distortion.
7.2.3 The authentic reference spectrum is obtained under BFB tuning
conditions (Section 7.1 and table 3) to normalize it to spectra from
other instruments.
7.2.4 The spectrum is edited by saving the 5 most intense mass
spectral peaks and all other mass spectral peaks greater than 10 percent
of the base peak. This spectrum is stored for reverse search and for
compound confirmation.
7.3 Assemble the purge and trap device. Pack the trap as shown in
Figure 2 and condition overnight at 170-180 [deg]C by backflushing with
an inert gas at a flow rate of 20-30 mL/min. Condition traps daily for a
minimum of 10 minutes prior to use.
7.3.1 Analyze the aqueous performance standard (Section 6.7.2)
according to the purge and trap procedure in Section 10. Compute the
area at the primary m/z (table 4) for each compound. Compare these areas
to those obtained by injecting one [micro]L of the methanolic standard
(Section 6.7.3) to determine compound recovery. The recovery shall be
greater than 20 percent for the water soluble compounds, and 60-110
percent for all other compounds. This recovery is demonstrated initially
for each purge and trap GC/MS system. The test is repeated only if the
purge and trap or GC/MS systems are modified in any way that might
result in a change in recovery.
7.3.2 Demonstrate that 100 ng toluene (or toluene-d8) produces an
area at m/z 91 (or 99) approx one-tenth that required to exceed the
linear range of the system. The exact value must be determined by
experience for each instrument. It is used to match the calibration
range of the instrument to the analytical range and detection limits
required.
7.4 Calibration by isotope dilution--the isotope dilution approach
is used for the purgeable organic compounds when appropriate labeled
compounds are available and when interferences do not preclude the
analysis. If labeled compounds are not available, or interferences are
present, internal standard methods (Section 7.5 or 7.6) are used. A
calibration curve encompassing the concentration range of interest is
prepared for each compound determined. The relative response (RR) vs
concentration ([micro]g/L) is plotted or computed using a linear
regression. An example of a calibration curve for toluene using toluene-
d8 is given in figure 5. Also shown are the 10
percent error limits (dotted lines). Relative response is determined
according to the procedures described below. A minimum of five data
points are required for calibration (Section 7.4.4).
7.4.1 The relative response (RR) of pollutant to labeled compound is
determined from isotope ratio values calculated from acquired data.
Three isotope ratios are used in this process:
RX=the isotope ratio measured in the pure pollutant
(figure 6A).
Ry=the isotope ratio of pure labeled compound (figure
6B).
Rm=the isotope ratio measured in the analytical mixture
of the pollutant and labeled compounds (figure 6C).
The correct way to calculate RR is: RR=(Ry-Rm)
(RX+1)/(Rm-RX)(Ry+1) If
Rm is not between 2Ry and 0.5RX, the
method does not apply and the sample is analyzed by internal or external
standard methods (Section 7.5 or 7.6).
7.4.2 In most cases, the retention times of the pollutant and
labeled compound are the same and isotope ratios (R's) can be calculated
from the EICP areas, where: R=(area at m1/z)/(area at
m2/z) If either of the areas is zero, it is assigned a value
of one in the calculations; that is, if: area of m1/z=50721,
and area of m2/z=0, then R=50721/1=50720. The m/z's are
always selected such that RXRy. When
there is a difference in retention times (RT) between the pollutant and
labeled compounds, special precautions are required to determine the
isotope ratios.
RX, Ry, and Rm are defined as
follows:
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RX=[area m1/z (at RT1)]/1
Ry=1/[area m2/z (at RT2)]
Rm=[area m1/z (at RT1)]/[area
m2/z (at RT2)]
7.4.3 An example of the above calculations can be taken from the
data plotted in figure 6 for toluene and toluene-d8. For these data,
RX=168920/1=168900, Ry=1/60960=0.00001640, and
Rm=96868/82508=1.174. The RR for the above data is then
calculated using the equation given in Section 7.4.1. For the example,
RR=1.174.
Note: Not all labeled compounds elute before their pollutant
analogs.
7.4.4 To calibrate the analytical system by isotope dilution,
analyze a 5 mL aliquot of each of the aqueous calibration standards
(Section 6.7.1) spiked with an appropriate constant amount of the
labeled compound spiking solution (Section 6.6), using the purge and
trap procedure in section 10. Compute the RR at each concentration.
7.4.5 Linearity--if the ratio of relative response to concentration
for any compound is constant (less than 20 percent coefficient of
variation) over the 5 point calibration range, an averaged relative
response/concentration ratio may be used for that compound; otherwise,
the complete calibration curve for that compound shall be used over the
5 point calibration range.
7.5 Calibration by internal standard--used when criteria for isotope
dilution (Section 7.4) cannot be met. The method is applied to
pollutants having no labeled analog and to the labeled compounds. The
internal stand ards used for volatiles analyses are brom o chlor o
methane, 2-bromo-1-chloropropane, and 1,4-dichlorobutane. Concentrations
of the labeled compounds and pollutants without labeled analogs are
computed relative to the nearest eluted internal standard, as shown in
table 2.
7.5.1 Response factors--calibration requires the determination of
response factors (RF) which are defined by the following equation:
RF=(AsxCis)/(AisxCs),
where As is the EICP area at the characteristic m/z for the
compound in the daily standard. Ais is the EICP area at the
characteristic m/z for the internal standard.
Cis is the concentration (ug/L) of the internal standard
Cs is the concentration of the pollutant in the daily
standard.
7.5.2 The response factor is determined at 10, 20, 50, 100, and 200
ug/L for the pollutants (optionally at five times these concentrations
for gases and water soluble pollutants--see Section 6.7), in a way
analogous to that for calibration by isotope dilution (Section 7.4.4).
The RF is plotted against concentration for each compound in the
standard (Cs) to produce a calibration curve.
7.5.3 Linearity--if the response factor (RF) for any compound is
constant (less than 35 percent coefficient of variation) over the 5
point calibration range, an averaged response factor may be used for
that compound; otherwise, the complete calibration curve for that
compound shall be used over the 5 point range.
7.6 Combined calibration--by adding the isotopically labeled
compounds and internal standards (Section 6.6) to the aqueous
calibration standards (Section 6.7.1), a single set of analyses can be
used to produce calibration curves for the isotope dilution and internal
standard methods. These curves are verified each shift (Section 11.5) by
purging the aqueous performance standard (Section 6.7.2). Recalibration
is required only if calibration and on-going performance (Section 11.5)
criteria cannot be met.
8. Quality Assurance/Quality Control
8.1 Each laboratory that uses this method is required to operate a
formal quality assurance program. The minimum requirements of this
program consist of an initial demonstration of laboratory capability,
analysis of samples spiked with labeled compounds to evaluate and
document data quality, and analysis of standards and blanks as tests of
continued performance. Laboratory performance is compared to established
performance criteria to determine if the results of analyses meet the
performance characteristics of the method.
8.1.1 The analyst shall make an initial demonstration of the ability
to generate acceptable accuracy and precision with this method. This
ability is established as described in Section 8.2.
8.1.2 The analyst is permitted to modify this method to improve
separations or lower the costs of measurements, provided all performance
specifications are met. Each time a modification is made to the method,
the analyst is required to repeat the procedure in Section 8.2 to
demonstrate method performance.
8.1.3 Analyses of blanks are required to demonstrate freedom from
contamination and that the compounds of interest and interfering
compounds have not been carried over from a previous analysis (Section
3). The procedures and criteria for analysis of a blank are described in
Sections 8.5 and 11.7.
8.1.4 The laboratory shall spike all samples with labeled compounds
to monitor method performance. This test is described in Section 8.3.
When results of these spikes indicate atypical method performance for
samples, the samples are diluted to bring method performance within
acceptable limits (Section 14.2).
8.1.5 The laboratory shall, on an on-going basis, demonstrate
through the analysis of the aqueous performance standard (Section 6.7.2)
that the analysis system is in control. This procedure is described in
Sections 11.1 and 11.5.
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8.1.6 The laboratory shall maintain rec ords to define the quality
of data that is generated. Development of accuracy statements is
described in Sections 8.4 and 11.5.2.
8.2 Initial precision and accuracy--to establish the ability to
generate acceptable precision and accuracy, the analyst shall perform
the following operations:
8.2.1 Analyze two sets of four 5-mL aliquots (8 aliquots total) of
the aqueous performance standard (Section 6.7.2) according to the method
beginning in Section 10.
8.2.2 Using results of the first set of four analyses in Section
8.2.1, compute the average recovery (X) in [micro]g/L and the standard
deviation of the recovery (s) in [micro]g/L for each compound, by
isotope dilution for pol lui tants with a labeled analog, and by
internal standard for labeled compounds and pollutants with no labeled
analog.
8.2.3 For each compound, compare s and X with the corresponding
limits for initial precision and accuracy found in table 5. If s and X
for all compounds meet the acceptance criteria, system performance is
acceptable and analysis of blanks and samples may begin. If individual X
falls outside the range for accuracy, system performance is unacceptable
for that compound.
Note: The large number of compounds in table 5 present a substantial
probability that one or more will fail one of the acceptance criteria
when all compoulds are analyzed. To determine if the analytical system
is out of control, or if the failure can be attributed to probability,
proceed as follows:
8.2.4 Using the results of the second set of four analyses, compute
s and X for only those compounds which failed the test of the first set
of four analyses (Section 8.2.3). If these compounds now pass, system
performance is acceptable for all compounds and analysis of blanks and
samples may begin. If, however, any of the same compounds fail again,
the analysis system is not performing properly for the compound(s) in
question. In this event, correct the problem and repeat the entire test
(Section 8.2.1).
8.3 The laboratory shall spike all samples with labeled compounds to
assess method performance on the sample matrix.
8.3.1 Spike and analyze each sample according to the method
beginning in Section 10.
8.3.2 Compute the percent recovery (P) of the labeled compounds
using the internal standard method (Section 7.5).
8.3.3 Compare the percent recovery for each compound with the
corresponding labeled compound recovery limit in table 5. If the
recovery of any compound falls outside its warning limit, method
performance is unacceptable for that compound in that sample. Therefore,
the sample matrix is complex and the sample is to be diluted and
reanalyzed, per Section 14.2.
8.4 As part of the QA program for the laboratory, method accuracy
for wastewater samples shall be assessed and records shall be
maintained. After the analysis of five wastewater samples for which the
labeled compounds pass the tests in Section 8.3.3, compute the average
percent recovery (P) and the standard deviation of the percent recovery
(sp) for the labeled compounds only. Express the accuracy
assessment as a percent recovery interval from P-2sp to
P+2sp. For example, if P=90% and sp=10%, the
accuracy interval is expressed as 70-110%. Update the accuracy
assessment for each compound on a regular basis (e.g. after each 5-10
new accuracy measurements).
8.5 Blanks--reagent water blanks are analyzed to demonstrate freedom
from carry-over (Section 3) and contamination.
8.5.1 The level at which the purge and trap system will carry
greater than 5 [micro]g/L of a pollutant of interest (table 1) into a
succeeding blank shall be determined by analyzing successively larger
concentrations of these compounds. When a sample contains this
concentration or more, a blank shall be analyzed immediately following
this sample to demonstrate no carry-over at the 5 [micro]g/L level.
8.5.2 With each sample lot (samples analyzed on the same 8 hr
shift), a blank shall be analyzed immediately after analysis of the
aqueous performance standard (Section 11.1) to demonstrate freedom from
contamination. If any of the compounds of interest (table 1) or any
potentially interfering compound is found in a blank at greater than 10
[micro]g/L (assuming a response factor of 1 relative to the nearest
eluted internal standard for compounds not listed in table 1), analysis
of samples is halted until the source of contamination is eliminated and
a blank shows no evidence of contamination at this level.
8.6 The specifications contained in this method can be met if the
apparatus used is calibrated properly, then maintained in a calibrated
state.
The standards used for calibration (Section 7), calibration
verification (Section 11.5) and for initial (Section 8.2) and on-going
(Section 11.5) precision and accuracy should be identical, so that the
most precise results will be obtained. The GC/MS instrument in
particular will provide the most reproducible results if dedicated to
the settings and conditions required for the analyses of volatiles by
this method.
8.7 Depending on specific pro gram requirements, field repli cates
may be collected to determine the precision of the sampling technique,
and spiked samples may be required to determine the accuracy of the
analysis when internal or external standard methods are used.
[[Page 289]]
9. Sample Collection, Preservation, and Handling
9.1 Grab samples are collected in glass containers having a total
volume greater than 20 mL. Fill sample bottles so that no air bubbles
pass through the sample as the bottle is filled. Seal each bottle so
that no air bubbles are entrapped. Maintain the hermetic seal on the
sample bottle until time of analysis.
9.2 Samples are maintained at 0-4 [deg]C from the time of collection
until analysis. If the sample contains residual chlorine, add sodium
thiosulfate preservative (10 mg/40 mL) to the empty sample bottles just
prior to shipment to the sample site. EPA Methods 330.4 and 330.5 may be
used for measurement of residual chlorine (Reference 8). If preservative
has been added, shake bottle vigorously for one minute immediately after
filling.
9.3 Experimental evidence indicates that some aromatic compounds,
notably benzene, toluene, and ethyl benzene are susceptible to rapid
biological degradation under certain environmental conditions.
Refrigeration alone may not be adequate to preserve these compounds in
wastewaters for more than seven days. For this reason, a separate sample
should be collected, acidified, and analyzed when these aromatics are to
be determined. Collect about 500 mL of sample in a clean container.
Adjust the pH of the sample to about 2 by adding HCl (1+1) while
stirring. Check pH with narrow range (1.4 to 2.8) pH paper. Fill a
sample container as described in Section 9.1. If residual chlorine is
present, add sodium thiosulfate to a separate sample container and fill
as in Section 9.1.
9.4 All samples shall be analyzed within 14 days of collection.
10. Purge, Trap, and GC/MS Analysis
10.1 Remove standards and samples from cold storage and bring to 20-
25 [deg].
10.2 Adjust the purge gas flow rate to 40 4
mL/min. Attach the trap inlet to the purging device and set the valve to
the purge mode (figure 3). Open the syringe valve located on the purging
device sample introduction needle (figure 1).
10.3 Remove the plunger from a 5-mL syringe and attach a closed
syringe valve. Open the sample bottle and carefully pour the sample into
the syringe barrel until it overflows. Replace the plunger and compress
the sample. Open the syringe valve and vent any residual air while
adjusting the sample volume to 5.0 mL. Because this process of taking an
aliquot destroys the validity of the sample for future analysis, fill a
second syringe at this time to protect against possible loss of data.
Add an appropriate amount of the labeled compound spiking solution
(Section 6.6) through the valve bore, then close the valve.
10.4 Attach the syringe valve assembly to the syringe valve on the
purging device. Open both syringe valves and inject the sample into the
purging chamber.
10.5 Close both valves and purge the sample for 11.0 0.1 minutes at 20-25 [deg]C.
10.6 After the 11 minute purge time, attach the trap to the
chromatograph and set the purge and trap apparatus to the desorb mode
(figure 4). Desorb the trapped compounds into the GC column by heating
the trap to 170-180 [deg]C while backflushing with carrier gas at 20-60
mL/min for four minutes. Start MS data acquisition upon start of the
desorb cycle, and start the GC column temperature program 3 minutes
later. Table 1 summarizes the recommended operating conditions for the
gas chromatograph. Included in this table are retention times and
detection limits that were achieved under these conditions. Other
columns may be used provided the requirements in Section 8 can be met.
If the priority pollutant gases produce GC peaks so broad that the
precision and recovery specifications (Section 8.2) cannot be met, the
column may be cooled to ambient or sub-ambient temperatures to sharpen
these peaks.
10.7 While analysis of the desorbed compounds proceeds, empty the
purging chamber using the sample introduction syringe. Wash the chamber
with two 5-mL portions of reagent water. After the purging device has
been emptied, allow the purge gas to vent through the chamber until the
frit is dry, so that it is ready for the next sample.
10.8 After desorbing the sample for four minutes, recondition the
trap by returning to the purge mode. Wait 15 seconds, then close the
syringe valve on the purging device to begin gas flow through the trap.
Maintain the trap temperature at 170-180 [deg]C. After approximately
seven minutes, turn off the trap heater and open the syringe valve to
stop the gas flow through the trap. When cool, the trap is ready for the
next sample.
11. System Performance
11.1 At the beginning of each 8 hr shift during which analyses are
performed, system calibration and performance shall be verified for all
pollutants and labeled compounds. For these tests, analysis of the
aqueous performance standard (Section 6.7.2) shall be used to verify all
performance criteria. Adjustment and/or recalibration (per Section 7)
shall be performed until all performance criteria are met. Only after
all performance criteria are met may blanks and samples be analyzed.
11.2 BFB spectrum validity--the criteria in table 3 shall be met.
11.3 Retention times--the absolute retention times of all compounds
shall approximate those given in Table 2.
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11.4 GC resolution--the valley height between toluene and toluene-d8
(at m/z 91 and 99 plotted on the same graph) shall be less than 10
percent of the taller of the two peaks.
11.5 Calibration verification and on-going precision and accuracy--
compute the concentration of each polutant (Table 1) by isotope dilution
(Section 7.4) for those compmunds which have labeled analogs. Compute
the concentration of each pollutant (Table 1) which has no labeled
analog by the internal standard method (Section 7.5). Compute the
concentration of the labeled compounds by the internal standard method.
These concentrations are computed based on the calibration data
determined in Section 7.
11.5.1 For each pollutant and labeled compound, compare the
concentration with the corresponding limit for on-going accuracy in
Table 5. If all compmunds meet the acceptance criteria, system
performance is acceptable and analysis of blanks and samples may
continue. If any individual value falls outside the range given, system
performance is unacceptable for that compound.
Note: The large number of compounds in Table 5 present a substantial
probability that one or more will fail the acceptance criteria when all
compounds are analyzed. To determine if the analytical system is out of
control, or if the failure may be attributed to probability, proceed as
follows:
11.5.1.1 Analyze a second aliquot of the aqueous performance
standard (Section 6.7.2).
11.5.1.2 Compute the concentration for only those compounds which
failed the first test (Section 11.5.1). If these compounds now pass,
system performance is acceptable for all compounds and analyses of
blanks and samples may proceed. If, however, any of the compounds fail
again, the measurement system is not performing properly for these
compounds. In this event, locate and correct the problem or recalibrate
the system (Section 7), and repeat the entire test (Section 11.1) for
all compounds.
11.5.2 Add results which pass the specification in 11.5.1.2 to
initial (Section 8.2) and previous on-going data. Update QC charts to
form a graphic representation of laboratory performance (Figure 7).
Develop a statement of accuracy for each pollutant and labeled compound
by calculating the average percentage recovery (R) and the standard
deviation of percent recovery (sr). Express the accuracy as a
recovery interval from R-2sr to R+2sr. For
example, if R=95% and sr=5%, the accuracy is 85-105 percent.
12. Qualitative Determination--Accomplished by Comparison of Data from
Analysis of a Sample or Blank with Data from Analysis of the Shift
Standard (Section 11.1). Identification is Confirmed When Spectra and
Retention Times Agree Per the Criteria Below
12.1 Labeled compounds and pollutants having no labeled analog:
12.1.1 The signals for all characteristic masses stored in the
spectral library (Section 7.2.4) shall be present and shall maximize
within the same two consecutive scans.
12.1.2 Either (1) the background corrected EICP areas, or (2) the
corrected relative intensities of the mass spectral peaks at the GC peak
maximum shall agree within a factor of two (0.5 to 2 times) for all
masses stored in the library.
12.1.3 The retention time relative to the nearest eluted internal
standard shall be within 7 scans or 20 seconds, whichever is greater.
12.2 Pollutants having a labeled analog:
12.2.1 The signals for all characteristic masses stored in the
spectral library (Section 7.2.4) shall be present and shall maximize
within the same two consecutive scans.
12.2.2 Either (1) the background corrected EICP areas, or (2) the
corrected relative intensities of the mass spectral peaks at the GC peak
maximum shall agree within a factor of two for all masses stored in the
spectral library.
12.2.3 The retention time difference between the pollutant and its
labeled analog shall agree within 2 scans or
6 seconds (whichever is greater) of this
difference in the shift standard (Section 11.1).
12.3 Masses present in the experimental mass spectrum that are not
present in the reference mass spectrum shall be accounted for by
contaminant or background ions. If the experimental mass spectrum is
contaminated, an experienced spectrometrist (Section 1.4) is to
determine the presence or absence of the compound.
13. Quantitative Determination
13.1 Isotope dilution--by adding a known amount of a labeled
compound to every sample prior to purging, correction for recovery of
the pollutant can be made because the pollutant and its labeled analog
exhibit the same effects upon purging, desorption, and gas
chromatography. Relative response (RR) values for sample mixtures are
used in conjunction with calibration curves described in Section 7.4 to
determine concentrations directly, so long as labeled compound spiking
levels are constant. For the toluene example given in Figure 6 (Section
7.4.3), RR would be equal to 1.174. For this RR value, the toluene
calibration curve given in Figure 5 indicates a concentration of 31.8
[micro]g/L.
[[Page 291]]
13.2 Internal standard--calculate the concentration using the
response factor determined from calibration data (Section 7.5) and the
following equation:
Concentration =(As x Cis)/(Ais x
RF) where the terms are as defined in Section 7.5.1.
13.3 If the EICP area at the quantitation mass for any compound
exceeds the calibration range of the system, the sample is diluted by
successive factors of 10 and these dilutions are analyzed until the area
is within the calibration range.
13.4 Report results for all pollutants and labeled compounds (Table
1) found in all standards, blanks, and samples, in [micro]g/L to three
significant figures. Results for samples which have been diluted are
reported at the least dilute level at which the area at the quantitation
mass is within the calibration range (Section 13.3) and the labeled
compound recovery is within the normal range for the Method (Section
14.2).
14. Analysis of Complex Samples
14.1 Untreated effluents and other samples frequently contain high
levels (1000 [micro]g/L) of the compounds of interest and of
interfering compounds. Some samples will foam excessively when purged;
others will overload the trap/or GC column.
14.2 Dilute 0.5 mL of sample with 4.5 mL of reagent water and
analyze this diluted sample when labeled compound recovery is outside
the range given in Table 5. If the recovery remains outside of the range
for this diluted sample, the aqueous performance standard shall be
analyzed (Section 11) and calibration verified (Section 11.5). If the
recovery for the labeled compmund in the aqueous performance standard is
outside the range given in Table 5, the analytical system is out of
control. In this case, the instrumelt shall be repaired, the performance
specifications in Section 11 shall be met, and the analysis of the
undiluted sample shall be repeated. If the recovery for the aqueous
performance standard is within the range given in Table 5, the method
does not work on the sample being analyzed and the result may not be
reported for regulatory compliance purposes.
14.3 Reverse search computer programs can misinterpret the spectrum
of chro ma tographically unresolved pollutant and labeled compound pairs
with overlapping spectra when a high level of the pollutant is present.
Examine each chromatogram for peaks greater than the height of the
internal standard peaks. These peaks can obscure the compounds of
interest.
15. Method Performance
15.1 The specifications for this method were taken from the inter-
laboratory validation of EPA Method 624 (reference 9). Method 1624 has
been shown to yield slightly better performance on treated effluents
than Method 624. Additional method performance data can be found in
Reference 10.
References
1. ``Performance Tests for the Evaluation of Computerized Gas
Chromatography/Mass Spectrometry Equipment and Laboratories,'' USEPA,
EMSL/Cincinnati, OH 45268, EPA-600/4-80-025 (April 1980).
2. Bellar, T.A. and Lichtenberg, J.J., ``Journal American Water
Works Association,'' 66, 739 (1974).
3. Bellar, T.A. and Lichtenberg, J.J., ``Semi-automated Headspace
Analysis of Drinking Waters and Industrial Waters for Purgeable Volatile
Organic Compounds,'' in Measurement of Organic Pollutants Water and
Wastewater, C.E. VanHall, ed., American Society for Testing Materials,
Philadelphia, PA, Special Technical Publication 686, (1978).
4. ``Working with Carcinogens,'' DHEW, PHS, NIOSH, Publication 77-
206 (1977).
5. ``OSHA Safety and Health Standards, General Industry,'' 29 CFR
part 1910, OSHA 2206, (1976).
6. ``Safety in Academic Chemistry Laboratories,'' American Chemical
Society Publication, Committee on Chemical Safety (1979).
7. ``Handbook of Analytical Quality Control in Water and Wastewater
Laboratories,'' USEPA, EMSL/Cincinnati, OH 45268, EPA-4-79-019 (March
1979).
8. ``Methods 330.4 and 330.5 for Total Residual Chlorine,'' USEPA,
EMSL/Cincinnati, OH 45268, EPA-4-79-020 (March 1979).
9. ``EPA Method Study 29 EPA Method 624--Purgeables,'' EPA 600/4-84-
054, National Technical Information Service, PB84-209915, Springfield,
Virginia 22161, June 1984.
10. ``Colby, B.N., Beimer, R.G., Rushneck, D.R., and Telliard, W.A.,
``Isotope Dilution Gas Chromatography-Mass Spectrometry for the
Determination of Priority Pollutants in Industrial Effluents,'' USEPA,
Effluent Guidelines Division, Washington, DC 20460 (1980).
Table 1--Volatile Organic Compounds Analyzed by Isotope Dilution Gc/MS
------------------------------------------------------------------------
CAS
Compound Storet registry EPA-EGD NPDES
------------------------------------------------------------------------
Acetone...................... 81552 67-64-1 516 V ........
Acrolein..................... 34210 107-02-8 002 V 001 V
Acrylonitrile................ 34215 107-13-1 003 V 002 V
Benzene...................... 34030 71-43-2 004 V 003 V
Bromodichloromethane......... 32101 75-27-4 048 V 012 V
[[Page 292]]
Bromoform.................... 32104 75-25-2 047 V 005 V
Bromomethane................. 34413 74-83-9 046 V 020 V
Carbon tetrachloride......... 32102 56-23-5 006 V 006 V
Chlorobenzene................ 34301 108-90-7 007 V 007 V
Chloroethane................. 34311 75-00-3 016 V 009 V
2-chloroethylvinyl ether..... 34576 110-75-8 019 V 010 V
Chloroform................... 32106 67-66-1 023 V 011 V
Chloromethane................ 34418 74-87-3 045 V 021 V
Dibromochloromethane......... 32105 124-48-1 051 V 008 V
1,1-dichloroethane........... 34496 75-34-3 013 V 014 V
1,2-dichloroethane........... 34536 107-06-2 010 V 015 V
1,1-dichloroethene........... 34501 75-35-4 029 V 016 V
Trans-1,2-dichloroethane..... 34546 156-60-5 030 V 026 V
1,2-dichloropropane.......... 34541 78-87-5 032 V 017 V
Cis-1,3-dichloropropene...... 34704 10061-01-5 ........ ........
Trans-1,3-dichloropropene.... 34699 10061-02-6 033 V ........
Diethyl ether................ 81576 60-29-7 515 V ........
P-dioxane.................... 81582 123-91-1 527 V ........
Ethylbenzene................. 34371 100-41-4 038 V 019 V
Methylene chloride........... 34423 75-09-2 044 V 022 V
Methyl ethyl ketone.......... 81595 78-93-3 514 V ........
1,1,2,2-tetrachloroethane.... 34516 79-34-5 015 V 023 V
Tetrachlorethene............. 34475 127-18-4 085 V 024 V
Toluene...................... 34010 108-88-3 086 V 025 V
1,1,1-trichloroethane........ 34506 71-55-6 011 V 027 V
1,1,2-trichloroethane........ 34511 79-00-5 014 V 028 V
Trichloroethene.............. 39180 79-01-6 087 V 029 V
Vinyl chloride............... 39175 75-01-4 088 V 031 V
------------------------------------------------------------------------
Table 2--Gas Chromatography of Purgeable Organic Compounds by Isotope
Dilution GC/MS
------------------------------------------------------------------------
Mean Minimum
EGD Ref retention level (2)
No. Compound EGD time ([micro]g/
(1) No. (Sec. L)
------------------------------------------------------------------------
181 Bromochloromethane (I.S.).............. 181 730 10
245 Chloromethane-d3....................... 181 147 50
345 Chloromethane.......................... 245 148 50
246 Bromomethane-d3........................ 181 243 50
346 Bromomethane........................... 246 246 50
288 Vinyl chloride-d3...................... 181 301 50
388 Vinyl chloride......................... 288 304 10
216 Chloroethane-d5........................ 181 378 50
316 Chloroethane........................... 216 386 50
244 Methylene chloride-d2.................. 181 512 10
344 Methylene chloride..................... 244 517 10
616 Acetone-d6............................. 181 554 50
716 Acetone................................ 616 565 50
002 Acrolein............................... 181 566 50
203 Acrylonitrile-d3....................... 181 606 50
303 Acrylonitrile.......................... 203 612 50
229 1,1-dichloroethene-d2.................. 181 696 10
329 1,1-dichloroethene..................... 229 696 10
213 1,1-dichloroethane-d3.................. 181 778 10
313 1,1-dichloroethane..................... 213 786 10
615 Diethyl ether-d10...................... 181 804 50
715 Diethyl ether.......................... 615 820 50
230 Trans-1,2-dichloroethene-d2............ 181 821 10
330 Trans-1,2-dichloroethene............... 230 821 10
614 Methyl ethyl ketone-d3................. 181 840 50
714 Methyl ethyl ketone.................... 614 848 50
223 Chloroform-13C1........................ 181 861 10
323 Chloroform............................. 223 861 10
210 1,2-dichloroethane-d4.................. 181 901 10
310 1,2-dichloroethane..................... 210 910 10
211 1,1,1-trichloroethane-13C2............. 181 989 10
311 1,1,1-trichloroethane.................. 211 999 10
527 p-dioxane.............................. 181 1001 10
206 Carbon tetrachloride-13C1.............. 182 1018 10
306 Carbon tetrachloride................... 206 1018 10
248 Bromodichloromethane-13C1.............. 182 1045 10
348 Bromodichloromethane................... 248 1045 10
232 1,2-dichloropropane-d6................. 182 1123 10
332 1.2-dichloropropane.................... 232 1134 10
233 Trans-1,3-dichloropropene-d4........... 182 1138 10
333 Trans-1,3-dichloropropene.............. 233 1138 10
287 Trichloroethene-13C1................... 182 1172 10
387 Trichloroethene........................ 287 1187 10
204 Benzene-d6............................. 182 1200 10
304 Benzene................................ 204 1212 10
251 Chlorodibromemethane-13C1.............. 182 1222 10
351 Chlorodibromomethane................... 251 1222 10
214 1,1,2-trichloroethane-13C2............. 182 1224 10
314 1,1,2-trichloroethane.................. 214 1224 10
019 2-chloroethylvinyl ether............... 182 1278 10
182 2-bromo-1-chloropropane (I.S.)......... 182 1306 10
247 Bromoform-13C1......................... 182 1386 10
347 Bromoform.............................. 247 1386 10
215 1,1,2,2-tetrachloroethane-d2........... 183 1525 10
315 1,1,2,2-tetrachloroethane.............. 215 1525 10
285 Tetrachloroethene-13C2................. 183 1528 10
385 Tetrachloroethene...................... 285 1528 10
183 1,4-dichlorobutale (int std)........... 183 1555 10
286 Toluene-d8............................. 183 1603 10
386 Toluene................................ 286 1619 10
[[Page 293]]
207 Chlorobenzene-d5....................... 183 1679 10
307 Chlorobenzene.......................... 207 1679 10
238 Ethylbenzene-d10....................... 183 1802 10
338 Ethylbenzene........................... 238 1820 10
185 Bromofluorobenzene..................... 183 1985 10
------------------------------------------------------------------------
(1) Reference numbers beginning with 0, 1 or 5 indicate a pollutant
quantified by the internal standard method; reference numbers
beginning with 2 or 6 indicate a labeled compound quantified by the
internal standard method; reference numbers beginning with 3 or 7
indicate a pollutant quantified by isotope dilution.
(2) This is a minimum level at which the analytical system shall give
recognizable mass spectra (background corrected) and acceptable
calibration points. Column: 2.4m (8 ft) x 2 mm i.d. glass, packed with
one percent SP-1000 coated on 60/80 Carbopak B. Carrier gas: helium at
40 mL/min. Temperature program: 3 min at 45 [deg]C, 8 [deg]C per min
to 240 [deg]C, hold at 240 [deg]C for 15 minutes.
Note: The specifications in this table were developed from data
collected from three wastewater laboratories.
Table 3--BFB Mass-Intensity Specifications
------------------------------------------------------------------------
Mass Intensity required
------------------------------------------------------------------------
50 15 to 40 percent of mass 95.
75 30 to 60 percent of mass 95.
95 base peak, 100 percent.
96 5 to 9 percent of mass 95.
173 <2 percent of mass 174.
174 50 percent of mass 95.
175 5 to 9 percent of mass 174
176 95 to 101 percent of mass 174
177 5 to 9 percent of mass 176.
------------------------------------------------------------------------
Table 4--Volatile Organic Compound Characteristic Masses
------------------------------------------------------------------------
Primary m/
Labeled compound Analog z's
------------------------------------------------------------------------
Acetone............................................ d6 58/64
Acrolein........................................... d2 56/58
Acrylonitrile...................................... d3 53/56
Benzene............................................ d6 78/84
Bromodichloromethane............................... 13C 83/86
Bromoform.......................................... 13C 173/176
Bromomethale....................................... d3 96/99
Carbon tetrachloride............................... 13C 47/48
Chlorobenzene...................................... d5 112/117
Chloroethane....................................... d5 64/71
2-chloroethylvinyl ether........................... d7 106/113
Chloroform......................................... 13C 85/86
Chloromethane...................................... d3 50/53
Dibromochloromethane............................... 13C 129/130
1,1-dichloroethane................................. d3 63/66
1,2-dichloroethane................................. d4 62/67
1,1-dichloroethene................................. d2 61/65
Trans-1,2-dichloroethene........................... d2 61/65
1,2-dichloropropane................................ d6 63/67
Cis-1,3-dichloropropene............................ d4 75/79
Trans-1,3-dichloropropene.......................... d4 75/79
Diethyl ether...................................... d10 74/84
p-dioxane.......................................... d8 88/96
Ethylbenzene....................................... d10 106/116
Methylene chloride................................. d2 84/88
Methyl ethyl ketone................................ d3 72/75
1,1,2,2-tetrachloroethane.......................... d2 83/84
Tetrachloroethene.................................. 13C2 166/172
Toluene............................................ d8 92/99
1,1,1-trichloroethane.............................. d3 97/102
1,1,2-trichloroethane.............................. 13C2 83/84
Trichloroethene.................................... 13C 95/133
Vinyl chloride..................................... d3 62/65
------------------------------------------------------------------------
Table 5--Acceptance Criteria for Performance Tests
----------------------------------------------------------------------------------------------------------------
Acceptance criteria at 20 [micro]g/L
------------------------------------------------------
Initial precision and Labeled On-going
accuracy section 8.2.3 compound accuracy
Compound ----------------------------- recovery sec. 11.5
sec. 8.3 ------------
s ([micro]g/ X ([micro]g/L) and 14.2
L) ------------- R ([micro]g/
P (percent) L)
----------------------------------------------------------------------------------------------------------------
Acetone.................................................. Note 1
Acrolein................................................. Note 2
Acrylonitrile............................................ Note 2
Benzene.................................................. 9.0 13.0-28.2 ns-196 4-33
Bromodichloromethane..................................... 8.2 6.5-31.5 ns-199 4-34
Bromoform................................................ 7.0 7.4-35.1 ns-214 6-36
Bromomethane............................................. 25.0 d-54.3 ns-414 d-61
Carbon tetrachloride..................................... 6.9 15.9-24.8 42-165 12-30
Chlorobenzene............................................ 8.2 14.2-29.6 ns-205 4-35
Chloroethane............................................. 14.8 2.1-46.7 ns-308 d-51
2-chloroethylvinyl ether................................. 36.0 d-69.8 ns-554 d-79
Chloroform............................................... 7.9 11.6-26.3 18-172 8-30
Chloromethane............................................ 26.0 d-55.5 ns-410 d-64
Dibromochloromethane..................................... 7.9 11.2-29.1 16-185 8-32
1,1-dichloroethane....................................... 6.7 11.4-31.4 23-191 9-33
1,2-dichloroethane....................................... 7.7 11.6-30.1 12-192 8-33
1,1-dichloroethene....................................... 11.7 d-49.8 ns-315 d-52
Trans-1,2-dichloroethene................................. 7.4 10.5-31.5 15-195 8-34
[[Page 294]]
1,2-dichloropropane...................................... 19.2 d-46.8 ns-343 d-51
Cis-1,3-dichloropropene.................................. 22.1 d-51.0 ns-381 d-56
Trans-1,3-dichloropropene................................ 14.5 d-40.2 ns-284 d-44
Diethyl ether............................................ Note 1
P-dioxane................................................ Note 1
Ethyl benzene............................................ 9.6 15.6-28.5 ns-203 5-35
Methylene chloride....................................... 9.7 d-49.8 ns-316 d-50
Methyl ethyl ketone...................................... Note 1
1,1,2,2-tetrachloroethane................................ 9.6 10.7-30.0 5-199 7-34
Tetrachloroethene........................................ 6.6 15.1-28.5 31-181 11-32
Toluene.................................................. 6.3 14.5-28.7 4-193 6-33
1,1,1-trichloroethane.................................... 5.9 10.5-33.4 12-200 8-35
1,1,2-trichloroethane.................................... 7.1 11.8-29.7 21-184 9-32
Trichloroethene.......................................... 8.9 16.6-29.5 35-196 12-34
Vinyl chloride........................................... 27.9 d-58.5 ns-452 d-65
----------------------------------------------------------------------------------------------------------------
d = detected; result must be greater than zero.
ns = no specification; limit would be below detection limit.
Note 1: Specifications not available for these compounds at time of release of this method.
Note 2: Specifications not developed for these compounds; use method 603.
[[Page 295]]
[GRAPHIC] [TIFF OMITTED] TC02JY92.055
[[Page 296]]
[GRAPHIC] [TIFF OMITTED] TC02JY92.056
Method 1625 Revision B--Semivolatile Organic Compounds by Isotope
Dilution GC/MS
1. Scope and Application
1.1 This method is designed to determine the semivolatile toxic
organic pollutants associated with the 1976 Consent Decree and
additional compounds amenable to extraction and analysis by capillary
column gas chromatography-mass spectrometry (GC/MS).
1.2 The chemical compounds listed in Tables 1 and 2 may be
determined in municipal and industrial discharges by this method. The
method is designed to meet the survey
[[Page 297]]
requirements of Effluent Guidelines Division (EGD) and the National
Pollutants Discharge Elimination System (NPDES) under 40 CFR 136.1. Any
modifications of this method, beyond those expressly permitted, shall be
considered as major modifications subject to application and approval of
alternate test procedures under 40 CFR 136.4 and 136.5.
1.3 The detection limit of this method is usually dependent on the
level of interferences rather than instrumental limitations. The limits
listed in Tables 3 and 4 represent the minimum quantity that can be
detected with no interferences present.
1.4 The GC/MS portions of this method are for use only by analysts
experienced with GC/MS or under the close supervision of such qualified
persons. Laboratories unfamiliar with analyses of environmental samples
by GC/MS should run the performance tests in reference 1 before
beginning.
2. Summary of Method
2.1 Stable isotopically labeled analogs of the compounds of interest
are added to a one liter wastewater sample. The sample is extracted at
pH 12-13, then at pH <2 with methylene chloride using continuous
extraction techniques. The extract is dried over sodium sulfate and
concentrated to a volume of one mL. An internal standard is added to the
extract, and the extract is injected into the gas chromatograph (GC).
The compounds are separated by GC and detected by a mass spectrometer
(MS). The labeled compounds serve to correct the variability of the
analytical technique.
2.2 Identification of a compound (qualitative analysis) is performed
by comparing the GC retention time and background corrected
characteristic spectral masses with those of authentic standards.
2.3 Quantitative analysis is performed by GC/MS using extracted ion
current profile (EICP) areas. Isotope dilution is used when labeled
compounds are available; otherwise, an internal standard method is used.
2.4 Quality is assured through reproducible calibration and testing
of the extraction and GC/MS systems.
3. Contamination and Interferences
3.1 Solvents, reagents, glassware, and other sample processing
hardware may yield artifacts and/or elevated baselines causing
misinterpretation of chromatograms and spectra. All materials shall be
demonstrated to be free from interferences under the conditions of
analysis by running method blanks initially and with each sample lot
(samples started through the extraction process on a given 8 hr shift,
to a maximum of 20). Specific selection of reagents and purification of
solvents by distillation in all-glass systems may be required. Glassware
and, where possible, reagents are cleaned by solvent rinse and baking at
450 [deg]C for one hour minimum.
3.2 Interferences coextracted from samples will vary considerably
from source to source, depending on the diversity of the industrial
complex or municipality being samples.
4. Safety
4.1 The toxicity or carcinogenicity of each compound or reagent used
in this method has not been precisely determined; however, each chemical
compound should be treated as a potential health hazard. Exposure to
these compounds should be reduced to the lowest possible level. The
laboratory is responsible for maintaining a current awareness file of
OSHA regulations regarding the safe handling of the chemicals specified
in this method. A reference file of data handling sheets should also be
made available to all personnel involved in these analyses. Additional
information on laboratory safety can be found in references 2-4.
4.2 The following compounds covered by this method have been
tentatively classified as known or suspected human or mammalian
carcinogens: benzidine benzo(a)anthracene, 3,3'-dichlorobenzidine,
benzo(a)pyrene, di ben zo(a,h)an thra cene, N-nitrosodimethylamine, and
[beta]-naphtylamine. Primary standards of these compounds shall be
prepared in a hood, and a NIOSH/MESA approved toxic gas respirator
should be worn when high concentrations are handled.
5. Apparatus and Materials
5.1 Sampling equipment for discrete or composite sampling.
5.1.1 Sample bottle, amber glass, 1.1 liters minimum. If amber
bottles are not available, samples shall be protected from light.
Bottles are detergent water washed, then solvent rinsed or baked at 450
[deg]C for one hour minimum before use.
5.1.2 Bottle caps--threaded to fit sample bottles. Caps are lined
with Teflon. Aluminum foil may be substituted if the sample is not
corrosive. Liners are detergent water washed, then reagent water
(Section 6.5) and solvent rinsed, and baked at approximately 200 [deg]C
for one hour minimum before use.
5.1.3 Compositing equipment--automatic or manual compositing system
incorporating glass containers for collection of a minimum 1.1 liters.
Sample containers are kept at 0 to 4 [deg]C during sampling. Glass or
Teflon tubing only shall be used. If the sampler uses a peristaltic
pump, a minimum length of compressible silicone rubber tubing may be
used in the pump only. Before use, the tubing is thoroughly rinsed with
methanol, followed by repeated rinsings with reagent water (Section 6.5)
to minimize sample contamination. An integrating flow meter is used to
collect proportional composite samples.
[[Page 298]]
5.2 Continuous liquid-liquid extractor--Teflon or glass conncecting
joints and stopcocks without lubrication (Hershberg-Wolf Extractor) one
liter capacity, Ace Glass 6841-10, or equivalent.
5.3 Drying column--15 to 20 mm i.d. Pyrex chromatographic column
equipped with coarse glass frit or glass wool plug.
5.4 Kuderna-Danish (K-D) apparatus
5.4.1 Concentrator tube--10mL, graduated (Kontes K-570050-1025, or
equivalent) with calibration verified. Ground glass stopper (size 19/22
joint) is used to prevent evaporation of extracts.
5.4.2 Evaporation flask--500 mL (Kontes K-570001-0500, or
equivalent), attached to concentrator tube with springs (Kontes K-
662750-0012).
5.4.3 Snyder column--three ball macro (Kontes K-503000-0232, or
equivalent).
5.4.4 Snyder column--two ball micro (Kontes K-469002-0219, or
equivalent).
5.4.5 Boiling chips--approx 10/40 mesh, extracted with methylene
chloride and baked at 450 [deg]C for one hr minimum.
5.5 Water bath--heated, with concentric ring cover, capable of
temperature control 2 [deg]C, installed in a fume
hood.
5.6 Sample vials--amber glass, 2-5 mL with Teflon-lined screw cap.
5.7 Analytical balance--capable of weighing 0.1 mg.
5.8 Gas chromatograph--shall have splitless or on-column injection
port for ca pil lary column, temperature program with 30 [deg]C hold,
and shall meet all of the performance specifications in Section 12.
5.8.1 Column--305 mx0.250.02 mm i.d. 5% phenyl, 94% methyl, 1% vinyl silicone
bonded phase fused silica capillary column (J & W DB-5, or equivalent).
5.9 Mass spectrometer--70 eV electron impact ionization, shall
repetitively scan from 35 to 450 amu in 0.95 to 1.00 second, and shall
produce a unit resolution (valleys be tween m/z 441-442 less than 10
percent of the height of the 441 peak), backgound cor rected mass
spectrum from 50 ng decaflu o ro tri phenylphosphine (DFTPP) introduced
through the GC inlet. The spectrum shall meet the mass-intensity
criteria in Table 5 (reference 5). The mass spectrometer shall be
interfaced to the GC such that the end of the capillary column
terminates within one centimeter of the ion source but does not
intercept the electron or ion beams. All portions of the column which
connect the GC to the ion source shall remain at or above the column
temperature during analysis to preclude condensation of less volatile
compounds.
5.10 Data system--shall collect and record MS data, store mass-
intensity data in spectral libraries, process GC/MS data, generate
reports, and shall compute and record response factors.
5.10.1 Data acquisition--mass spectra shall be collected
continuously throughout the analysis and stored on a mass storage
device.
5.10.2 Mass spectral libraries--user created libraries containing
mass spectra obtained from analysis of authentic standards shall be
employed to reverse search GC/MS runs for the compounds of interest
(Section 7.2).
5.10.3 Data processing--the data system shall be used to search,
locate, identify, and quantify the compounds of interest in each GC/MS
analysis. Software routines shall be employed to compute retention times
and peak areas. Displays of spectra, mass chromatograms, and library
comparisons are required to verify results.
5.10.4 Response factors and multipoint calibrations--the data system
shall be used to record and maintain lists of response factors (response
ratios for isotope dilution) and multipoint calibration curves (Section
7). Computations of relative standard deviation (coefficient of
variation) are useful for testing calibration linearity. Statistics on
initial (Section 8.2) and on-going (Section 12.7) performance shall be
computed and maintained.
6. Reagents and Standards
6.1 Sodium hydroxide--reagent grade, 6N in reagent water.
6.2 Sulfuric acid--reagent grade, 6N in reagent water.
6.3 Sodium sulfate--reagent grade, granular anhydrous, rinsed with
methylene chloride (20 mL/g) and conditioned at 450 [deg]C for one hour
minimum.
6.4 Methylene chloride--distilled in glass (Burdick and Jackson, or
equivalent).
6.5 Reagent water--water in which the compounds of interest and
interfering compounds are not detected by this method.
6.6 Standard solutions--purchased as solutions or mixtures with
certification to their purity, concentration, and authenticity, or pre
pared from materials of known purity and com position. If compound
purity is 96 percent or greater, the weight may be used without
correction to compute the concentration of the standard. When not being
used, standards are stored in the dark at -20 to -10 [deg]C in screw-
capped vials with Teflon-lined lids. A mark is placed on the vial at the
level of the solution so that solvent evaporation loss can be detected.
The vials are brought to room temperature prior to use. Any precipitate
is redissolved and solvent is added if solvent loss has occurred.
6.7 Preparation of stock solutions--prepare in methylene chloride,
benzene, p-dioxane, or a mixture of these solvents per the steps below.
Observe the safety precautions in Section 4. The large number of labeled
and unlabeled acid, base/neutral, and Appendix C compounds used for
combined calibration (Section 7) and calibration verification (12.5)
require high
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concentratimns (approx 40 mg/mL) when individual stock solutions are
prepared, so that dilutions of mixtures will permit calibration with all
compounds in a single set of solutions. The working range for most
compounds is 10-200 [micro]g/mL. Compounds with a reduced MS response
may be prepared at higher concentrations.
6.7.1 Dissolve an appropriate amount of assayed reference material
in a suitable solvent. For example, weigh 400 mg naphthalene in a 10 mL
ground glass stoppered volumetric flask and fill to the mark with
benzene. After the naphthalene is completely dissolved, transfer the
solution to a 15 mL vial with Teflon-lined cap.
6.7.2 Stock standard solutions should be checked for signs of
degradation prior to the preparation of calibration or performance test
standards. Quality control check samples that can be used to determine
the accuracy of calibration standards are available from the US
Environmental Protection Agency, Environmental Monitoring and Support
Laboratory, Cincinnati, Ohio 45268.
6.7.3 Stock standard solutions shall be replaced after six months,
or sooner if comparison with quality control check samples indicates a
change in concentration.
6.8 Labeled compound spiking solution--from stock standard solutions
prepared as above, or from mixtures, prepare the spiking solution at a
concentration of 200 [micro]g/mL, or at a concentration appropriate to
the MS response of each compound.
6.9 Secondary standard--using stock solutions (Section 6.7), prepare
a secondary standard containing all of the compounds in Tables 1 and 2
at a concentration of 400 [micro]g/mL, or higher concentration
appropriate to the MS response of the compound.
6.10 Internal standard solution--prepare 2,2'-difluorobiphenyl (DFB)
at a concentration of 10 mg/mL in benzene.
6.11 DFTPP solution--prepare at 50 [micro]g/mL in acetone.
6.12 Solutions for obtaining authentic mass spectra (Section 7.2)--
prepare mixtures of compounds at concentrations which will assure
authentic spectra are obtained for storage in libraries.
6.13 Calibration solutions--combine 0.5 mL of the solution in
Section 6.8 with 25, 50, 125, 250, and 500 uL of the solution in section
6.9 and bring to 1.00 mL total volume each. This will produce
calibration solutions of nominal 10, 20, 50, 100, and 200 [micro]g/mL of
the pollutants and a constant nominal 100 [micro]g/mL of the labeled
compounds. Spike each solution with 10 [micro]L of the internal standard
solution (Section 6.10). These solutions permit the relative response
(labeled to unlabeled) to be measured as a function of concentration
(Section 7.4).
6.14 Precision and recovery standard--used for determination of
initial (Section 8.2) and on-going (Section 12.7) precision and
recovery. This solution shall contain the pollutants and labeled
compounds at a nominal concentration of 100 [micro]g/mL.
6.15 Stability of solutions--all standard solutions (Sections 6.8-
6.14) shall be analyzed within 48 hours of preparation and on a monthly
basis thereafter for signs of degradation. Standards will remain
acceptable if the peak area at the quantitation mass relative to the DFB
internal standard remains within 15 percent of the
area obtained in the initial analysis of the standard.
7. Calibration
7.1 Assemble the GC/MS and establish the operating conditions in
Table 3. Analyze standards per the procedure in Section 11 to
demonstrate that the analytical system meets the detection limits in
Tables 3 and 4, and the mass-intensity criteria in Table 5 for 50 ng
DFTPP.
7.2 Mass spectral libraries--detection and identification of
compounds of interest are dependent upon spectra stored in user created
libraries.
7.2.1 Obtain a mass spectrum of each pollutant, labeled compound,
and the internal standard by analyzing an authentic standard either
singly or as part of a mixture in which there is no interference between
closely eluted components. That only a single compound is present is
determined by examination of the spectrum. Fragments not attributable to
the compound under study indicate the presence of an interfering
compound.
7.2.2 Adjust the analytical conditions and scan rate (for this test
only) to produce an undistorted spectrum at the GC peak maximum. An
undistorted spectrum will usually be obtained if five complete spectra
are collected across the upper half of the GC peak. Software algorithms
designed to ``enhance'' the spectrum may eliminate distortion, but may
also eliminate authentic masses or introduce other distortion.
7.2.3 The authentic reference spectrum is obtained under DFTPP
tuning conditions (Section 7.1 and Table 5) to normalize it to spectra
from other instruments.
7.2.4 The spectrum is edited by saving the 5 most intense mass
spectral peaks and all other mass spectral peaks greater than 10 percent
of the base peak. This edited spectrum is stored for reverse search and
for compound confirmation.
7.3 Analytical range--demonstrate that 20 ng anthracene or
phenanthrene produces an area at m/z 178 approx one-tenth that required
to exceed the linear range of the system. The exact value must be
determined by experience for each instrument. It is used to match the
calibration range of the instrument to the analytical range and
detection limits required, and to diagnose instrument sensitivity
problems (Section 15.4). The 20 ug/mL calibration standard (Section
6.13) can be used to demonstrate this performance.
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7.3.1 Polar compound detection--demonstrate that unlabeled
pentachlorophenol and benzidine are detectable at the 50 [micro]g/mL
level (per all criteria in Section 13). The 50 [micro]g/mL calibration
standard (Section 6.13) can be used to demonstrate this performance.
7.4 Calibration with isotope dilution--isotope dilution is used when
(1) labeled compounds are available, (2) interferences do not preclude
its use, and (3) the quantitation mass extracted ion current profile
(EICP) area for the compound is in the calibration range. If any of
these conditions preclude isotope dilution, internal standard methods
(Section 7.5 or 7.6) are used.
7.4.1 A calibration curve encompassing the concentration range is
prepared for each compound to be determined. The relative response
(pollutant to labeled) vs concentration in standard solutions is plotted
or computed using a linear regression. The example in Figure 1 shows a
calibration curve for phenol using phenol-d5 as the isotopic diluent.
Also shown are the 10 percent error limits
(dotted lines). Relative Reponse (RR) is determined according to the
procedures described below. A minimum of five data points are employed
for calibration.
7.4.2 The relative response of a pollutant to its labeled analog is
determined from isotope ratio values computed from acquired data. Three
isotope ratios are used in this process:
RX = the isotope ratio measured for the pure pollutant.
Ry = the isotope ratio measured for the labeled compound.
Rm = the isotope ratio of an analytical mixture of
pollutant and labeled compounds.
The m/z's are selected such that RX
Ry. If Rm is not between 2Ry and
0.5RX, the method does not apply and the sample is analyzed
by internal or external standard methods.
7.4.3 Capillary columns usually separate the pollutant-labeled pair,
with the labeled compound eluted first (Figure 2). For this case,
RX = [area m1/z]/1, at the retention time of the
pollutant (RT2). Ry = 1/[area m2/z, at
the retention time of the labeled compound RT1).
Rm = [area at m1/z (at RT2)]/[area at
RT1)], as measured in the mixture of the pollutant and
labeled compounds (Figure 2), and RR = Rm.
7.4.4 Special precautions are taken when the pollutant-labeled pair
is not separated, or when another labeled compound with interfering
spectral masses overlaps the pollutant (a case which can occur with
isomeric compounds). In this case, it is necessary to determine the
respective contributions of the pollutant and labeled compounds to the
respective EICP areas. If the peaks are separated well enough to permit
the data system or operator to remove the contributions of the compounds
to each other, the equations in Section 7.4.3 apply. This usually occurs
when the height of the valley between the two GC peaks at the same m/z
is less than 10 percent of the height of the shorter of the two peaks.
If significant GC and spectral overlap occur, RR is computed using the
following equation:
RR = (Ry - Rm) (RX + 1)/
(Rm - RX) (Ry + 1), where RX
is measured as shown in Figure 3A, Ry is measured as shown in
Figure 3B, and Rm is measured as shown in Figure 3C. For
example, RX = 46100/4780 = 9.644, Ry = 2650/43600
= 0.0608, Rm = 49200/48300 = 1.019. amd RR = 1.114.
7.4.5 To calibrate the analytical system by isotope dilution,
analyze a 1.0 [micro]L aliquot of each of the calibration standards
(Section 6.13) using the procedure in Section 11. Compute the RR at each
concentration.
7.4.6 Linearity--if the ratio of relative response to concentration
for any compound is constant (less than 20 percent coefficient of
variation) over the 5 point calibration range, and averaged relative
response/concentration ratio may be used for that compound; otherwise,
the complete calibration curve for that compound shall be used over the
5 point calibration range.
7.5 Calibration by internal standard--used when criteria for istope
dilution (Section 7.4) cannot be met. The internal standard to be used
for both acid and base/neutral analyses is 2,2'-difluorobiphenyl. The
internal standard method is also applied to determination of compounds
having no labeled analog, and to measurement of labeled compounds for
intra-laboratory statistics (Sections 8.4 and 12.7.4).
7.5.1 Response factors--calibration requires the determination of
response factors (RF) which are defined by the following equation:
RF = (As x Cis)/(Ais x
Cs), where
As is the area of the characteristic mass for the
compmund in the daily standard
Ais is the area of the characteristic mass for the
internal standard
Cis is the concentration of the internal standard
([micro]g/mL)
Cs is the concentration of the compound in the daily
standard ([micro]g/mL)
7.5.1.1 The response factor is determined for at least five
concentrations appropriate to the response of each compound (Section
6.13); nominally, 10, 20, 50, 100, and 200 [micro]g/mL. The amount of
internal standard added to each extract is the same (100 [micro]g/mL) so
that Cis remains constant. The RF is plotted vs concentration
for each compound in the standard (Cs) to produce a
calibration curve.
7.5.1.2 Linearity--if the response factor (RF) for any compound is
constant (less than 35 percent coefficient of variation) over the 5
point calibration range, an averaged response factor may be used for
that compound; otherwise, the complete calibration
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curve for that compound shall be used over the 5 point range.
7.6 Combined calibration--by using calibration solutions (Section
6.13) containing the pollutants, labeled compounds, and the internal
standard, a single set of analyses can be used to produce calibration
curves for the isotope dilution and internal standard methods. These
curves are verified each shift (Section 12.5) by analyzing the 100
[micro]g/mL calibration standard (Section 6.13). Recalibration is
required only if calibration verification (Section 12.5) criteria cannot
be met.
8. Quality Assurance/Quality Control
8.1 Each laboratory that uses this method is required to operate a
formal quality assurance program. The minimum requirements of this
program consist of an initial demonstration of laboratory capability,
analysis of samples spiked with labeled compounds to evaluate and
document data quality, and analysis of standards and blanks as tests of
continued performance. Laboratory performance is compared to established
performance criteria to determine if the results of analyses meet the
performance characteristics of the method.
8.1.1 The analyst shall make an initial demonstration of the ability
to generate acceptable accuracy and precision with this method. This
ability is established as described in Section 8.2.
8.1.2 The analyst is permitted to modify this method to improve
separations or lower the costs of measurements, provided all performance
specifications are met. Each time a modification is made to the method,
the analyst is required to repeat the procedure in Section 8.2 to
demonstrate method performance.
8.1.3 Analyses of blanks are required to demonstrate freedom from
contamination. The procedures and criteria for analysis of a blank are
described in Section 8.5.
8.1.4 The laboratory shall spike all samples with labeled compounds
to monitor method performance. This test is described in Section 8.3.
When results of these spikes indicate atypical method performance for
samples, the samples are diluted to bring method performance within
acceptable limits (Section 15).
8.1.5 The laboratory shall, on an on-going basis, demonstrate
through calibration verification and the analysis of the precision and
recovery standard (Section 6.14) that the analysis system is in control.
These procedures are described in Sections 12.1, 12.5, and 12.7.
8.1.6 The laboratory shall maintain records to define the quality of
data that is generated. Development of accuracy statements is described
in Section 8.4.
8.2 Initial precision and accuracy--to establish the ability to
generate acceptable precision and accuracy, the analyst shall perform
the following operations:
8.2.1 Extract, concentrate, and analyze two sets of four one-liter
aliquots (8 aliquots total) of the precision and recovery standard
(Section 6.14) according to the procedure in Section 10.
8.2.2 Using results of the first set of four analyses, compute the
average recovery (X) in [micro]g/mL and the standard deviation of the
recovery (s) in [thetas]g/[micro]L for each compound, by isotope
dilution for pollutants with a labeled analog, and by internal standard
for labeled compounds and pollutants with no labeled analog.
8.2.3 For each compound, compare s and X with the corresponding
limits for initial precision and accuracy in Table 8. If s and X for all
compounds meet the acceptance criteria, system performance is acceptable
and analysis of blanks and samples may begin. If, however, any
individual s exceeds the precision limit or any individual X falls
outside the range for accuracy, system performance is unacceptable for
that compound.
Note: The large number of compounds in Table 8 present a substantial
probability that one or more will fail the acceptance criteria when all
compounds are analyzed. To determine if the analytical system is out of
control, or if the failure can be attributed to probability, proceed as
follows:
8.2.4 Using the results of the second set of four analyses, compute
s and X for only those compounds which failed the test of the first set
of four analyses (Section 8.2.3). If these compounds now pass, system
performance is acceptable for all compounds and analysis of blanks and
samples may begin. If, however, any of the same compoulds fail again,
the analysis system is not performing properly for these compounds. In
this event, correct the problem and repeat the entire test (Section
8.2.1).
8.3 The laboratory shall spike all samples with labeled compounds to
assess method performance on the sample matrix.
8.3.1 Analyze each sample according to the method in Section 10.
8.3.2 Compute the percent recovery (P) of the labeled compounds
using the internal standard methmd (Section 7.5).
8.3.3 Compare the labeled compound recovery for each compound with
the corresponding limits in Table 8. If the recovery of any compounds
falls outside its warning limit, method performance is unacceptable for
that compound in that sample, Therefore, the sample is complex and is to
be diluted and reanalyzed per Section 15.4.
8.4 As part of the QA program for the laboratory, method accuracy
for wastewater samples shall be assessed and records shall be
maintained. After the analysis of five wastewater samples for which the
labeled compounds pass the tests in Section 8.3, compute the average
percent recovery (P)
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and the standard deviation of the percent recovery (sp) for
the labeled compounds only. Express the accuracy assessment as a percent
recovery interval from P--2 sp to P+2sp. For
example, if P=90% and sp=10%, the accuracy interval is
expressed as 70-100%. Update the accuracy assessment for each compound
on a regular basis (e.g. after each 5-10 new accuracy measurements).
8.5 Blanks--reagent water blanks are analyzed to demonstrate freedom
from contamination.
8.5.1 Extract and concentrate a blank with each sample lot (samples
started through the extraction process on the same 8 hr shift, to a
maximum of 20 samples). Analyze the blank immediately after analysis of
the precision and recovery standard (Section 6.14) to demonstrate
freedom from contamination.
8.5.2 If any of the compounds of interest (Tables 1 and 2) or any
potentially interfering compound is found in a blank at greater than 10
[micro]g/L (assuming a response factor of 1 relative to the internal
standard for compounds not listed in Tables 1 and 2), analysis of
samples is halted until the source of contamination is eliminated and a
blank shows no evidence of contamination at this level.
8.6 The specifications contained in this method can be met if the
apparatus used is calibrated properly, then maintained in a calibrated
state. The standards used for calibration (Section 7), calibration
verification (Section 12.5), and for initial (Section 8.2) and on-going
(Section 12.7) precision and recovery should be identical, so that the
most precise results will be obtained. The GC/MS instrument in
particular will provide the most reproducible results if dedicated to
the settings and conditions required for the analysis of semi-volatiles
by this method.
8.7 Depending on specific program requirements, field replicates may
be collected to determine the precision of the sampling technique, and
spiked samples may be required to determine the accuracy of the analysis
when internal or external standard methods are used.
9. Sample Collection, Preservation, and Handling
9.1 Collect samples in glass containers following conventional
sampling practices (Reference 7). Composite samples are collected in
refrigerated glass containers (Section 5.1.3) in accordance with the
requirements of the sampling program.
9.2 Maintain samples at 0-4 [deg]C from the time collectimn until
extraction. If residual chlorine is present, add 80 mg sodium
thiosulfate per liter of water. EPA Methods 330.4 and 330.5 may be used
to measure residual chlorine (Reference 8).
9.3 Begin sample extraction within seven days of collection, and
analyze all extracts within 40 days of extraction.
10. Sample Extraction and Concentration (See Figure 4)
10.1 Labeled compound spiking--measure 1.00
0.01 liter of sample into a glass container. For untreated effluents,
and samples which are expected to be difficult to extract and/or
concentrate, measure an additional 10.0 0.1 mL
and dilute to a final volume of 1.00 0.01 liter
with reagent water in a glass container.
10.1.1 For each sample or sample lot (to a maximum of 20) to be
extracted at the same time, place three 1.00 0.10
liter aliquots of reagent water in glass containers.
10.1.2 Spike 0.5 mL of the labeled compound spiking solution
(Section 6.8) into all samples and one reagant water aliquot.
10.1.3 Spike 1.0 mL of the precision and recovery standard (Section
6.14) into the two remaining reagent water aliquots.
10.1.4 Stir and equilibrate all solutions for 1-2 hr.
10.2 Base/neutral extraction--place 100-150 mL methylene chloride in
each continuous extractor and 200-300 in each distilling flask.
10.2.1 Pour the sample(s), blank, and standard aliquots into the
extractors. Rinse the glass containers with 50-100 mL methylene chloride
and add to the respective extractor.
10.2.2 Adjust the pH of the waters in the extractors to 12-13 with
6N NaOH while monitoring with a pH meter. Begin the extraction by
heating the flask until the methylene chloride is boiling. When properly
adjusted, 1-2 drops of methylene chloride per second will fall from the
condensor tip into the water. After 1-2 hours of extraction, test the pH
and readjust to 12-13 if required. Extract for 18-24 hours.
10.2.3 Remove the distilling flask, estimate and record the volume
of extract (to the nearest 100 mL), and pour the contents through a
drying column containing 7 to 10 cm anhydrous sodium sulfate. Rinse the
distilling flask with 30-50 mL of methylene chloride and pour through
the drying column. Collect the solution in a 500 mL K-D evaporator flask
equipped with a 10 mL concentrator tube. Seal, label as the base/neutral
fraction, and concentrate per Sections 10.4 to 10.5.
10.3 Acid extraction--adjust the pH of the waters in the extractors
to 2 or less using 6N sulfuric acid. Charge clean distilling flasks with
300-400 mL of methylene chloride. Test and adjust the pH of the waters
after the first 1-2 hr of extraction. Extract for 18-24 hours.
10.3.1 Repeat Section 10.2.3, except label as the acid fraction.
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10.4 Concentration--concentrate the extracts in separate 500 mL K-D
flasks equipped with 10 mL concentrator tubes.
10.4.1 Add 1 to 2 clean boiling chips to the flask and attach a
three-ball macro Snyder column. Prewet the column by adding
approximately one mL of methylene chloride through the top. Place the K-
D apparatus in a hot water bath so that the entire lower rounded surface
of the flask is bathed with steam. Adjust the vertical position of the
apparatus and the water temperature as required to complete the
concentration in 15 to 20 minutes. At the proper rate of distillation,
the balls of the column will actively chatter but the chambers will not
flood. When the liquid has reached an apparent volume of 1 mL, remove
the K-D apparatus from the bath and allow the solvent to drain and cool
for at least 10 minutes. Remove the Snyder column and rinse the flask
and its lower joint into the concentrator tube with 1-2 mL of methylene
chloride. A 5-mL syringe is recommended for this operation.
10.4.2 For performance standards (Sections 8.2 and 12.7) and for
blanks (Section 8.5), combine the acid and base/neutral extracts for
each at this point. Do not combine the acid and base/neutral extracts
for samples.
10.5 Add a clean boiling chip and attach a two ball micro Snyder
column to the concentrator tube. Prewet the column by adding approx 0.5
mL methylene chloride through the top. Place the apparatus in the hot
water bath. Adjust the vertical position and the water temperature as
required to complete the concentration in 5-10 minutes. At the proper
rate of distillation, the balls of the column will actively chatter but
the chambers will not flood. When the liquid reaches an apparent volume
of approx 0.5 mL, remove the apparatus from the water bath and allow to
drain and cool for at least 10 minutes. Remove the micro Snyder column
and rinse its lower joint into the concentrator tube with approx 0.2 mL
of methylene chloride. Adjust the final volume to 1.0 mL.
10.6 Transfer the concentrated extract to a clean screw-cap vial.
Seal the vial with a Teflon-lined lid, and mark the level on the vial.
Label with the sample number and fraction, and store in the dark at -20
to -10 [deg]C until ready for analysis.
11. GC/MS Analysis
11.1 Establish the operating conditions given in Table 3 or 4 for
analysis of the base/neutral or acid extracts, respectively. For
analysis of combined extracts (Section 10.4.2), use the operating
conditions in Table 3.
11.2 Bring the concentrated extract (Section 10.6) or standard
(Sections 6.13 through 6.14) to room temperature and verify that any
precipitate has redissolved. Verify the level on the extract (Sections
6.6 and 10.6) and bring to the mark with solvent if required.
11.3 Add the internal standard solution (Section 6.10) to the
extract (use 1.0 uL of solution per 0.1 mL of extract) immediately prior
to injection to minimize the possibility of loss by evaporation,
adsorption, or reaction. Mix thoroughly.
11.4 Inject a volume of the standard solution or extract such that
100 ng of the internal standard will be injected, using on-column or
splitless injection. For 1 mL extracts, this volume will be 1.0 uL.
Start the GC column initial isothermal hold upon injection. Start MS
data collection after the solvent peak elutes. Stop data collection
after the benzo (ghi) perylene or pentachlorophenol peak elutes for the
base/neutral or acid fraction, respectively. Return the column to the
initial temperature for analysis of the next sample.
12. System and Laboratory Performance
12.1 At the beginning of each 8 hr shift during which analyses are
performed, GC/MS system performance and calibration are verified for all
pollutants and labeled compounds. For these tests, analysis of the 100
[micro]g/mL calibration standard (Section 6.13) shall be used to verify
all performance criteria. Adjustment and/or recalibration (per Section
7) shall be performed until all performance criteria are met. Only after
all performance criteria are met may samples, blanks, and precision and
recovery standards be analyzed.
12.2 DFTPP spectrum validity--inject 1 [micro]L of the DFTPP
solution (Section 6.11) either separately or within a few seconds of
injection of the standard (Section 12.1) analyzed at the beginning of
each shift. The criteria in Table 5 shall be met.
12.3 Retention times--the absolute retention time of 2,2'-
difluorobiphenyl shall be within the range of 1078 to 1248 seconds and
the relative retention times of all pollutants and labeled compounds
shall fall within the limits given in Tables 3 and 4.
12.4 GC resolution--the valley height between anthracene and
phenanthrene at m/z 178 (or the analogs at m/z 188) shall not exceed 10
percent of the taller of the two peaks.
12.5 Calibration verification--compute the concentration of each
pollutant (Tables 1 and 2) by isotope dilution (Section 7.4) for those
compounds which have labeled analogs. Compute the concentration of each
pollutant which has no labeled analog by the internal standard method
(Section 7.5). Compute the concentration of the labeled compounds by the
internal standard method. These concentrations are computed based on the
calibration data determined in Section 7.
12.5.1 For each pollutant and labeled compound being tested, compare
the concentration with the calibration verification limit
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in Table 8. If all compounds meet the acceptance criteria, calibration
has been verified and analysis of blanks, samples, and precision and
recovery standards may proceed. If, however, any compound fails, the
measurement system is not performing properly for that compound. In this
event, prepare a fresh calibration standard or correct the problem
causing the failure and repeat the test (Section 12.1), or recalibrate
(Section 7).
12.6 Multiple peaks--each compound injected shall give a single,
distinct GC peak.
12.7 On-going precision and accuracy.
12.7.1 Analyze the extract of one of the pair of precision and
recovery standards (Section 10.1.3) prior to analysis of samples from
the same lot.
12.7.2 Compute the concentration of each pollutant (Tables 1 and 2)
by isotope dilution (Section 7.4) for those compounds which have labeled
analogs. Compute the concentration of each pollutant which has no
labeled analog by the internal standard method (Section 7.5). Compute
the concentration of the labeled compounds by the internal standard
method.
12.7.3 For each pollutant and labeled compound, compare the
concentration with the limits for on-going accuracy in Table 8. If all
compounds meet the acceptance criteria, system performance is acceptable
and analysis of blanks and samples may proceed. If, however, any
individual concentration falls outside of the range given, system
performance is unacceptable for that compound.
Note: The large number of compounds in Table 8 present a substantial
probability that one or more will fail when all compounds are analyzed.
To determine if the extraction/concentration system is out of control or
if the failure is caused by probability, proceed as follows:
12.7.3.1 Analyze the second aliquot of the pair of precision and
recovery standard (Section 10.1.3).
12.7.3.2 Compute the concentration of only those pollutants or
labeled compounds that failed the previous test (Section 12.7.3). If
these compounds now pass, the extraction/concentration processes are in
control and analysis of blanks and samples may proceed. If, however, any
of the same compounds fail again, the extraction/concentration processes
are not being performed properly for these compounds. In this event,
correct the problem, re-extract the sample lot (Section 10) and repeat
the on-going precision and recovery test (Section 12.7).
12.7.4 Add results which pass the specifications in Section 12.7.2
to initial and previous on-going data. Update QC charts to perform a
graphic representation of continued laboratory performance (Figure 5).
Develop a statement of laboratory accuracy for each pollutant and
labeled compound by calculating the average percent recovery (R) and the
standard deviation of percent recovery (sr). Express the
accuracy as a recovery interval from R-2sr to
R+2sr. For example, if R=95% and sr=5%, the
accuracy is 85-105%.
13. Qualitative Determination
13.1 Qualititative determination is accomplished by comparison of
data from analysis of a sample or blank with data from analysis of the
shift standard (Section 12.1) and with data stored in the spectral
libraries (Section 7.2.4). Identification is confirmed when spectra and
retention times agree per the criteria below.
13.2 Labeled compounds and pollutants having no labeled analog:
13.2.1 The signals for all characteristic masses stored in the
spectral library (Section 7.2.4) shall be present and shall maximize
within the same two consecutive scans.
13.2.2 Either (1) the background corrected EICP areas, or (2) the
corrected relative intensities of the mass spectral peaks at the GC peak
maximum shall agree within a factor of two (0.5 to 2 times) for all
masses stored in the library.
13.2.3 The retention time relative to the nearest eluted internal
standard shall be within 15 scans or 15 seconds, whichever is greater of this difference in
the shift standard (Section 12.1).
13.3 Pollutants having a labled analog:
13.3.1 The signals for all characteristic masses stored in the
spectral library (Section 7.2.4) shall be present and shall maximize
within the same two consecutive scans.
13.3.2. Either (1) the background corrected EICP areas, or (2) the
corrected relative intensities of the mass spectral peaks at the GC peak
maximum shall agree within a factor of two for all masses stored in the
spectral library.
13.3.3. The retention time difference between the pollutant and its
labeled analog shall agree within 6 scans or
6 seconds (whichever is greater) of this
difference in the shift standard (Section 12.1).
13.4 Masses present in the experimental mass spectrum that are not
present in the reference mass spectrum shall be accounted for by
contaminant or background ions. If the experimental mass spectrum is
contaminated, an experienced spectrometrist (Section 1.4) is to
determine the presence or absence of the cmmpound.
14. Quantitative Determination
14.1 Isotope dilution--by adding a known amount of a labeled
compound to every sample prior to extraction, correction for recovery of
the pollutant can be made because the pollutant and its labeled analog
exhibit the same effects upon extraction, concentration, and gas
chromatography. Relative response (RR) values for mixtures are used in
conjunction with calibration curves described in
[[Page 305]]
Section 7.4 to determine concentrations directly, so long as labeled
compound spiking levels are constant. For the phenml example given in
Figure 1 (Section 7.4.1), RR would be equal to 1.114. For this RR value,
the phenol calibration curve given in Figure 1 indicates a concentration
of 27 [micro]g/mL in the sample extract (Cex).
14.2 Internal standard--compute the concentration in the extract
using the response factor determined from calibration data (Section 7.5)
and the following equation: Cex([micro]g/mL)=(As x
Cis/(Ais x RF) where Cex is the
concentration of the compound in the extract, and the other terms are as
defined in Section 7.5.1.
14.3 The concentration of the pollutant in water is computed using
the volumes of the original water sample (Section 10.1) and the final
extract volume (Section 10.5), as follows: Concentration in water
([micro]g/L)=(Cex x Vex)/Vs where
Vex is the extract volume in mL, and Vs is the
sample volume in liters.
14.4 If the EICP area at the quantitiation mass for any compound
exceeds the calibration range of the system, the extract of the dilute
aliquot (Section 10.1) is analyzed by isotope dilution; otherwise, the
extract is diluted by a factor of 10, 9 [micro]L of internal standard
solution (Section 6.10) are added to a 1.0 mL aliquot, and this diluted
extract is analyzed by the internal standard method (Section 14.2).
Quantify each compound at the highest concentration level within the
calibration range.
14.5 Report results for all pollutants and labeled compounds (Tables
1 and 2) found in all standards, blanks, and samples in [micro]g/L, to
three significant figures. Results for samples which have been diluted
are reported at the least dilute level at which the area at the
quantitation mass is within the calibration range (Section 14.4) and the
labeled compound recovery is within the normal range for the method
(Section 15.4).
15. Analysis of Complex Samples
15.1 Untreated effluents and other samples frequently contain high
levels (1000 [micro]g/L) of the compounds of interest,
interfering compounds, and/or polymeric materials. Some samples will not
concentrate to one mL (Section 10.5); others will overload the GC column
and/or mass spectrometer.
15.2 Analyze the dilute aliquot (Section 10.1) when the sample will
not concentrate to 1.0 mL. If a dilute aliquot was not extracted, and
the sample holding time (Section 9.3) has not been exceeded, dilute an
aliquot of the sample with reagent water and re-extract (Section 10.1);
otherwise, dilute the extract (Section 14.4) and analyze by the internal
standard method (Section 14.2).
15.3 Recovery of internal standard-- the EICP area of the internal
standard should be within a factor of two of the area in the shift
standard (Section 12.1). If the absolute areas of the labeled compounds
are within a factor of two of the respective areas in the shift
standard, and the internal standard area is less than one-half of its
respective area, then internal standard loss in the extract has
occurred. In this case, use one of the labeled compounds (perferably a
polynuclear aromatic hydrocarbon) to compute the concentration of a
pollutant with no labeled analog.
15.4 Recovery of labeled compounds-- in most samples, labeled
compound recoveries will be similar to those from reagent water (Section
12.7). If the labeled compound recovery is outside the limits given in
Table 8, the dilute extract (Section 10.1) is analyzed as in Section
14.4. If the recoveries of all labeled compounds and the internal
staldard are low (per the criteria above), then a loss in instrument
sensitivity is the most likely cause. In this case, the 100 [micro]g/mL
calibration standard (Section 12.1) shall be analyzed and calibration
verified (Section 12.5). If a loss in sensitivity has occurred, the
instrument shall be repaired, the performance specifications in Section
12 shall be met, and the extract reanalyzed. If a loss in instrument
sensitivity has not occurred, the method does not work on the sample
being analyzed and the result may not be reported for regulatory
compliance purposes.
16. Method Performance
16.1 Interlaboratory performance for this method is detailed in
references 9 and 10.
16.2 A chromatogram of the 100 [micro]g/mL acid/base/neutral
calibration standard (Section 6.13) is shown in Figure 6.
References
1. ``Performance Tests for the Evaluation of Computerized Gas
Chromatography/Mass Spectrometry Equipment and Laboratories'' USEPA,
EMSL/Cincinnati, OH 45268, EPA-600/4-80-025 (April 1980).
2. ``Working with Carcinogens,'' DHEW, PHS, CDC, NIOSH, Publication
77-206, (August 1977).
3. ``OSHA Safety and Health Standards, General Industry'' OSHA 2206,
29 CFR part 1910 (January 1976).
4. ``Safety in Academic Chemistry Laboratories, '' ACS Committee on
Chemical Safety (1979).
5. ``Reference Compound to Calibrate Ion Abundance Measurement in
Gas Chromatography-Mass Spectrometry Systems,'' J.W. Eichelberger, L.E.
Harris, and W.L. Budde, Anal. Chem., 47, 955 (1975).
6. ``Handbook of Analytical Quality Control in Water and Wastewater
Laboratories,'' USEPA, EMSL/Cincinnati, OH 45268, EPA-600/4-79-019
(March 1979).
7. ``Standard Practice for Sampling Water,'' ASTM Annual Book of
Standards, ASTM, Philadelphia, PA, 76 (1980).
[[Page 306]]
8. ``Methods 330.4 and 330.5 for Total Residual Chlorine,'' USEPA,
EMSL/ Cincinnati, OH 45268, EPA 600/4-70-020 (March 1979).
9. Colby, B.N., Beimer, R.G., Rushneck, D.R., and Telliard, W.A.,
``Isotope Dilution Gas Chromatography-Mass Spectrometry for the
determination of Priority Pollutants in Industrial Effluents.'' USEPA,
Effluent Guidelines Division, Washington, DC 20460 (1980).
10. ``Inter-laboratory Validation of US Environmental Protection
Agency Method 1625,'' USEPA, Effluent Guidelines Division, Washington,
DC 20460 (June 15, 1984).
Table 1--Base/Neutral Extractable Compounds
------------------------------------------------------------------------
CAS
Compound STORET registry EPA-EGD NPDES
------------------------------------------------------------------------
Acenaphthene................. 34205 83-32-9 001 B 001 B
Acenaphthylene............... 34200 208-96-8 077 B 002 B
Anthracene................... 34220 120-12-7 078 B 003 B
Benzidine.................... 39120 92-87-5 005 B 004 B
Benzo(a)anthracene........... 34526 56-55-3 072 B 005 B
Benzo(b)fluoranthene......... 34230 205-99-2 074 B 007 B
Benzo(k)fluoranthene......... 34242 207-08-9 075 B 009 B
Benzo(a)pyrene............... 34247 50-32-8 073 B 006 B
Benzo(ghi)perylene........... 34521 191-24-2 079 B 008 B
Biphenyl (Appendix C)........ 81513 92-52-4 512 B ........
Bis(2-chloroethyl) ether..... 34273 111-44-4 018 B 011 B
Bis(2-chloroethyoxy)methane.. 34278 111-91-1 043 B 010 B
Bis(2-chloroisopropyl) ether. 34283 108-60-1 042 B 012 B
Bis(2-ethylhexyl) phthalate.. 39100 117-81-7 066 B 013 B
4-bromophenyl phenyl ether... 34636 101-55-3 041 B 014 B
Butyl benzyl phthalate....... 34292 85-68-7 067 B 015 B
n-C10 (Appendix C)........... 77427 124-18-5 517 B ........
n-C12 (Appendix C)........... 77588 112-40-2 506 B ........
n-C14 (Appendix C)........... 77691 629-59-4 518 B ........
n-C16 (Appendix C)........... 77757 544-76-3 519 B ........
n-C18 (Appendix C)........... 77804 593-45-3 520 B ........
n-C20 (Appendix C)........... 77830 112-95-8 521 B ........
n-C22 (Appendix C)........... 77859 629-97-0 522 B ........
n-C24 (Appendix C)........... 77886 646-31-1 523 B ........
n-C26 (Appendix C)........... 77901 630-01-3 524 B ........
n-C28 (Appendix C)........... 78116 630-02-4 525 B ........
n-C30 (Appendix C)........... 78117 638-68-6 526 B ........
Carbazole (4c)............... 77571 86-74-8 528 B ........
2-chloronaphthalene.......... 34581 91-58-7 020 B 016 B
4-chlorophenyl phenyl ether.. 34641 7005-72-3 040 B 017 B
Chrysene..................... 34320 218-01-9 076 B 018 B
P-cymene (Appendix C)........ 77356 99-87-6 513 B ........
Dibenzo(a,h)anthracene....... 34556 53-70-3 082 B 019 B
Dibenzofuran (Appendix C and 81302 132-64-9 505 B ........
4c).........................
Dibenzothiophene (Synfuel)... 77639 132-65-0 504 B ........
Di-n-butyl phthalate......... 39110 84-74-2 068 B 026 B
1,2-dichlorobenzene.......... 34536 95-50-1 025 B 020 B
1,3-dichlorobenzene.......... 34566 541-73-1 026 B 021 B
1,4-dichlorobenzene.......... 34571 106-46-7 027 B 022 B
3,3'-dichlorobenzidine....... 34631 91-94-1 028 B 023 B
Diethyl phthalate............ 34336 84-66-2 070 B 024 B
2,4-dimethylphenol........... 34606 105-67-9 034 A 003 A
Dimethyl phthalate........... 34341 131-11-3 071 B 025 B
2,4-dinitrotoluene........... 34611 121-14-2 035 B 027 B
2,6-dinitrotoluene........... 34626 606-20-2 036 B 028 B
Di-n-octyl phthalate......... 34596 117-84-0 069 B 029 B
Diphenylamine (Appendix C)... 77579 122-39-4 507 B ........
Diphenyl ether (Appendix C).. 77587 101-84-8 508 B ........
1,2-diphenylhydrazine........ 34346 122-66-7 037 B 030 B
Fluoranthene................. 34376 206-44-0 039 B 031 B
Fluorene..................... 34381 86-73-7 080 B 032 B
Hexachlorobenzene............ 39700 118-74-1 009 B 033 B
Hexachlorobutadiene.......... 34391 87-68-3 052 B 034 B
Hexachloroethane............. 34396 67-72-1 012 B 036 B
Hexachlorocyclopentadiene.... 34386 77-47-4 053 B 035 B
Indeno(1,2,3-cd)pyrene....... 34403 193-39-5 083 B 037 B
Isophorone................... 34408 78-59-1 054 B 038 B
Naphthalene.................. 34696 91-20-3 055 B 039 B
B-naphthylamine (Appendix C). 82553 91-59-8 502 B ........
Nitrobenzene................. 34447 98-95-3 056 B 040 B
N-nitrosodimethylamine....... 34438 62-75-9 061 B 041 B
N-nitrosodi-n-propylamine.... 34428 621-64-7 063 B 042 B
N-nitrosodiphenylamine....... 34433 86-30-3 062 B 043 B
[[Page 307]]
Phenanthrene................. 34461 85-01-8 081 B 044 B
Phenol....................... 34694 108-95-2 065 A 010 A
a-Picoline (Synfuel)......... 77088 109-06-89 503 B ........
Pyrene....................... 34469 129-00-0 084 B 045 B
styrene (Appendix C)......... 77128 100-42-5 510 B ........
a-terpineol (Appendix C)..... 77493 98-55-5 509 B ........
1,2,3-trichlorobenzene (4c).. 77613 87-61-6 529 B ........
1,2,4-trichlorobenzene....... 34551 120-82-1 008 B 046 B
------------------------------------------------------------------------
Table 2--Acid Extractable Compounds
------------------------------------------------------------------------
CAS
Compound STORET registry EPA-EGD NPDES
------------------------------------------------------------------------
4-chloro-3-methylphenol...... 34452 59-50-7 022 A 008 A
2-chlorophenol............... 34586 95-57-8 024 A 001 A
2,4-dichlorophenol........... 34601 120-83-2 031 A 002 A
2,4-dinitrophenol............ 34616 51-28-5 059 A 005 A
2-methyl-4,6-dinitrophenol... 34657 534-52-1 060 A 004 A
2-nitrophenol................ 34591 88-75-5 057 A 006 A
4-nitrophenol................ 34646 100-02-7 058 A 007 A
Pentachlorophenol............ 39032 87-86-5 064 A 009 A
2,3,6-trichlorophenol (4c)... 77688 93-37-55 530 A ........
2,4,5-trichlorophenol (4c)... ........ 95-95-4 531 A ........
2,4,6-trichlorophenol........ 34621 88-06-2 021 A 011 A
------------------------------------------------------------------------
Table 3--Gas Chromatography of Base/Neutral Extractable Compounds
------------------------------------------------------------------------
Retention time Detection
EGD ------------------------------------ limit \2\
No.\1\ Compound Mean ([micro]g/
(Sec. EGD Ref Relative L)
------------------------------------------------------------------------
164 2,2'- 1163 164 1.000-1.000 10
difluorobipheny
l (int std)....
061 N- 385 164 ns 50
nitrosodimethyl
amine..........
603 alpha picoline- 417 164 0.326-0.393 50
d7.............
703 alpha picoline.. 426 603 1.006-1.028 50
610 styrene-d5...... 546 164 0.450-0.488 10
710 styrene......... 549 610 1.002-1.009 10
613 p-cymene-d14.... 742 164 0.624-0.652 10
713 p-cymene........ 755 613 1.008-1.023 10
265 phenol-d5....... 696 164 0.584-0.613 10
365 phenol.......... 700 265 0.995-1.010 10
218 bis(2- 696 164 0.584-0.607 10
chloroethyl)
ether-d8.......
318 bis(2- 704 218 1.007-1.016 10
chloroethyl)
ether..........
617 n-decane-d22.... 698 164 0.585-0.615 10
717 n-decane........ 720 617 1.022-1.038 10
226 1,3- 722 164 0.605-0.636 10
dichlorobenzene-
d4.............
326 1,3- 724 226 0.998-1.008 10
dichlorobenzene
227 1,4- 737 164 0.601-0.666 10
dichlorobenzene-
d4.............
327 1,4- 740 227 0.997-1.009 10
dichlorobenzene
225 1,2- 758 164 0.632-0.667 10
dichlorobenzene-
d4.............
325 1,2- 760 225 0.995-1.008 10
dichlorobenzene
242 bis(2- 788 164 0.664-0.691 10
chloroisopropyl
) ether-d12....
342 bis(2- 799 242 1.010-1.016 10
chloroisopropyl
) ether........
212 hexachloroethane- 819 164 0.690-0.717 10
13C............
312 hexachloroethane 823 212 0.999-1.001 10
063 N-nitrosodi-n- 830 164 ns 20
propylamine....
256 nitrobenzene-d5. 845 164 0.706-0.727 10
356 nitrobenzene.... 849 256 1.002-1.007 10
254 isophorone-d8... 881 164 0.747-0.767 10
354 isophorone...... 889 254 0.999-1.017 10
234 2,4-dimethyl 921 164 0.781-0.803 10
phenol-d3......
334 2,4- 924 234 0.999-1.003 10
dimethylphenol.
043 bis(2- 939 164 ns 10
chloroethoxy)
methane........
208 1,2,4- 955 164 0.813-0.830 10
trichlorobenzen
e-d3...........
308 1,2,4- 958 208 1.000-1.005 10
trichlorobenzen
e..............
255 naphthalene-d8.. 963 164 0.819-0.836 10
355 naphthalene..... 967 255 1.001-1.006 10
609 alpha-terpineol- 973 164 0.829-0.844 10
d3.............
[[Page 308]]
709 alpha-terpineol. 975 609 0.998-1.008 10
606 n-dodecane-d26.. 953 164 0.730-0.908 10
706 n-dodecane...... 981 606 0.986-1.051 10
529 1,2,3- 1003 164 ns 10
trichlorobenzen
e..............
252 hexachlorobutadi 1005 164 0.856-0.871 10
ene-13C4.......
352 hexachlorobutadi 1006 252 0.999-1.002 10
ene............
253 hexachlorocyclop 1147 164 0.976-0.986 10
entadiene-13C4.
353 hexachlorocyclop 1142 253 0.999-1.001 10
entadiene......
220 2- 1185 164 1.014-1.024 10
chloronaphthale
ne-d7..........
320 2- 1200 220 0.997-1.007 10
chloronaphthale
ne.............
518 n-tetradecane... 1203 164 ns 10
612 Biphenyl-d10.... 1205 164 1.016-1.027 10
712 Biphenyl........ 1195 612 1.001-1.006 10
608 Diphenyl ether- 1211 164 1.036-1.047 10
d10............
708 Diphenyl ether.. 1216 608 0.997-1.009 10
277 Acenaphthylene- 1265 164 1.080-1.095 10
d8.............
377 Acenaphthylene.. 1247 277 1.000-1.004 10
271 Dimethyl 1269 164 1.083-1.102 10
phthalate-d4...
371 Dimethyl 1273 271 0.998-1.005 10
phthalate......
236 2,6- 1283 164 1.090-1.112 10
dinitrotoluene-
d3.............
336 2,6- 1300 236 1.001-1.005 10
dinitrotoluene.
201 Acenaphthene-d10 1298 164 1.107-1.125 10
301 Acenaphthene.... 1304 201 0.999-1.009 10
605 Dibenzofuran-d8. 1331 164 1.134-1.155 10
705 Dibenzofuran.... 1335 605 0.998-1.007 10
602 Beta- 1368 164 1.163-1.189 50
naphthylamine-
d7.............
702 Beta- 1371 602 0.996-1.007 50
naphthylamine..
280 Fluorene-d10.... 1395 164 1.185-1.214 10
380 Fluorene........ 1401 281 0.999-1.008 10
240 4-chlorophenyl 1406 164 1.194-1.223 10
phenyl ether-d5
340 4-chlorophenyl 1409 240 0.990-1.015 10
phenyl ether...
270 Diethyl 1409 164 1.197-1.229 10
phthalate-d4...
370 Diethyl 1414 270 0.996-1.006 10
phthalate......
619 n-hexadecane-d34 1447 164 1.010-1.478 10
719 n-hexadecane.... 1469 619 1.013-1.020 10
235 2,4- 1359 164 1.152-1.181 10
dinitrotoluene-
d3.............
335 2,4- 1344 235 1.000-1.002 10
dinitrotoluene.
237 1,2- 1433 164 1.216-1.248 20
diphenylhydrazi
ne-d8..........
337 1,2- 1439 237 0.999-1.009 20
diphenylhydrazi
ne (\3\).......
607 Diphenylamine- 1437 164 1.213-1.249 20
d10............
707 Diphenylamine... 1439 607 1.000-1.007 20
262 N- 1447 164 1.225-1.252 20
nitrosodiphenyl
amine-d6.......
362 N- 1464 262 1.000-1.002 20
nitrosodiphenyl
amine (\4\)....
041 4-bromophenyl 1498 164 1.271-1.307 10
phenyl ether...
209 Hexachlorobenzen 1521 164 1.288-1.327 10
e-13C6.........
309 Hexachlorobenzen 1522 209 0.999-1.001 10
e..............
281 Phenanthrene-d10 1578 164 1.334-1.380 10
520 n-octadecane.... 1580 164 ns 10
381 Phenanthrene.... 1583 281 1.000-1.005 10
278 Anthracene-d10.. 1588 164 1.342-1.388 10
378 Anthracene...... 1592 278 0.998-1.006 10
604 Dibenzothiophene- 1559 164 1.314-1.361 10
d8.............
704 Dibenzothiophene 1564 604 1.000-1.006 10
528 Carbazole....... 1650 164 ns 20
621 n-eicosane-d42.. 1655 164 1.184-1.662 10
721 n-eicosane...... 1677 621 1.010-1.021 10
268 Di-n-butyl 1719 164 1.446-1.510 10
phthalate-d4...
368 Di-n-butyl 1723 268 1.000-1.003 10
phthalate......
239 Fluoranthene-d10 1813 164 1.522-1.596 10
339 Fluoranthene.... 1817 239 1.000-1.004 10
284 Pyrene-d10...... 1844 164 1.523-1.644 10
384 Pyrene.......... 1852 284 1.001-1.003 10
205 Benzidine-d8.... 1854 164 1.549-1.632 50
305 Benzidine....... 1853 205 1.000-1.002 50
522 n-docosane...... 1889 164 ns 10
623 n-tetracosane- 1997 164 1.671-1.764 10
d50............
723 n-tetracosane... 2025 612 1.012-1.015 10
067 Butylbenzyl 2060 164 ns 10
phthalate......
276 Chrysene-d12.... 2081 164 1.743-1.837 10
376 Chrysene........ 2083 276 1.000-1.004 10
[[Page 309]]
272 Benzo(a)anthrace 2082 164 1.735-1.846 10
ne-d12.........
372 Benzo(a)anthrace 2090 272 0.999-1.007 10
ne.............
228 3,3'- 2088 164 1.744-1.848 50
dichlorobenzidi
ne-d6..........
328 3,3'- 2086 228 1.000-1.001 50
dichlorobenzidi
ne.............
266 Bis(2- 2123 164 1.771-1.880 10
ethylhexyl)
phthalate-d4...
366 Bis(2- 2124 266 1.000-1.002 10
ethylhexyl)
phthalate......
524 n-hexacosane.... 2147 164 ns 10
269 di-n-octyl 2239 164 1.867-1.982 10
phthalate-d4...
369 di-n-octyl 2240 269 1.000-1.002 10
phthalate......
525 n-octacosane.... 2272 164 ns 10
274 Benzo(b)fluorant 2281 164 1.902-2.025 10
hene-d12.......
354 Benzo(b)fluorant 2293 274 1.000-1.005 10
hene...........
275 Benzo(k)fluorant 2287 164 1.906-2.033 10
hene-d12.......
375 Benzo(k)fluorant 2293 275 1.000-1.005 10
hene...........
273 Benzo(a)pyrene- 2351 164 1.954-2.088 10
d12............
373 Benzo(a)pyrene.. 2350 273 1.000-1.004 10
626 N-triacontane- 2384 164 1.972-2.127 10
d62............
726 N-triacontane... 2429 626 1.011-1.028 10
083 Indeno(1,2,3- 2650 164 ns 20
cd)pyrene......
082 Dibenzo(a,h)anth 2660 164 ns 20
racene.........
279 Benzo(ghi)peryle 2741 164 2.187-2.524 20
ne-d12.........
379 Benzo(ghi)peryle 2750 279 1.001-1.006 20
ne.............
------------------------------------------------------------------------
\1\ Reference numbers beginning with 0, 1 or 5 indicate a pollutant
quantified by the internal standard method; reference numbers
beginning with 2 or 6 indicate a labeled compound quantified by the
internal standard method; reference numbers beginning with 3 or 7
indicate a pollutant quantified by isotope dilution.
\2\ This is a minimum level at which the entire GC/MS system must give
recognizable mass spectra (background corrected) and acceptable
calibration points.
\3\ Detected as azobenzene.
\4\ Detected as diphenylamine.
ns = specification not available at time of release of method.
Column: 30 2 m x 0.25 0.02
mm i.d. 94% methyl, 4% phenyl, 1% vinyl bonded phase fused silica
capillary.
Temperature program: 5 min at 30 [deg]C; 30 - 280 [deg]C at 8 [deg]C per
min; isothermal at 280 [deg]C until benzo(ghi)perylene elutes.
Gas velocity: 30 5 cm/sec.
Table 4--Gas Chromatography of Acid Extractable Compounds
------------------------------------------------------------------------
Retention time Detection
EGD ------------------------------------ limit 2
No. 1 Compound Mean ([micro]g/
(Sec. EGD Ref Relative L)
------------------------------------------------------------------------
164 2,2'- 1163 164 1.000-1.000 10
difluorobipheny
l (int std)....
224 2-chlorophenol- 701 164 0.587-0.618 10
d4.............
324 2-chlorophenol.. 705 224 0.997-1.010 10
257 2-nitrophenol-d4 898 164 0.761-0.783 20
357 2-nitrophenol... 900 257 0.994-1.009 20
231 2,4- 944 164 0.802-0.822 10
dichlorophenol-
d3.............
331 2,4- 947 231 0.997-1.006 10
dichlorophenol.
222 4-chloro-3- 1086 164 0.930-0.943 10
methylphenol-d2
322 4-chloro-3- 1091 222 0.998-1.003 10
methylphenol...
221 2,4,6- 1162 164 0.994-1.005 10
trichlorophenol-
d2.............
321 2,4,6- 1165 221 0.998-1.004 10
trichlorophenol
531 2,4,5- 1170 164 ns 10
trichlorophenol
530 2,3,6- 1195 164 ns 10
trichlorophenol
259 2,4- 1323 164 1.127-1.149 50
dinitrophenol-
d3.............
359 2,4- 1325 259 1.000-1.005 50
dinitrophenol..
258 4-nitrophenol-d4 1349 164 1.147-1.175 50
358 4-nitrophenol... 1354 258 0.997-1.006 50
260 2-methyl-4,6- 1433 164 1.216-1.249 20
dinitrophenol-
d2.............
360 2-methyl-4,6- 1435 260 1.000-1.002 20
dinitrophenol..
264 Pentachloropheno 1559 164 1.320-1.363 50
l-13C6.........
364 Pentachloropheno 1561 264 0.998-1.002 50
l..............
------------------------------------------------------------------------
1 Reference numbers beginning with 0, 1 or 5 indicate a pollutant
quantified by the internal standard method; reference numbers
beginning with 2 or 6 indicate a labeled compound quantified by the
internal standard method; reference numbers beginning with 3 or 7
indicate a pollutant quantified by isotope dilution.
2 This is a minimum level at which the entire GC/MS system must give
recognizable mass spectra (background corrected) and acceptable
calibration points.
ns=specification not available at time of release of method.
Column: 30 2mx0.25 0.02mm
i.d. 94% methyl, 4% phenyl, 1% vinyl bonded phase fused silica
capillary.
Temperature program: 5 min at 30 [deg]C; 8 [deg]C/min. to 250[deg]C or
until pentachlorophenol elutes.
Gas velocity: 30 5 cm/sec.
[[Page 310]]
Table 5--DFTPP Mass Intensity Specifications
------------------------------------------------------------------------
Mass Intensity required
------------------------------------------------------------------------
51 30-60 percent of mass 198.
68 Less than 2 percent of mass 69.
70 Less than 2 percent of mass 69.
127 40-60 percent of mass 198.
197 Less than 1 percent of mass 198.
199 5-9 percent of mass 198.
275 10-30 percent of mass 198.
365 greater than 1 percent of mass 198
441 present and less than mass 443
442 40-100 percent of mass 198.
443 17-23 percent of mass 442.
------------------------------------------------------------------------
Table 6--Base/Neutral Extractable Compound Characteristic Masses
------------------------------------------------------------------------
Labeled Primary m/
Compound analog z
------------------------------------------------------------------------
Acenaphthene..................................... d10 154/164
Acenaphthylene................................... d8 152/160
Anthracene....................................... d10 178/188
Benzidine........................................ d8 184/192
Benzo(a)anthracene............................... d12 228/240
Benzo(b)fluoranthene............................. d12 252/264
Benzo(k)fluoranthene............................. d12 252/264
Benzo(a)pyrene................................... d12 252/264
Benzo(ghi)perylene............................... d12 276/288
Biphenyl......................................... d10 154/164
Bis(2-chloroethyl) ether......................... d8 93/101
Bis(2-chloroethoxy)methane....................... ......... 93
Bis(2-chloroisopropyl) ether..................... d12 121/131
Bis(2-ethylhexyl) phthalate...................... d4 149/153
4-bromophenyl phenyl ether....................... ......... 248
Butyl benzyl phthalate........................... ......... 149
n-C10............................................ d22 55/66
n-C12............................................ d26 55/66
n-C14............................................ ......... 55
n-C16............................................ d34 55/66
n-C18............................................ ......... 55
n-C20............................................ d42 55/66
n-C22............................................ ......... 55
n-C24............................................ d50 55/66
n-C26............................................ ......... 55
n-C28............................................ ......... 55
n-C30............................................ d62 55/66
Carbazole........................................ d8 167/175
2-chloronaphthalene.............................. d7 162/169
4-chlorophenyl phenyl ether...................... d5 204/209
Chrysene......................................... d12 228/240
p-cymene......................................... d14 114/130
Dibenzo(a,h)anthracene........................... ......... 278
Dibenzofuran..................................... d8 168/176
Dibenzothiophene................................. d8 184/192
Di-n-butyl phthalate............................. d4 149/153
1,2-dichlorobenzene.............................. d4 146/152
1,3-dichlorobenzene.............................. d4 146/152
1,4-dichlorobenzene.............................. d4 146/152
3,3'-dichlorobenzidine........................... d6 252/258
Diethyl phthalate................................ d4 149/153
2,4-dimethylphenol............................... d3 122/125
Dimethyl phthalate............................... d4 163/167
2,4-dinitrotoluene............................... d3 164/168
2,6-dinitrotoluene............................... d3 165/167
Di-n-octyl phthalate............................. d4 149/153
Diphenylamine.................................... d10 169/179
Diphenyl ether................................... d10 170/180
1,2-diphenylhydrazine \1\........................ d10 77/82
Fluoranthene..................................... d10 202/212
Fluorene......................................... d10 166/176
Hexachlorobenzene................................ 13C6 284/292
Hexachlorobutadiene.............................. 13C4 225/231
Hexachloroethane................................. 13C 201/204
Hexachlorocyclopentadiene........................ 13C4 237/241
Ideno(1,2,3-cd)pyrene............................ ......... 276
Isophorone....................................... d8 82/88
Naphthalene...................................... d8 128/136
B-naphthylamine.................................. d7 143/150
Nitrobenzene..................................... d5 123/128
N-nitrosodimethylamine........................... ......... 74
N-nitrosodi-n-propylamine........................ ......... 70
N-nitrosodiphenylamile \2\....................... d6 169/175
Phenanthrene..................................... d10 178/188
Phenol........................................... d5 94/71
a-picoline....................................... d7 93/100
Pyrene........................................... d10 202/212
Styrene.......................................... d5 104/109
a-terpineol...................................... d3 59/62
1,2,3-trichlorobenzene........................... d3 180/183
1,2,4-trichlorobenzene........................... d3 180/183
------------------------------------------------------------------------
\1\ Detected as azobenzene.
\2\ Detected as diphenylamine.
Table 77--Acid Extractable Compound Characteristic Masses
------------------------------------------------------------------------
Labeled Primary m/
Compound analog z
------------------------------------------------------------------------
4-chloro-3-methylphenol.......................... d2 107/109
2-chlorophenol................................... d4 128/132
2,4-dichlorophenol............................... d3 162/167
2,4-dinitrophenol................................ d3 184/187
2-methyl-4,6-dinitrophenol....................... d2 198/200
2-nitrophenol.................................... d4 139/143
4-nitrophenol.................................... d4 139/143
Pentachlorophenol................................ 13C6 266/272
2,3,6-trichlorophenol............................ d2 196/200
2,4,5-trichlorophenol............................ d2 196/200
2,4,6-trichlorophenol............................ d2 196/200
------------------------------------------------------------------------
Table 8--Acceptance Criteria for Performance Tests
----------------------------------------------------------------------------------------------------------------
Acceptance criteria
-----------------------------------------------------------------
Initial precision and Labeled Calibration On-going
EGD Compound accuracy section compound verification accuracy
No.1 8.2.3 ([micro]g/L) recovery Sec. sec. 12.5 sec. 11.6 R
----------------------- 8.3 and 14.2 P ([micro]g/ ([micro]g/
s X (percent) mL) L)
----------------------------------------------------------------------------------------------------------------
301 Acenaphthene.......................... 21 79-134 .............. 80-125 72-144
201 Acenaphthene-d10...................... 38 38-147 20-270 71-141 30-180
377 Acenapht ylene........................ 38 69-186 .............. 60-166 61-207
277 Acenaphthylene-d8..................... 31 38-146 23-239 66-152 33-168
[[Page 311]]
378 Anthracene............................ 41 58-174 .............. 60-168 50-199
278 Anthracene-d10........................ 49 31-194 14-419 58-171 23-242
305 Benzidine............................. 119 16-518 .............. 34-296 11-672
205 Benzidine-d8.......................... 269 ns-ns ns-ns ns-ns ns-ns
372 Benzo(a)anthracene.................... 20 65-168 .............. 70-142 62-176
272 Benzo(a)anthracene-d12................ 41 25-298 12-605 28-357 22-329
374 Benzo(b)fluoranthene.................. 183 32-545 .............. 61-164 20-ns
274 Benzo(b)fluoranthene-d12.............. 168 11-577 ns-ns 14-ns ns-ns
375 Benzo(k)fluoranthene.................. 26 59-143 .............. 13-ns 53-155
275 Benzo(k)fluoranthene-d12.............. 114 15-514 ns-ns 13-ns ns-685
373 Benzo(a)pyrene........................ 26 62-195 .............. 78-129 59-206
273 Benzo(a)pyrene-d12.................... 24 35-181 21-290 12-ns 32-194
379 Benzo(ghi)perylene.................... 21 72-160 .............. 69-145 58-168
279 Benzo(ghi)perylene-d12................ 45 29-268 14-529 13-ns 25-303
712 Biphenyl (Appendix C)................. 41 75-148 .............. 58-171 62-176
612 Biphenyl-d12.......................... 43 28-165 ns-ns 52-192 17-267
318 Bis(2-chloroethyl) ether.............. 34 55-196 .............. 61-164 50-213
218 Bis(2-chloroethyl) ether-d8........... 33 29-196 15-372 52-194 25-222
043 Bis(2-chloroethoxy)methane*........... 27 43-153 .............. 44-228 39-166
342 Bis(2-chloroisopropyl) ether.......... 17 81-138 .............. 67-148 77-145
242 Bis(2-chloroisopropyl)ether-d12....... 27 35-149 20-260 44-229 30-169
366 Bis(2-ethylhexyl) phthalate........... 31 69-220 .............. 76-131 64-232
266 Bis(2-ethylhexyl) phthalate-d4........ 29 32-205 18-364 43-232 28-224
041 4-bromophenyl phenyl ether*........... 44 44-140 .............. 52-193 35-172
067 Butyl benzyl phthalate*............... 31 19-233 .............. 22-450 35-170
717 n-C10 (Appendix C).................... 51 24-195 .............. 42-235 19-237
617 n-C10-d22............................. 70 ns-298 ns-ns 44-227 ns-504
706 n-C12 (Appendix C).................... 74 35-369 .............. 60-166 29-424
606 n-C12-d26............................. 53 ns-331 ns-ns 41-242 ns-408
518 n-C14 (Appendix C)*................... 109 ns-985 .............. 37-268 ns-ns
719 n-C16 (Appendix C).................... 33 80-162 .............. 72-138 71-181
619 n-C16-d34............................. 46 37-162 18-308 54-186 28-202
520 n-C18 (Appendix C)*................... 39 42-131 .............. 40-249 35-167
721 n-C20 (Appendix C).................... 59 53-263 .............. 54-184 46-301
621 n-C20-d42............................. 34 34-172 19-306 62-162 29-198
522 n-C22 (Appendix C)*................... 31 45-152 .............. 40-249 39-195
723 n-C24 (Appendix C).................... 11 80-139 .............. 65-154 78-142
623 n-C24-d50............................. 28 27-211 15-376 50-199 25-229
524 n-C26 (Appendix C)*................... 35 35-193 .............. 26-392 31-212
525 n-C28 (Appendix C)*................... 35 35-193 .............. 26-392 31-212
726 n-C30 (Appendix C).................... 32 61-200 .............. 66-152 56-215
626 n-C30-d62............................. 41 27-242 13-479 24-423 23-274
528 Carbazole (4c)*....................... 38 36-165 .............. 44-227 31-188
320 2-chloronaphthalene................... 100 46-357 .............. 58-171 35-442
220 2-chloronaphthalene-d7................ 41 30-168 15-324 72-139 24-204
322 4-chloro-3-methylphenol............... 37 76-131 .............. 85-115 62-159
222 4-chloro-3-methylphenol-d2............ 111 30-174 ns-613 68-147 14-314
324 2-chlorophenol........................ 13 79-135 .............. 78-129 76-138
224 2-chlorophenol-d4..................... 24 36-162 23-255 55-180 33-176
340 4-chlorophenyl phenyl ether........... 42 75-166 .............. 71-142 63-194
240 4-chlorophenyl phenyl ether-d5........ 52 40-161 19-325 57-175 29-212
376 Chrysene.............................. 51 59-186 .............. 70-142 48-221
276 Chrysene-d12.......................... 69 33-219 13-512 24-411 23-290
713 p-cymene (Appendix C)................. 18 76-140 .............. 79-127 72-147
613 p-cymene-d14.......................... 67 ns-359 ns-ns 66-152 ns-468
082 Dibenzo(a,h)anthracene*............... 55 23-299 .............. 13-761 19-340
705 Dibenzofuran (Appendix C)............. 20 85-136 .............. 73-136 79-146
605 Dibenzofuran-d8....................... 31 47-136 28-220 66-150 39-160
704 Dibenzothiophene (Synfuel)............ 31 79-150 .............. 72-140 70-168
604 Dibenzothiophene-d8................... 31 48-130 29-215 69-145 40-156
368 Di-n-butyl phthalate.................. 15 76-165 .............. 71-142 74-169
268 Di-n-butyl phthalate-d4............... 23 23-195 13-346 52-192 22-209
325 1,2-dichlorobenzene................... 17 73-146 .............. 74-135 70-152
225 1,2-dichlorobenzene-d4................ 35 14-212 ns-494 61-164 11-247
326 1,3-dichlorobenzene................... 43 63-201 .............. 65-154 55-225
226 1,3-dichlorobenzene-d4................ 48 13-203 ns-550 52-192 ns-260
327 1,4-dichlorobenzene................... 42 61-194 .............. 62-161 53-219
[[Page 312]]
227 1,4-dichlorobenzene-d4................ 48 15-193 ns-474 65-153 11-245
328 3,3'-dichlorobenzidine................ 26 68-174 .............. 77-130 64-185
228 3,3'-dichlorobenzidine-d6............. 80 ns-562 ns-ns 18-558 ns-ns
331 2,4-dichlorophenol.................... 12 85-131 .............. 67-149 83-135
231 2,4-dichlorophenol-d3................. 28 38-164 24-260 64-157 34-182
370 Diethyl phthalate..................... 44 75-196 .............. 74-135 65-222
270 Diethyl phthalate-d4.................. 78 ns-260 ns-ns 47-211 ns-ns
334 2,4-dimethylphenol.................... 13 62-153 .............. 67-150 60-156
234 2,4-dimethylphenol-d3................. 22 15-228 ns-449 58-172 14-242
371 Dimethyl phthalate.................... 36 74-188 .............. 73-137 67-207
271 Dimethyl phthalate-d4................. 108 ns-640 ns-ns 50-201 ns-ns
359 2,4-dinitrophenol..................... 18 72-134 .............. 75-133 68-141
259 2,4-dinitrophenol-d3.................. 66 22-308 ns-ns 39-256 17-378
335 2,4-dinitrotoluene.................... 18 75-158 .............. 79-127 72-164
235 2,4-dinitrotoluene-d3................. 37 22-245 10-514 53-187 19-275
336 2,6-dinitrotoluene.................... 30 80-141 .............. 55-183 70-159
236 2,6-dinitrotoluene-d3................. 59 44-184 17-442 36-278 31-250
369 Di-n-octyl phthalate.................. 16 77-161 .............. 71-140 74-166
269 Di-n-octyl phthalate-d4............... 46 12-383 ns-ns 21-467 10-433
707 Diphenylamine (Appendix C)............ 45 58-205 .............. 57-176 51-231
607 Diphenylamine-d10..................... 42 27-206 11-488 59-169 21-249
708 Diphenyl ether (Appendix C)........... 19 82-136 .............. 83-120 77-144
608 Diphenyl ether-d10.................... 37 36-155 19-281 77-129 29-186
337 1,2-diphenylhydrazine................. 73 49-308 .............. 75-134 40-360
237 1,2-diphenylhydrazine-d10............. 35 31-173 17-316 58-174 26-200
339 Fluoranthene.......................... 33 71-177 .............. 67-149 64-194
239 Fluoranthene-d10...................... 35 36-161 20-278 47-215 30-187
380 Fluorene.............................. 29 81-132 .............. 74-135 70-151
280 Fluorene-d10.......................... 43 51-131 27-238 61-164 38-172
309 Hexachlorobenzene..................... 16 90-124 .............. 78-128 85-132
209 Hexachlorobenzene-13C6................ 81 36-228 13-595 38-265 23-321
352 hexachlorobutadiene................... 56 51-251 .............. 74-135 43-287
252 hexachlorobutadiene-13C4.............. 63 ns-316 ns-ns 68-148 ns-413
312 hexachloroethane...................... 227 21-ns .............. 71-141 13-ns
212 hexachloroethane-13C1................. 77 ns-400 ns-ns 47-212 ns-563
353 hexachlorocyclopentadiene............. 15 69-144 .............. 77-129 67-148
253 hexachlorocyclopentadiene-13C4........ 60 ns-ns ns-ns 47-211 ns-ns
083 ideno(1,2,3-cd)pyrene*................ 55 23-299 .............. 13-761 19-340
354 isophorone............................ 25 76-156 .............. 70-142 70-168
254 isophorone-d8......................... 23 49-133 33-193 52-194 44-147
360 2-methyl-4,6-dinitrophenol............ 19 77-133 .............. 69-145 72-142
260 2-methyl-4,6-dinitrophenol-d2......... 64 36-247 16-527 56-177 28-307
355 naphthalene........................... 20 80-139 .............. 73-137 75-149
255 naphthalene-d8........................ 39 28-157 14-305 71-141 22-192
702 B-naphthylamine (Appendix C).......... 49 10-ns .............. 39-256 ns-ns
602 B-naphthylamine-d7.................... 33 ns-ns ns-ns 44-230 ns-ns
356 nitrobenzene.......................... 25 69-161 .............. 85-115 65-169
256 nitrobenzene-d5....................... 28 18-265 ns-ns 46-219 15-314
357 2-nitrophenol......................... 15 78-140 .............. 77-129 75-145
257 2-nitrophenol-d4...................... 23 41-145 27-217 61-163 37-158
358 4-nitrophenol......................... 42 62-146 .............. 55-183 51-175
258 4-nitrophenol-d4...................... 188 14-398 ns-ns 35-287 ns-ns
061 N-nitrosodimethylamile*............... 198 21-472 .............. 40-249 12-807
063 N-nitrosodi-n-proplyamine*............ 198 21-472 .............. 40-249 12-807
362 N-nitrosodiphenylamine................ 45 65-142 .............. 68-148 53-173
262 N-nitrosodiphenylamine-d6............. 37 54-126 26-256 59-170 40-166
364 pentachlorophenol..................... 21 76-140 .............. 77-130 71-150
264 pentachlorophenol-13C6................ 49 37-212 18-412 42-237 29-254
381 phenanthrene.......................... 13 93-119 .............. 75-133 87-126
281 phenanthrene-d10...................... 40 45-130 24-241 67-149 34-168
365 phenol................................ 36 77-127 .............. 65-155 62-154
265 phenol-d5............................. 161 21-210 ns-ns 48-208 ns-ns
703 a-picoline (Synfuel).................. 38 59-149 .............. 60-165 50-174
603 a-picoline-d7......................... 138 11-380 ns-ns 31-324 ns-608
384 pyrene................................ 19 76-152 .............. 76-132 72-159
284 pyrene-d10............................ 29 32-176 18-303 48-210 28-196
710 styrene (Appendix C).................. 42 53-221 .............. 65-153 48-244
[[Page 313]]
610 styrene-d5............................ 49 ns-281 ns-ns 44-228 ns-348
709 a-terpineol (Appendix C).............. 44 42-234 .............. 54-186 38-258
609 a-terpineol-d3........................ 48 22-292 ns-672 20-502 18-339
529 1,2,3-trichlorobenzene (4c)*.......... 69 15-229 .............. 60-167 11-297
308 1,2,4-trichlorobenzene................ 19 82-136 .............. 78-128 77-144
208 1,2,4-trichlorobenzene-d3............. 57 15-212 ns-592 61-163 10-282
530 2,3,6-trichlorophenol (4c)*........... 30 58-137 .............. 56-180 51-153
531 2,4,5-trichlorophenol (4c)*........... 30 58-137 .............. 56-180 51-153
321 2,4,6-trichlorophenol................. 57 59-205 .............. 81-123 48-244
221 2,4,6-trichlorophenol-d2.............. 47 43-183 21-363 69-144 34-226
----------------------------------------------------------------------------------------------------------------
\1\ Reference numbers beginning with 0, 1 or 5 indicate a pollutant quantified by the internal standard method;
reference numbers beginning with 2 or 6 indicate a labeled compound quantified by the internal standard
method; reference numbers beginning with 3 or 7 indicate a pollutant quantified by isotope dilution.
* Measured by internal standard; specification derived from related compound.
ns=no specification; limit is outside the range that can be measured reliably.
[[Page 314]]
[GRAPHIC] [TIFF OMITTED] TC02JY92.057
[[Page 315]]
[GRAPHIC] [TIFF OMITTED] TC02JY92.058
[[Page 316]]
[GRAPHIC] [TIFF OMITTED] TC02JY92.059
[[Page 317]]
Attachment 1 to Method 1625
Introduction
To support measurement of several semivolatile pollutants, EPA has
developed this attachment to EPA Method 1625B.\1\ The modifications
listed in this attachment are approved only for monitoring wastestreams
from the Centralized Waste Treatment Point Source Category (40 CFR Part
437) and the Landfills Point Source Category (40 CFR Part 445). EPA
Method 1625B (the Method) employs sample extraction with methylene
chloride followed by analysis of the extract using capillary column gas
chromatography-mass spectrometry (GC/MS). This attachment addresses the
addition of the semivolatile pollutants listed in Tables 1 and 2 to all
applicable standard, stock, and spiking solutions utilized for the
determination of semivolatile organic compounds by EPA Method 1625B.
---------------------------------------------------------------------------
\1\ EPA Method 1625 Revision B, Semivolatile Organic Compounds by
Isotope Dilution GC/MS, 40 CFR Part 136, Appendix A.
---------------------------------------------------------------------------
1.0 EPA METHOD 1625 REVISION B MODIFICATION SUMMARY
The additional semivolatile organic compounds listed in Tables 1 and
2 are added to all applicable calibration, spiking, and other solutions
utilized in the determination of semivolatile compounds by EPA Method
1625. The instrument is to be calibrated with these compounds, and all
procedures and quality control tests described in the Method must be
performed.
2.0 SECTION MODIFICATIONS
Note: All section and figure numbers in this Attachment reference
section and figure numbers in EPA Method 1625 Revision B unless noted
otherwise. Sections not listed here remain unchanged.
Section 6.7 The stock standard solutions described in this section are
modified such that the analytes in Tables 1 and 2 of this
attachment are required in addition to those specified in the
Method.
Section 6.8 The labeled compound spiking solution in this section is
modified to include the labeled compounds listed in Tables 5
and 6 of this attachment.
Section 6.9 The secondary standard is modified to include the additional
analytes listed in Tables 1 and 2 of this attachment.
Section 6.12 The solutions for obtaining authentic mass spectra are to
include all additional analytes listed in Tables 1 and 2 of
this attachment.
Section 6.13 The calibration solutions are modified to include the
analytes listed in Tables 1 and 2 and the labeled compounds
listed in Tables 5 and 6 of this attachment.
Section 6.14 The precision and recovery standard is modified to include
the analytes listed in Tables 1 and 2 and the labeled
compounds listed in Tables 5 and 6 of this attachment.
Section 6.15 The solutions containing the additional analytes listed in
Tables 1 and 2 of this attachment are to be analyzed for
stability.
Section 7.2.1 This section is modified to include the analytes listed in
Tables 1 and 2 and the labeled compounds listed in Tables 5
and 6 of this attachment.
Section 7.4.5 This section is modified to include the analytes listed in
Tables 1 and 2 and the labeled compounds listed in Tables 5
and 6 in the calibration.
Section 8.2 The initial precision and recovery (IPR) requirements are
modified to include the analytes listed in Tables 1 and 2 and
the labeled compounds listed in Tables 5 and 6 of this
attachment. Additional IPR performance criteria are supplied
in Table 7 of this attachment.
Section 8.3 The labeled compounds listed in Tables 3 and 4 of this
attachment are to be included in the method performance tests.
Additional method performance criteria are supplied in Table 7
of this attachment.
Section 8.5.2 The acceptance criteria for blanks includes the analytes
listed in Tables 1 and 2 of this attachment.
Section 10.1.2 The labeled compound solution must include the labeled
compounds listed in Tables 5 and 6 of this attachment.
Section 10.1.3 The precision and recovery standard must include the
analytes listed in Tables 1 and 2 and the labeled compounds
listed in Tables 5 and 6 of this attachment.
Section 12.5 Additional QC requirements for calibration verification are
supplied in Table 7 of this attachment.
Section 12.7 Additional QC requirements for ongoing precision and
recovery are supplied in Table 7 of this attachment.
[[Page 318]]
Table 1--Base/Neutral Extractable Compounds
------------------------------------------------------------------------
Pollutant
-----------------------
Compound CAS
Registry EPA-EGD
------------------------------------------------------------------------
acetophenone 1.................................. 98-86-2 758
aniline 2....................................... 62-53-3 757
-2,3-dichloroaniline1........................... 608-27-5 578
-o-cresol 1..................................... 95-48-7 771
pyridine 2...................................... 110-86-1 1330
------------------------------------------------------------------------
CAS = Chemical Abstracts Registry.
EGD = Effluent Guidelines Division.
\1\ Analysis of this pollutant is approved only for the Centralized
Waste Treatment industry.
\2\ Analysis of this pollutant is approved only for the Centralized
Waste Treatment and Landfills industries.
Table 2--Acid Extractable Compounds
------------------------------------------------------------------------
Pollutant
-------------------------
Compound CAS
Registry EPA-EGD
------------------------------------------------------------------------
p-cresol 1.................................... 106-44-5 1744
------------------------------------------------------------------------
CAS = Chemical Abstracts Registry.
EGD = Effluent Guidelines Division.
1 Analysis of this pollutant is approved only for the Centralized Waste
Treatment and Landfills industries.
Table 3--Gas Chromatography 1 of Base/Neutral Extractable Compounds
----------------------------------------------------------------------------------------------------------------
Retention time 2
EGD No. Compound ------------------------------------------------ Minimum level
Mean (Sec. EGD Ref Relative 3 ([micro]g/L)
----------------------------------------------------------------------------------------------------------------
758..................... acetophenone 4........ 818 658 1.003-1.005 10
757..................... aniline 5............. 694 657 0.994-1.023 10
578..................... 2,3-dichloroaniline 4. 1160 164 1.003-1.007 10
771..................... o-cresol 4............ 814 671 1.005-1.009 10
1330.................... pyridine 5............ 378 1230 1.005-1.011 10
----------------------------------------------------------------------------------------------------------------
EGD = Effluent Guidelines Division.
1 The data presented in this table were obtained under the chromatographic conditions given in the footnote to
Table 3 of EPA Method 1625B.
2 Retention times are approximate and are intended to be consistent with the retention times for the analytes in
EPAMethod 1625B.
3 See the definition in footnote 2 to Table 3 of EPA Method 1625B.
4 Analysis of this pollutant is approved only for the Centralized Waste Treatment industry.
5 Analysis of this pollutant is approved only for the Centralized Waste Treatment and Landfills industries.
Table 4--Gas Chromatography 1 of Acid Extractable Compounds
----------------------------------------------------------------------------------------------------------------
Retention time 2
EGD No. Compound ------------------------------------------------ Minimum level
Mean (Sec. EGD Ref Relative ([micro]/L) 3
----------------------------------------------------------------------------------------------------------------
1744.................... p-cresol 4............ 834 1644 1.004-1.008 20
----------------------------------------------------------------------------------------------------------------
EGD = Effluent Guidelines Division.
1 The data presented in this table were obtained under the chromatographic conditions given in the footnote to
Table 4 of EPA Method 1625B.
2 Retention times are approximate and are intended to be consistent with the retention times for the analytes in
EPAMethod 1625B.
3 See the definition in footnote 2 to Table 4 of EPA Method 1625B.
4 Analysis of this pollutant is approved only for the Centralized Waste Treatment and Landfills industries.
Table 5--Base/Neutral Extractable Compound Characteristic m/z's
------------------------------------------------------------------------
Primary m/
Compound Labeled Analog z 1
------------------------------------------------------------------------
acetophenone 2............................ d5 105/110
aniline 3................................. d7 93/100
o-cresol 2................................ d7 108/116
2,3-dichloroaniline 2..................... n/a 161
pyridine 3................................ d5 79/84
------------------------------------------------------------------------
m/z = mass to charge ratio.
[[Page 319]]
1 Native/labeled.
2 Analysis of this pollutant is approved only for the Centralized Waste
Treatment industry.
3 Analysis of this pollutant is approved only for the Centralized Waste
Treatment and Landfills industries.
Table 6--Acid Extractable Compound Characteristic m/z's
------------------------------------------------------------------------
Primary m/
Compound Labeled Analog z 1
------------------------------------------------------------------------
p-cresol 2................................ d7 108/116
------------------------------------------------------------------------
m/z = mass to charge ratio.
1 Native/labeled.
2 Analysis of this pollutant is approved only for the Centralized Waste
Treatment and Landfills industries.
Table 7--Acceptance Criteria for Performance Tests
----------------------------------------------------------------------------------------------------------------
Acceptance criteria
---------------------------------------
Initial precision and On-going
accuracy section 8.2 Labeled Calibration accuracy
EGD No. Compound ([micro]g/L) compound verification sec. 12.7 R
-------------------------- recovery sec. 12.5 ([micro]g/
s sec. 8.3 [micro]g/mL) L)
([micro]g/ X and 14.2 P
L) (percent)
----------------------------------------------------------------------------------------------------------------
758.................... acetophenone 1....... 34 44-167 ........... 85-115 45-162
658.................... acetophenone-d 5 1... 51 23-254 45-162 85-115 22-264
757.................... aniline 2............ 32 30-171 ........... 85-115 33-154
657.................... aniline-d 7 2........ 71 15-278 33-154 85-115 12-344
771.................... o-cresol 1........... 40 31-226 ........... 85-115 35-196
671.................... o-cresol-d 7 1....... 23 30-146 35-196 85-115 31-142
1744................... p-cresol 2........... 59 54-140 ........... 85-115 37-203
1644................... p-cresol-d7 2........ 22 11-618 37-203 85-115 16-415
578.................... 2,3-dichloroaniline 1 13 40-160 ........... 85-115 44-144
1330................... pyridine 2........... 28 10-421 ........... 83-117 18-238
1230................... pyridine-d 5 2....... ns 7-392 19-238 85-115 4-621
----------------------------------------------------------------------------------------------------------------
s = Standard deviation of four recovery measurements.
X = Average recovery for four recovery measurements.
EGD = Effluent Guidelines Division.
ns = no specification; limit is outside the range that can be measured reliably.
1 Analysis of this pollutant is approved only for the Centralized Waste Treatment industry.
2 Analysis of this pollutant is approved only for the Centralized Waste Treatment and Landfills industries.
[49 FR 43261, Oct. 26, 1984; 50 FR 692, 695, Jan. 4, 1985, as amended at
51 FR 23702, June 30, 1986; 62 FR 48405, Sept. 15, 1997; 65 FR 3044,
Jan. 19, 2000; 65 FR 81295, 81298, Dec. 22, 2000]
Appendix B to Part 136--Definition and Procedure for the Determination
of the Method Detection Limit--Revision 1.11
Definition
The method detection limit (MDL) is defined as the minimum
concentration of a substance that can be measured and reported with 99%
confidence that the analyte concentration is greater than zero and is
determined from analysis of a sample in a given matrix containing the
analyte.
Scope and Application
This procedure is designed for applicability to a wide variety of
sample types ranging from reagent (blank) water containing analyte to
wastewater containing analyte. The MDL for an analytical procedure may
vary as a function of sample type. The procedure requires a complete,
specific, and well defined analytical method. It is essential that all
sample processing steps of the analytical method be included in the
determination of the method detection limit.
The MDL obtained by this procedure is used to judge the significance
of a single measurement of a future sample.
The MDL procedure was designed for applicability to a broad variety
of physical and chemical methods. To accomplish this, the procedure was
made device- or instrument-independent.
Procedure
1. Make an estimate of the detection limit using one of the
following:
(a) The concentration value that corresponds to an instrument
signal/noise in the range of 2.5 to 5.
(b) The concentration equivalent of three times the standard
deviation of replicate instrumental measurements of the analyte in
reagent water.
(c) That region of the standard curve where there is a significant
change in sensitivity, i.e., a break in the slope of the standard curve.
[[Page 320]]
(d) Instrumental limitations.
It is recognized that the experience of the analyst is important to
this process. However, the analyst must include the above considerations
in the initial estimate of the detection limit.
2. Prepare reagent (blank) water that is as free of analyte as
possible. Reagent or interference free water is defined as a water
sample in which analyte and interferent concentrations are not detected
at the method detection limit of each analyte of interest. Interferences
are defined as systematic errors in the measured analytical signal of an
established procedure caused by the presence of interfering species
(interferent). The interferent concentration is presupposed to be
normally distributed in representative samples of a given matrix.
3. (a) If the MDL is to be determined in reagent (blank) water,
prepare a laboratory standard (analyte in reagent water) at a
concentration which is at least equal to or in the same concentration
range as the estimated method detection limit. (Recommend between 1 and
5 times the estimated method detection limit.) Proceed to Step 4.
(b) If the MDL is to be determined in another sample matrix, analyze
the sample. If the measured level of the analyte is in the recommended
range of one to five times the estimated detection limit, proceed to
Step 4.
If the measured level of analyte is less than the estimated
detection limit, add a known amount of analyte to bring the level of
analyte between one and five times the estimated detection limit.
If the measured level of analyte is greater than five times the
estimated detection limit, there are two options.
(1) Obtain another sample with a lower level of analyte in the same
matrix if possible.
(2) The sample may be used as is for determining the method
detection limit if the analyte level does not exceed 10 times the MDL of
the analyte in reagent water. The variance of the analytical method
changes as the analyte concentration increases from the MDL, hence the
MDL determined under these circumstances may not truly reflect method
variance at lower analyte concentrations.
4. (a) Take a minimum of seven aliquots of the sample to be used to
calculate the method detection limit and process each through the entire
analytical method. Make all computations according to the defined method
with final results in the method reporting units. If a blank measurement
is required to calculate the measured level of analyte, obtain a
separate blank measurement for each sample aliquot analyzed. The average
blank measurement is subtracted from the respective sample measurements.
(b) It may be economically and technically desirable to evaluate the
estimated method detection limit before proceeding with 4a. This will:
(1) Prevent repeating this entire procedure when the costs of analyses
are high and (2) insure that the procedure is being conducted at the
correct concentration. It is quite possible that an inflated MDL will be
calculated from data obtained at many times the real MDL even though the
level of analyte is less than five times the calculated method detection
limit. To insure that the estimate of the method detection limit is a
good estimate, it is necessary to determine that a lower concentration
of analyte will not result in a significantly lower method detection
limit. Take two aliquots of the sample to be used to calculate the
method detection limit and process each through the entire method,
including blank measurements as described above in 4a. Evaluate these
data:
(1) If these measurements indicate the sample is in desirable range
for determination of the MDL, take five additional aliquots and proceed.
Use all seven measurements for calculation of the MDL.
(2) If these measurements indicate the sample is not in correct
range, reestimate the MDL, obtain new sample as in 3 and repeat either
4a or 4b.
5. Calculate the variance (S\2\) and standard deviation (S) of the
replicate measurements, as follows:
[GRAPHIC] [TIFF OMITTED] TC15NO91.208
where:
X[iota]; i=1 to n, are the analytical results in the final method
reporting units obtained from
[[Page 321]]
the n sample aliquots and [Sigma] refers to the sum of the X values from
i=l to n.
6. (a) Compute the MDL as follows:
MDL = t(n-1,1-[alpha]=0.99) (S)
where:
MDL = the method detection limit
t(n-1,1-[alpha]=.99) = the students' t value appropriate for
a 99% confidence level and a standard deviation estimate with n-1
degrees of freedom. See Table.
S = standard deviation of the replicate analyses.
(b) The 95% confidence interval estimates for the MDL derived in 6a
are computed according to the following equations derived from
percentiles of the chi square over degrees of freedom distribution
([chi]\2\/df).
LCL = 0.64 MDL
UCL = 2.20 MDL
where: LCL and UCL are the lower and upper 95% confidence limits
respectively based on seven aliquots.
7. Optional iterative procedure to verify the reasonableness of the
estimate of the MDL and subsequent MDL determinations.
(a) If this is the initial attempt to compute MDL based on the
estimate of MDL formulated in Step 1, take the MDL as calculated in Step
6, spike the matrix at this calculated MDL and proceed through the
procedure starting with Step 4.
(b) If this is the second or later iteration of the MDL calculation,
use S2 from the current MDL calculation and S2
from the previous MDL calculation to compute the F-ratio. The F-ratio is
calculated by substituting the larger S2 into the numerator
S2A and the other into the denominator
S2B. The computed F-ratio is then compared with
the F-ratio found in the table which is 3.05 as follows: if
S2A/S2B<3.05, then compute
the pooled standard deviation by the following equation:
[GRAPHIC] [TIFF OMITTED] TC15NO91.209
if S2A/
S2B3.05, respike at the most recent
calculated MDL and process the samples through the procedure starting
with Step 4. If the most recent calculated MDL does not permit
qualitative identification when samples are spiked at that level, report
the MDL as a concentration between the current and previous MDL which
permits qualitative identification.
(c) Use the Spooled as calculated in 7b to compute The
final MDL according to the following equation:
MDL=2.681 (Spooled)
where 2.681 is equal to t(12,1-[alpha]=.99).
(d) The 95% confidence limits for MDL derived in 7c are computed
according to the following equations derived from precentiles of the chi
squared over degrees of freedom distribution.
LCL=0.72 MDL
UCL=1.65 MDL
where LCL and UCL are the lower and upper 95% confidence limits
respectively based on 14 aliquots.
Tables of Students' t Values at the 99 Percent Confidence Level
------------------------------------------------------------------------
Degrees
of
Number of replicates freedom tcn-1,.99)
(n-1)
------------------------------------------------------------------------
7............................................... 6 3.143
8............................................... 7 2.998
9............................................... 8 2.896
10.............................................. 9 2.821
11.............................................. 10 2.764
16.............................................. 15 2.602
21.............................................. 20 2.528
26.............................................. 25 2.485
31.............................................. 30 2.457
61.............................................. 60 2.390
00.............................................. 00 2.326
------------------------------------------------------------------------
Reporting
The analytical method used must be specifically identified by number
or title ald the MDL for each analyte expressed in the appropriate
method reporting units. If the analytical method permits options which
affect the method detection limit, these conditions must be specified
with the MDL value. The sample matrix used to determine the MDL must
also be identified with MDL value. Report the mean analyte level with
the MDL and indicate if the MDL procedure was iterated. If a laboratory
standard or a sample that contained a known amount analyte was used for
this determination, also report the mean recovery.
[[Page 322]]
If the level of analyte in the sample was below the determined MDL
or exceeds 10 times the MDL of the analyte in reagent water, do not
report a value for the MDL.
[49 FR 43430, Oct. 26, 1984; 50 FR 694, 696, Jan. 4, 1985, as amended at
51 FR 23703, June 30, 1986]
Appendix C to Part 136--Inductively Coupled Plasma--Atomic Emission
Spectrometric Method for Trace Element Analysis of Water and Wastes
Method 200.7
1. Scope and Application
1.1 This method may be used for the determination of dissolved,
suspended, or total elements in drinking water, surface water, and
domestic and industrial wastewaters.
1.2 Dissolved elements are determined in filtered and acidified
samples. Appropriate steps must be taken in all analyses to ensure that
potential interferences are taken into account. This is especially true
when dissolved solids exceed 1500 mg/L. (See Section 5.)
1.3 Total elements are determined after appropriate digestion
procedures are performed. Since digestion techniques increase the
dissolved solids content of the samples, appropriate steps must be taken
to correct for potential interference effects. (See Section 5.)
1.4 Table 1 lists elements for which this method applies along with
recommended wavelengths and typical estimated instrumental detection
limits using conventional pneumatic nebulization. Actual working
detection limits are sample dependent and as the sample matrix varies,
these concentrations may also vary. In time, other elements may be added
as more information becomes available and as required.
1.5 Because of the differences between various makes and models of
satisfactory instruments, no detailed instrumental operating
instructions can be provided. Instead, the analyst is referred to the
instruction provided by the manufacturer of the particular instrument.
2. Summary of Method
2.1 The method describes a technique for the simultaneous or
sequential multielement determination of trace elements in solution. The
basis of the method is the measurement of atomic emission by an optical
spectroscopic technique. Samples are nebulized and the aero sol that is
produced is trans ported to the plasma torch where excitation occurs.
Characteristic atomic-line emission spectra are produced by a radio-
frequency inductively coupled plasma (ICP). The spectra are dispersed by
a grating spectrometer and the intensities of the lines are monitored by
photomultiplier tubes. The photocurrents from the photomultiplier tubes
are processed and controlled by a computer system. A background
correction technique is required to compensate for variable background
contribution to the determination of trace elements. Background must be
measured adjacent to analyte lines on samples during analysis. The
position selected for the background intensity measurement, on either or
both sides of the analytical line, will be determined by the complexity
of the spectrum adjacent to the analyte line. The position used must be
free of spectral interference and reflect the same change in background
intensity as occurs at the analyte wavelength measured. Background
correction is not required in cases of line broadening where a
background correction measure ment would actually degrade the analyti
cal result. The possibility of additional interferences named in 5.1
(and tests for their presence as described in 5.2) should also be
recognized and appropriate corrections made.
3. Definitions
3.1 Dissolved--Those elements which will pass through a 0.45
[micro]m membrane filter.
3.2 Suspended--Those elements which are retained by a 0.45 [micro]m
membrane filter.
3.3 Total--The concentration determined on an unfiltered sample
following vigorous digestion (Section 9.3), or the sum of the dissolved
plus suspended concentrations. (Section 9.1 plus 9.2).
3.4 Total recoverable--The concentration determined on an unfiltered
sample following treatment with hot, dilute mineral acid (Section 9.4).
3.5 Instrumental detection limit--The concentration equivalent to a
signal, due to the analyte, which is equal to three times the standard
deviation of a series of ten replicate measurements of a reagent blank
signal at the same wavelength.
3.6 Sensitivity--The slope of the analytical curve, i.e., functional
relationship between emission intensity and concentration.
3.7 Instrument check standard--A multiele ment standard of known
concentrations pre pared by the analyst to monitor and verify instrument
performance on a daily basis. (See 7.6.1)
3.8 Interference check sample--A solution containing both
interfering and analyte elemelts of known concentration that can be used
to verify background and interelement correction factors. (See 7.6.2.)
3.9 Quality control sample--A solution obtained from an outside
source having known, concentration values to be used to verify the
calibration standards. (See 7.6.3)
3.10 Calibration standards--A series of known standard solutions
used by the analyst for calibration of the instrument (i.e., preparation
of the analytical curve). (See 7.4)
[[Page 323]]
3.11 Linear dynamic range--The concentration range over which the
analytical curve remains linear.
3.12 Reagent blank--A volume of deionized, distilled water
containing the same acid matrix as the calibration standards carried
through the entire analytical scheme. (See 7.5.2)
3.13 Calibration blank--A volume of deionized, distilled water
acidified with HNO3 and HCl. (See 7.5.1)
3.14 Methmd of standard addition-- The standard addition technique
involves the use of the unknown and the unknown plus a known amount of
standard. (See 10.6.1.)
4. Safety
4.1 The toxicity of carcinogenicity of each reagent used in this
method has not been precisely defined; however, each chemical compound
should be treated as a potential health hazard. From this viewpoint,
exposure to these chemicals must be reduced to the lowest possible level
by whatever means available. The laboratory is repsonsible for
maintaining a current awareness file of OSHA regulations regarding the
safe handling of the chemicals specified in this method. A reference
file of material data handling sheets should also be made available to
all personnel involved in the chemical analysis. Additional references
to laboratory safety are available and have been identified
(14.7,14.8 and 14.9) for the information of the analyst.
5. Interferences
5.1 Several types of interference effects may contribute to
inaccuracies in the determination of trace elements. They can be
summarized as follows:
5.1.1 Spectral interferences can be categorized as (1) overlap of a
spectral line from another element; (2) unresolved overlap of molecular
band spectra; (3) background contribution from continuous or
recombination phenomena; and (4) background contribution from stray
light from the line emission of high concentration elements. The first
of these effects can be compensated by utilizing a computer correction
of the raw data, requiring the monitoring and measurement of the
interfering element. The second effect may require selection of an
alternate wavelength. The third and fourth effects can usually be
compensated by a background correction adjacent to the analyte line. In
addition, users of simultaneous multi-element instrumentation must
assume the responsibility of verifying the absence of spectral
interference from an element that could occur in a sample but for which
there is no channel in the instrument array. Listed in Table 2 are some
interference effects for the recommended wavelengths given in Table 1.
The data in Table 2 are intended for use only as a rudimentary guide for
the indication of potential spectral interferences. For this purpose,
linear relations between concentration and intensity for the analytes
and the interferents can be assumed. The Interference information, which
was collected at the Ames Laboratory,\1\ is expressed as analyte
concentration equivalents (i.e., false analyte concentrations) arising
from 100 mg/L of the interferent element. The suggested use of this
information is as follows: Assume that arsenic (at 193.696 nm) is to be
determined in a sample containing approximately 10 mg/L of aluminum.
According to Table 2, 100 mg/L of aluminum would yield a false signal
for arsenic equivalent to approximately 1.3 mg/L. Therefore, 10 mg/L of
aluminum would result in a false signal for arsenic equivalent to
approximately 0.13 mg/L. The reader is cautioned that other analytical
systems may exhibit somewhat different levels of interference than those
shown in Table 2, and that the interference effects must be evaluated
for each individual system.
---------------------------------------------------------------------------
\1\ Ames Laboratory, USDOE, Iowa State University, Ames Iowa 50011.
---------------------------------------------------------------------------
Only those interferents listed were investigated and the blank
spaces in Table 2 indicate that measurable interferences were not
observed for the interferent concentrations listed in Table 3.
Generally, interferences were discernible if they produced peaks or
background shifts corresponding to 2-5% of the peaks generated by the
analyte concentrations also listed in Table 3.
At present, information on the listed silver and potassium
wavelengths are not available but it has been reported that second order
energy from the magnesium 383.231 nm wavelength interferes with the
listed potassium line at 766.491 nm.
5.1.2 Physical interferences are generally considered to be effects
associated with the sample nebulization and transport processes. Such
properties as change in viscosity and surface tension can cause
significant inaccuracies especially in samples which may contain high
dissolved solids and/or acid concentrations. The use of a peristaltic
pump may lessen these interferences. If these types of interferences are
operative, they must be reduced by dilution of the sample and/or
utilization of standard addition techniques. Another problem which can
occur from high dissolved solids is salt buildup at the tip of the
nebulizer. This affects aersol flow rate causing instrumental drift.
Wetting the argon prior to nebulization, the use of a tip washer, or
sample dilution have been used to control this problem. Also, it has
been reported that better control of the argon flow rate improves
instrument performance. This is accomplished with the use of mass flow
controllers.
[[Page 324]]
5.1.3 Chemical Interferences are characterized by molecular compound
formation, ionization effects and solute vaporization effects. Normally
these effects are not pronounced with the ICP technique, however, if
observed they can be minimized by careful selection of operating
conditions (that is, incident power, observation position, and so
forth), by buffering of the sample, by matrix matching, and by standard
addition procedures. These types of interferences can be highly
dependent on matrix type and the specific analyte element.
5.2 It is recommended that whenever a new or unusual sample matrix
is encountered, a series of tests be performed prior to reporting
concentration data for analyte elements. These tests, as outlined in
5.2.1 through 5.2.4, will ensure the analyst that neither positive nor
negative interference effects are operative on any of the analyte
elements thereby distorting the accuracy of the reported values.
5.2.1 Serial dilution. If the analyte concentration is sufficiently
high (minimally a factor of 10 above the instrumental detection limit
after dilution), an analysis of a dilution should agree within 5 percent
of the original determination (or within some acceptable control limit
(14.3) that has been established for that matrix.). If not, a chemical
or physical interference effect should be suspected.
5.2.2 Spike addition. The recovery of a spike addition added at a
minimum level of 10X the instrumental detection limit (maximum 100X) to
the original determination should be recovered to within 90 to 110
percent or within the established control limit for that matrix. If not,
a matrix effect should be suspected. The use of a standard addition
analysis procedure can usually compensate for this effect.
Caution: The standard addition technique does not detect coincident
spectral overlap. If suspected, use of computerized compensation, an
alternate wavelength, or comparison with an alternate method is
recommended (See 5.2.3).
5.2.3 Comparison with alternate method of analysis. When
investigating a new sample matrix, comparison tests may be performed
with other analytical techniques such as atomic absorption spectrometry,
or other approved methodology.
5.2.4 Wavelength scanning of analyte line region. If the appropriate
equipment is available, wavelength scanning can be performed to detect
potential spectral interferences.
6. Apparatus
6.1 Inductively Coupled Plasma-Atomic Emission Spectrometer.
6.1.1 Computer controlled atomic emission spectrometer with
background correction.
6.1.2 Radiofrequency generator.
6.1.3 Argon gas supply, welding grade or better.
6.2 Operating conditions--Because of the differences between various
makes and models of satisfactory instruments, no detailed operating
instructions can be provided. Instead, the analyst should follow the
instructions provided by the manufacturer of the particular instrument.
Sensitivity, instrumental detection limit, precision, linear dynamic
range, and interference effects must be investigated and established for
each individual analyte line on that particular instrument. It is the
responsibility of the analyst to verify that the instrument
configuration and operating conditions used satisfy the analytical
requirements and to maintain quality control data confirming instrument
performance and analytical results.
7. Reagents and Standards
7.1 Acids used in the preparation of standards and for sample
processing must be ultra-high purity grade or equivalent. Redistilled
acids are acceptable.
7.1.1 Acetic acid, conc. (sp gr 1.06).
7.1.2 Hydrochloric acid, conc. (sp gr 1.19).
7.1.3 Hydrochloric acid, (1+1): Add 500 mL conc. HCl (sp gr 1.19) to
400 mL deionized, distilled water and dilute to 1 liter.
7.1.4 Nitric acid, conc. (sp gr 1.41).
7.1.5 Nitric acid, (1+1): Add 500 mL conc. HNO3 (sp gr
1.41) to 400 mL deionized, distilled water and dilute to 1 liter.
7.2 Deionized, distilled water: Prepare by passing distilled water
through a mixed bed of cation and anion exchange resins. Use deionized,
distilled water for the preparation of all reagents, calibration
standards and as dilution water. The purity of this water must be
equivalent to ASTM Type II reagent water of Specification D 1193 (14.6).
7.3 Standard stock solutions may be purchased or prepared from ultra
high purity grade chemicals or metals. All salts must be dried for 1 h
at 105 [deg]C unless otherwise specified.
(CAUTION: Many metal salts are extremely toxic and may be fatal if
swallowed. Wash hands thoroughly after handling.)
Typical stock solution preparation procedures follow:
7.3.1 Aluminum solution, stock, 1 mL=100[micro]g Al: Dissolve 0.100
g of aluminum metal in an acid mixture of 4 mL of (1+1) HCl and 1 mL of
conc. HNO3 in a beaker. Warm gently to effect solution. When
solution is complete, transfer quantitatively to a liter flask add an
additional 10 mL of (1+1) HCl and dilute to 1,000 mL with deionized,
distilled water.
7.3.2 Antimony solution stock, 1 mL=100 [micro]g Sb: Dissolve 0.2669
g K(SbO)C4H4O6 in deionized distilled
water, add 10 mL (1+1) HCl and dilute to 1,000 mL with deionized,
distilled water.
[[Page 325]]
7.3.3 Arsenic solution, stock, 1 mL=100 [micro]g As: Dissolve 0.1320
g of As2O3 in 100 mL of deionized, distilled water
containing 0.4 g NaOH. Acidify the solution with 2 mL conc.
HNO3 and dilute to 1,000 mL with deionized, distilled water.
7.3.4 Barium solution, stock, 1 mL=100 [micro]g Ba: Dissolve 0.1516
g BaCl2 (dried at 250 [deg]C for 2 hrs) in 10 mL deionized,
distilled water with 1 mL (1+1) HCl. Add 10.0 mL (1+1) HCl and dilute to
1,000 with mL deionized, distilled water.
7.3.5 Beryllium solution, stock, 1 mL=100 [micro]g Be: Do not dry.
Dissolve 1.966 g BeSO4[middot]4H2O, in deionized,
distilled water, add 10.0 mL conc. HNO3 and dilute to 1,000
mL with deionized, distilled water.
7.3.6 Boron solution, stock, 1 mL=100[micro]g B: Do not dry.
Dissolve 0.5716 g anhydrous H3BO3 in deionized,
distilled water and dilute to 1,000 mL. Use a reagent meeting ACS
specifications, keep the bottle tightly stoppered and store in a
desiccator to prevent the entrance of atmospheric moisture.
7.3.7 Cadmium solution, stock, 1 mL=100 [micro]g Cd: Dissolve 0.1142
g CdO in a minimum amount of (1+1) HNO3. Heat to increase
rate of dissolution. Add 10.0 mL conc. HNO3 and dilute to
1,000 mL with deionized, distilled water.
7.3.8 Calcium solution, stock, 1 mL=100 [micro]g Ca: Suspend 0.2498
g CaCO3 dried at 180 [deg]C for 1 h before weighing in
deionized, distilled water and dissolve cautiously with a minimum amount
of (1+1) HNO3. Add 10.0 mL conc. HNO3 and dilute
to 1,000 mL with deionized, distilled water.
7.3.9 Chromium solution, stock, 1 mL=100 [micro]g Cr: Dissolve
0.1923 g of CrO3 in deionized, distilled water. When solution
is complete, acidify with 10 mL conc. HNO3 and dilute to
1,000 mL with deionized, distilled water.
7.3.10 Cobalt solution, stock, 1 mL=100 [micro]g Co: Dissolve 0.1000
g of cobalt metal in a minimum amount of (1+1) HNO3. Add 10.0
mL (1+1) HCl and dilute to 1,000 mL with deionized, distilled water.
7.3.11 Copper solution, stock, 1 mL=100 [micro]g Cu: Dissolve 0.1252
g CuO in a minimum amount of (1+1) HNO3. Add 10.0 mL conc.
HNO3 and dilute to 1,000 mL with deionized, distilled water.
7.3.12 Iron solution, stock, 1 mL=100 [micro]g Fe: Dissolve 0.1430 g
Fe2O3 in a warm mixture of 20 mL (1+1) HCl and 2
mL of conc. HNO3. Cool, add an additional 5 mL of conc.
HNO3 and dilute to 1,000 mL with deionized, distilled water.
7.3.13 Lead solution, stock, 1 mL=100 [micro]g Pb: Dissolve 0.1599 g
Pb(NO3)2 in a minimum amount of (1+1)
HNO3. Add 10.0 mL conc. HNO3 and dilute to 1,000
mL with deionized, distilled water.
7.3.14 Magnesium solution, stock, 1 mL=100 [micro]g Mg: Dissolve
0.1658 g MgO in a minimum amount of (1+1) HNO3. Add 10.0 mL
conc. HNO3 and dilute to 1,000 mL with deionized, distilled
water.
7.3.15 Manganese solution, stock, 1 mL=100 [micro]g Mn: Dissolve
0.1000 g of manganese metal in the acid mixture 10 mL conc. HCl and 1 mL
conc. HNO3, and dilute to 1,000 mL with deionized, distilled
water.
7.3.16 Molybdenum solution, stock, 1 mL=100 [micro]g Mo: Dissolve
0.2043 g (NH4)2 MoO4 in deionized,
distilled water and dilute to 1,000 mL.
7.3.17 Nickel solution, stock, 1 mL=100 [micro]g Ni: Dissolve 0.1000
g of nickel metal in 10 mL hot conc. HNO3, cool and dilute to
1,000 mL with deionized, distilled water.
7.3.18 Potassium solution, stock, 1 mL=100 [micro]g K: Dissolve
0.1907 g KCl, dried at 110 [deg]C, in deionized, distilled water and
dilute to 1,000 mL.
7.3.19 Selenium solution, stock, 1 mL=100 [micro]g Se: Do not dry.
Dissolve 0.1727 g H2SeO3 (actual assay 94.6%) in
deionized, distilled water and dilute to 1,000 mL.
7.3.20 Silica solution, stock, 1 mL=100 [micro]g SiO2: Do
not dry. Dissolve 0.4730 g
Na2SiO3[middot]9H2O in deionized,
distilled water. Add 10.0 mL conc. HNO3 and dilute to 1,000
mL with deionized, distilled water.
7.3.21 Silver solution, stock, 1 mL=100 [micro]g Ag: Dissolve 0.1575
g AgNO3 in 100 mL of deionized, distilled water and 10 mL
conc. HNO3. Dilute to 1,000 mL with deionized, distilled
water.
7.3.22 Sodium solution, stock, 1 mL=100 [micro]g Na: Dissolve 0.2542
g NaCl in deionized, distilled water. Add 10.0 mL conc. HNO3
and dilute to 1,000 mL with deionized, distilled water.
7.3.23 Thallium solution, stock, 1 mL=100 [micro]g Tl: Dissolve
0.1303 g TlNO3 in deionized, distilled water. Add 10.0 mL
conc. HNO3 and dilute to 1,000 mL with deionized, distilled
water.
7.3.24 Vanadium solution, stock, 1 mL=100 [micro]g V: Dissolve
0.2297 NH4 VO3 in a minimum amount of conc.
HNO3. Heat to increase rate of dissolution. Add 10.0 mL conc.
HNO3 and dilute to 1,000 mL with deionized, distilled water.
7.3.25 Zinc solution, stock, 1 mL=100 [micro]g Zn: Dissolve 0.1245 g
ZnO in a minimum amount of dilute HNO3. Add 10.0 mL conc.
HNO3 and dilute to 1,000 mL deionized, distilled water.
7.4 Mixed calibration standard solutions--Prepare mixed calibration
standard solutions by combining appropriate volumes of the stock
solutions in volumetric flasks. (See 7.4.1 thru 7.4.5) Add 2 mL of (1+1)
HNO3 and 10 mL of (1+1) HC1 and dilute to 100 mL with
deionized, distilled water. (See Notes 1 and 6.) Prior to preparing the
mixed standards, each stock solution should be analyzed separately to
determine possible spectral interference or the presence of impurities.
Care should be taken when preparing the
[[Page 326]]
mixed standards that the elemelts are compatible and stable. Transfer
the mixed standard solutions to a FEP fluorocarbon or unused
polyethylene bottle for storage. Fresh mixed standards should be
prepared as needed with the realization that concentration can change on
aging. Calibration standards must be initially verified using a quality
control sample and monitored weekly for stability (See 7.6.3). Although
not specifically required, some typical calibration standard
combinations follow when using those specific wavelengths listed in
Table 1.
7.4.1 Mixed standard solution I--Manganese, beryllium, cadmium,
lead, and zinc.
7.4.2 Mixed standard solution II--Barium, copper, iron, vanadium,
and cobalt.
7.4.3 Mixed standard solution III--Molybdenum, silica, arsenic, and
selenium.
7.4.4 Mixed standard solution IV--Calcium, sodium, potassium,
aluminum, chromium and nickel.
7.4.5 Mixed standard solution V-- Antimony, boron, magnesium,
silver, and thallium.
Note: 1. If the addition of silver to the recommended acid
combination results in an initial precipitation, add 15 mL of deionized
distilled water and warm the flask until the solution clears. Cool and
dilute to 100 mL with deionized, distilled water. For this acid
combination the silver concentration should be limited to 2 mg/L. Silver
under these conditions is stable in a tap water matrix for 30 days.
Higher concentrations of silver require additional HCl.
7.5 Two types of blanks are required for the analysis. The
calibration blank (3.13) is used in establishing the analytical curve
while the reagent blank (3.12) is used to correct for possible
contamination resulting from varying amounts of the acids used in the
sample processing.
7.5.1 The calibration blank is prepared by diluting 2 mL of (1+1)
HNO3 and 10 mL of (1+1) HCl to 100 mL with deionized,
distilled water. (See Note 6.) Prepare a sufficient quantity to be used
to flush the system between standards and samples.
7.5.2 The reagent blank must contain all the reagents and in the
same volumes as used in the processing of the samples. The reagent blank
must be carried through the complete procedure and contain the same acid
concentration in the final solution as the sample solution used for
analysis.
7.6 In addition to the calibration standards, an instrument check
standard (3.7), an interference check sample (3.8) and a quality control
sample (3.9) are also required for the analyses.
7.6.1 The instrument check standard is prepared by the analyst by
combining compatible elements at a concentration equivalent to the
midpoint of their respective calibration curves. (See 12.1.1.)
7.6.2 The interference check sample is prepared by the analyst in
the following manner. Select a representative sample which contains
minimal concentrations of the analytes of interest but known
concentration of interfering elements that will provide an adequate test
of the correction factors. Spike the sample with the elements of
interest at the approximate concentration of either 100 [micro]g/L or 5
times the estimated detection limits given in Table 1. (For effluent
samples of expected high concentrations, spike at an appropriate level.)
If the type of samples analyzed are varied, a synthetically prepared
sample may be used if the above criteria and intent are met.
7.6.3 The quality control sample should be prepared in the same acid
matrix as the calibration standards at a concentration near 1 mg/L and
in accordance with the instructions provided by the supplier. The
Quality Assurance Branch of EMSL-Cincinnati will either supply a quality
control sample or information where one of equal quality can be
procured. (See 12.1.3.)
8. Sample Handling and Preservation
8.1 For the determination of trace elements, contamination and loss
are of prime concern. Dust in the laboratory environment, impurities in
reagents and impurities on laboratory apparatus which the sample
contacts are all sources of potential contamination. Sample containers
can introduce either positive or negative errors in the measurement of
trace elements by (a) contributing contaminants through leaching or
surface desorption and (b) by depleting concentrations through
adsorption. Thus the collection and treatment of the sample prior to
analysis requires particular attention. Laboratory glassware including
the sample bottle (whether polyethylene, polyproplyene or FEP-
fluorocarbon) should be thoroughly washed with detergent and tap water;
rinsed with (1+1) nitric acid, tap water, (1+1) hydrochloric acid, tap
and finally deionized, distilled water in that order (See Notes 2 and
3).
Note: 2. Chromic acid may be useful to remove organic deposits from
glassware; however, the analyst should be cautioned that the glassware
must be thoroughly rinsed with water to remove the last traces of
chromium. This is especially important if chromium is to be included in
the analytical scheme. A commercial product, NOCHROMIX, available from
Godax Laboratories, 6 Varick St., New York, NY 10013, may be used in
place of chromic acid. Chromic acid should not be used with plastic
bottles.
Note: 3. If it can be documented through an active analytical
quality control program using spiked samples and reagent blanks, that
certain steps in the cleaning procedure
[[Page 327]]
are not required for routine samples, those steps may be eliminated from
the procedure.
8.2 Before collection of the sample a decision must be made as to
the type of data desired, that is dissolved, suspended or total, so that
the appropriate preservation and pretreatment steps may be accomplished.
Filtration, acid preservation, etc., are to be performed at the time the
sample is collected or as soon as possible thereafter.
8.2.1 For the determination of dissolved elements the sample must be
filtered through a 0.45-[micro]m membrane filter as soon as practical
after collection. (Glass or plastic filtering apparatus are recommended
to avoid possible contamination.) Use the first 50-100 mL to rinse the
filter flask. Discard this portion and collect the required volume of
filtrate. Acidify the filtrate with (1+1) HNO3 to a pH of 2
or less. Normally, 3 mL of (1+1) acid per liter should be sufficient to
preserve the sample.
8.2.2 For the determination of suspended elements a measured volume
of unpreserved sample must be filtered through a 0.45-[micro]m membrane
filter as soon as practical after collection. The filter plus suspended
material should be transferred to a suitable container for storage and/
or shipment. No preservative is required.
8.2.3 For the determination of total or total recoverable elements,
the sample is acidified with (1+1) HNO3 to pH 2 or less as
soon as possible, preferably at the time of collection. The sample is
not filtered before processing.
9. Sample Preparation
9.1 For the determinations of dissolved elements, the filtered,
preserved sample may often be analyzed as received. The acid matrix and
concentration of the samples and calibration standards must be the same.
(See Note 6.) If a precipitate formed upon acidification of the sample
or during transit or storage, it must be redissolved before the analysis
by adding additional acid and/or by heat as described in 9.3.
9.2 For the determination of suspended elements, transfer the
membrane filter containing the insoluble material to a 150-mL Griffin
beaker and add 4 mL conc. HNO3. Cover the beaker with a watch
glass and heat gently. The warm acid will soon dissolve the membrane.
Increase the temperature of the hot plate and digest the material. When
the acid has nearly evaporated, cool the beaker and watch glass and add
another 3 mL of conc. HNO3. Cover and continue heating until
the digestion is complete, generally indicated by a light colored
digestate. Evaporate to near dryness (2 mL), cool, and 10 mL HCl (1+1)
and 15 mL deionized, distilled water per 100 mL dilution and warm the
beaker gently for 15 min. to dissolve any precipitated or residue
material. Allow to cool, wash down the watch glass and beaker walls with
deionized distilled water and filter the sample to remove insoluble
material that could clog the nebulizer. (See Note 4.) Adjust the volume
based on the expected concentrations of elements present. This volume
will vary depending on the elements to be determined (See Note 6). The
sample is now ready for analysis. Concentrations so determined shall be
reported as ``suspended.''
Note: 4. In place of filtering, the sample after diluting and mixing
may be centrifuged or allowed to settle by gravity overnight to remove
insoluble material.
9.3 For the determination of total elements, choose a measured
volume of the well mixed acid preserved sample appropriate for the
expected level of elements and transfer to a Griffin beaker. (See Note
5.) Add 3 mL of conc. HNO3. Place the beaker on a hot plate
and evaporate to near dryness cautiously, making certain that the sample
does not boil and that no area of the bottom of the beaker is allowed to
go dry. Cool the beaker and add another 5 mL portion of conc.
HNO3. Cover the beaker with a watch glass and return to the
hot plate. Increase the temperature of the hot plate so that a gently
reflux action occurs. Continue heating, adding additional acid as
necessary, until the digestion is complete (generally indicated when the
digestate is light in color or does not change in appearance with
continued refluxing.) Again, evaporate to near dryness and cool the
beaker. Add 10 mL of 1+1 HCl and 15 mL of deionized, distilled water per
100 mL of final solution and warm the beaker gently for 15 min. to
dissolve any precipitate or residue resulting from evaporation. Allow to
cool, wash down the beaker walls and watch glass with deionized
distilled water and filter the sample to remove insoluble material that
could clog the nebulizer. (See Note 4.) Adjust the sample to a
predetermined volume based on the expected concentrations of elements
present. The sample is now ready for analysis (See Note 6).
Concentrations so determined shall be reported as ``total.''
Note: 5. If low determinations of boron are critical, quartz
glassware should be used.
Note: 6. If the sample analysis solution has a different acid
concentration from that given in 9.4, but does not introduce a physical
interference or affect the analytical result, the same calibration
standards may be used.
9.4 For the determination of total recoverable elements, choose a
measured volume of a well mixed, acid preserved sample appropriate for
the expected level of elements and transfer to a Griffin beaker. (See
Note 5.) Add 2 mL of (1+1) HNO3 and 10 mL of (1+1) HCl to the
sample and heat on a steam bath
[[Page 328]]
or hot plate until the volume has been reduced to near 25 mL making
certain the sample does not boil. After this treatment, cool the sample
and filter to remove insoluble material that could clog the nebulizer.
(See Note 4.) Adjust the volume to 100 mL and mix. The sample is now
ready for analysis. Concentrations so determined shall be reported as
``total.''
10. Procedure
10.1 Set up instrument with proper operating parameters established
in Section 6.2. The instrument must be allowed to become thermally
stable before beginning. This usually requires at least 30 min. of
operation prior to calibration.
10.2 Initiate appropriate operating configuration of computer.
10.3 Profile and calibrate instrument according to instrument
manufacturer's recommended procedures, using the typical mixed
calibration standard solutions described in Section 7.4. Flush the
system with the calibration blank (7.5.1) between each standard. (See
Note 7.) (The use of the average intensity of multiple exposures for
both standardization and sample analysis has been found to reduce random
error.)
Note: 7. For boron concentrations greater than 500 [micro]g/L
extended flush times of 1 to 2 minutes may be required.
10.4 Before beginning the sample run, reanalyze the highest mixed
calibration standard as if it were a sample. Concentration values
obtained should not deviate from the actual values by more than 5 percent (or the established control limits whichever
is lower). If they do, follow the recommendations of the instrument
manufacturer to correct for this condition.
10.5 Begin the sample run flushing the system with the calibration
blank solution (7.5.1) between each sample. (See Note 7.) Analyze the
instrument check standard (7.6.1) and the calibration blank (7.5.1) each
10 samples.
10.6 If it has been found that methods of standard addition are
required, the following procedure is recommended.
10.6.1 The standard addition technique (14.2) involves preparing new
standards in the sample matrix by adding known amounts of standard to
one or more aliquots of the processed sample solution. This technique
compensates for a sample constitutent that enhances or depresses the
analyte signal thus producing a different slope from that of the
calibration standards. It will not correct for additive interference
which causes a baseline shift. The simplest version of this technique is
the single-addition method. The procedure is as follows. Two identical
aliquots of the sample solution, each of volume VX, are
taken. To the first (labeled A) is added a small volume Vs of
a standard analyte solution of concentration cs. To the
second (labeled B) is added the same volume Vs of the
solvent. The analytical signals of A and B are measured and corrected
for nonanalyte signals. The unknown sample concentration cX
is calculated:
[GRAPHIC] [TIFF OMITTED] TC15NO91.128
where SA and SB are the analytical signals
(corrected for the blank) of solutions A and B, respectively.
Vs and cs should be chosen so that SA
is roughly twice SB on the average. It is best if
Vs is made much less than VX, and thus
cs is much greater than cX, to avoid excess
dilution of the sample matrix. If a separation or concentration step is
used, the additions are best made first and carried through the entire
procedure. For the results from this technique to be valid, the
following limitations must be taken into consideration:
1. The analytical curve must be linear.
2. The chemical form of the analyte added must respond the same as
the analyte in the sample.
3. The interference effect must be constant over the working range
of concern.
4. The signal must be corrected for any additive interference.
11. Calculation
11.1 Reagent blanks (7.5.2) should be subtracted from all samples.
This is particularly important for digested samples requiring large
quantities of acids to complete the digestion.
11.2 If dilutions were performed, the appropriate factor must be
applied to sample values.
11.3 Data should be rounded to the thousandth place and all results
should be reported in mg/L up to three significant figures.
12. Quality Control (Instrumental)
12.1 Check the instrument standardization by analyzing appropriate
quality control check standards as follow:
12.1.1 Analyze and appropriate instrument check standard (7.6.1)
containing the elements of interest at a frequency of 10%. This check
standard is used to determine instrument drift. If agreement is not
within 5% of the expected values or within the
established control limits, whichever is lower, the analysis is out of
control. The analysis should be terminated, the problem corrected, and
the instrument recalibrated.
[[Page 329]]
Analyze the calibration blank (7.5.1) at a frequency of 10%. The
result should be within the established control limits of 2 standard
deviations of the meal value. If not, repeat the analysis two more times
and average the three results. If the average is not wihin the control
limit, terminate the analysis, correct the problem and recalibrate the
instrument.
12.1.2 To verify interelement and background correction factors
analyze the interference check sample (7.6.2) at the beginning, end, and
at periodic intervals throughout the sample run. Results should fall
within the established control limits of 1.5 times the standard
deviation of the mean value. If not, terminate the analysis, correct the
problem and recalibrate the instrument.
12.1.3 A quality control sample (7.6.3) obtained from an outside
source must first be used for the initial verification of the
calibration standards. A fresh dilution of this sample shall be analyzed
every week thereafter to monitor their stability. If the results are not
within 5% of the true value listed for the control
sample, prepare a new calibration standard and recalibrate the
instrument. If this does not correct the problem, prepare a new stock
standard and a new calibration standard and repeat the calibration.
13. Precision and Accuracy
13.1 An interlaboratory study of metal analyses by this method was
conducted by the Quality Assurance Branch (QAB) of the Environmental
Monitoring Systems Laboratory--Cincinnati (EMSL-CI). Synthetic
concentrates containing various levels of the twenty-five elements
listed in Table 4 were added to reagent water, surface water, drinking
water and three effluents. These samples were digested by both the total
digestion procedure (9.3) and the total recoverable procedure (9.4).
Results for both digestions for the twenty-five elements in reagent
water are given in Table 4; results for the other matrices can be found
in Reference 14.10.
14. References
14.1 Winge, R.K., V.J. Peterson, and V.A. Fassel, ``Inductively
Coupled Plasma-Atomic Emission Spectroscopy: Prominent Lines, EPA-600/4-
79-017.
14.2 Winefordner, J.D., ``Trace Analysis: Spectroscopic Methods for
Elements,'' Chemical Analysis, Vol, 46, pp. 41-42.
14.3 Handbook for Analytical Quality Control in Water and Wastewater
Laboratories, EPA-600/4-79-019.
14.4 Garbarino, J.R. and Taylor, H.E., ``An Inductively-Coupled
Plasma Atomic Emission Spectrometric Method for Routine Water Quality
Testing,'' Applied Spectroscopy 33, No. 3 (1979).
14.5 ``Methods for Chemical Analysis of Water and Wastes,'' EPA-600/
4-79-020.
14.6 Annual Book of ASTM Standards, Part 31.
14.7 ``Carcinogens--Working With Carcinogens,'' Department of
Health, Education, and Welfare, Public Health Service, Center for
Disease Control, National Institute for Occupational Safety and Health,
Publication No. 77-206, August 1977.
14.8 ``OSHA Safety and Health Standards, General Industry,'' (29 CFR
Part 1910), Occupational Safety and Health Administration, OSHA 2206,
(Revised, January 1976).
14.9 ``Safety in Academic Chemistry Laboratories, American Chemical
Society Publication, Committee on Chemical Safety, 3rd Edition, 1979.
14.10 Maxfield R. and Minak B., ``EPA Method Study 27, Method 200.7
Trace Metals by ICP,'' National Technical Information Service, Order No.
PB 85-248-656, November 1983.
Table 1--Recommended Wavelengths \1\ and Estimated Instrumental
Detection Limits
------------------------------------------------------------------------
Estimated
detection
Element Wavelength, limit,
nm [micro]g/
L2
------------------------------------------------------------------------
Aluminum....................................... 308.215 45
Arsenic........................................ 193.696 53
Antimony....................................... 206.833 32
Barium......................................... 455.403 2
Beryllium...................................... 313.042 0.3
Boron.......................................... 249.773 5
Cadmium........................................ 226.502 4
Calcium........................................ 317.933 10
Chromium....................................... 267.716 7
Cobalt......................................... 228.616 7
Copper......................................... 324.754 6
Iron........................................... 259.940 7
Lead........................................... 220.353 42
Magnesium...................................... 279.079 30
Manganese...................................... 257.610 2
Molybdenum..................................... 202.030 8
Nickel......................................... 231.604 15
Potassium...................................... 766.491 3
Selenium....................................... 196.026 75
Silica (SiO2).................................. 288.158 58
Silver......................................... 328.068 7
Sodium......................................... 588.995 29
Thallium....................................... 190.864 40
Vanadium....................................... 292.402 8
Zinc........................................... 213.856 2
------------------------------------------------------------------------
\1\The wavelengths listed are recommended because of their sensitivity
and overall acceptance. Other wavelengths may be substituted if they
can provide the needed sensitivity and are treated with the same
corrective techniques for spectral interference. (See 5.1.1).
\2\The estimated instrumental detection limits as shown are taken from
``Inductively Coupled Plasma-Atomic Emission Spectroscopy-Prominent
Lines,'' EPA-600/4-79-017. They are given as a guide for an
instrumental limit. The actual method detection limits are sample
dependent and may vary as the sample matrix varies.
\3\Highly dependent on operating conditions and plasma position.
[[Page 330]]
Table 1--Analyte Concentration Equivalents (mg/L) Arising From Interferents at the 100 mg/L Level
--------------------------------------------------------------------------------------------------------------------------------------------------------
Interferent--
Analyte Wavelength, -----------------------------------------------------------------------
nm A1 Ca Cr Cu Fe Mg Mn Ni Ti V
--------------------------------------------------------------------------------------------------------------------------------------------------------
Aluminum........................................................... 308.214 ..... ..... ..... ..... ...... ...... 0.21 ..... ..... 1.4
Antimony........................................................... 206.833 0.47 ..... 2.9 ..... 0.08 ...... ..... ..... 0.25 0.45
Arsenic............................................................ 193.696 1.3 ..... 0.44 ..... ...... ...... ..... ..... ..... 1.1
Barium............................................................. 455.403 ..... ..... ..... ..... ...... ...... ..... ..... ..... .....
Beryllium.......................................................... 313.042 ..... ..... ..... ..... ...... ...... ..... ..... 0.04 0.05
Boron.............................................................. 249.773 0.04 ..... ..... ..... 0.32 ...... ..... ..... ..... .....
Cadmium............................................................ 226.502 ..... ..... ..... ..... 0.03 ...... ..... 0.02 ..... .....
Calcium............................................................ 317.933 ..... ..... 0.08 ..... 0.01 0.01 0.04 ..... 0.03 0.03
Chromium........................................................... 267.716 ..... ..... ..... ..... 0.003 ...... 0.04 ..... ..... 0.04
Cobalt............................................................. 228.616 ..... ..... 0.03 ..... 0.005 ...... ..... 0.03 0.15 .....
Copper............................................................. 324.754 ..... ..... ..... ..... 0.003 ...... ..... ..... 0.05 0.02
Iron............................................................... 259.940 ..... ..... ..... ..... ...... ...... 0.12 ..... ..... .....
Lead............................................................... 220.353 0.17 ..... ..... ..... ...... ...... ..... ..... ..... .....
Magnesium.......................................................... 279.079 ..... 0.02 0.11 ..... 0.13 ...... 0.25 ..... 0.07 0.12
Manganese.......................................................... 257.610 0.005 ..... 0.01 ..... 0.002 0.002 ..... ..... ..... .....
Molybdenum......................................................... 202.030 0.05 ..... ..... ..... 0.03 ...... ..... ..... ..... .....
Nickel............................................................. 231.604 ..... ..... ..... ..... ...... ...... ..... ..... ..... .....
Selenium........................................................... 196.026 0.23 ..... ..... ..... 0.09 ...... ..... ..... ..... .....
Silicon............................................................ 288.158 ..... ..... 0.07 ..... ...... ...... ..... ..... ..... 0.01
Sodium............................................................. 588.995 ..... ..... ..... ..... ...... ...... ..... ..... 0.08 .....
Thallium........................................................... 190.864 0.30 ..... ..... ..... ...... ...... ..... ..... ..... .....
Vanadium........................................................... 292.402 ..... ..... 0.05 ..... 0.005 ...... ..... ..... 0.02 .....
Zinc............................................................... 213.856 ..... ..... ..... 0.14 ...... ...... ..... 0.29 ..... .....
--------------------------------------------------------------------------------------------------------------------------------------------------------
Table 3--Interferent and Analyte Elemental Concentrations Used for Interference Measuremelts in Table 2
----------------------------------------------------------------------------------------------------------------
Analytes (mg/L) Interferents (mg/L)
----------------------------------------------------------------------------------------------------------------
Al.................. 10 ......... Al.................. 1,000 .................
AS.................. 10 ......... Ca.................. 1,000 .................
B................... 10 ......... Cr.................. 200 .................
Ba.................. 1 ......... Cu.................. 200 .................
Be.................. 1 ......... Fe.................. 1,000 .................
Ca.................. 1 ......... Mg.................. 1,000 .................
Cd.................. 10 ......... Mn.................. 200 .................
Co.................. 1 ......... Ni.................. 200
Cr.................. 1 ......... Ti.................. 200
Cu.................. 1 ......... V................... 200 .................
Fe.................. 1
Mg.................. 1
Mn.................. 1
Mo.................. 10
Na.................. 10
Ni.................. 10
Pb.................. 10
Sb.................. 10
Se.................. 10
Si.................. 1
Tl.................. 10
V................... 1
Zn.................. 10
----------------------------------------------------------------------------------------------------------------
Table 4--ICP Precision and Recovery Data
----------------------------------------------------------------------------------------------------------------
Concentration Total digestion (9.3) Recoverable digestion
Analyte [micro]g/L [micro]g/L (9.4) [micro]g/L
----------------------------------------------------------------------------------------------------------------
Aluminum...................................... 69-4792 X=0.9273(C)+3.6 X=0.9380(C)+22.1
................ S=0.0559(X)+18.6 S=0.0873(X)+31.7
................ SR=0.0507(X)+3.5 SR=0.0481(X)+18.8
Antimony...................................... 77-1406 X=0.7940(C)-17.0 X=0.8908(C)+0.9
................ S=0.1556(X)-0.6 S=0.0982(X)+8.3
................ SR=0.1081(X)+3.9 SR=0.0682(X)+2.5
Arsenic....................................... 69-1887 X=1.0437(C)-12.2 X=1.0175(C)+3.9
................ S=0.1239(X)+2.4 S=0.1288(X)+6.1
................ SR=0.0874(X)+6.4 SR=0.0643(X)+10.3
[[Page 331]]
Barium........................................ 9-377 X=0.7683(C)+0.47 X=0.8380(C)+1.68
................ S=0.1819(X)+2.78 S=0.2540(X)+0.30
................ SR=0.1285(X)+2.55 SR=0.0826(X)+3.54
Beryllium..................................... 3-1906 X=0.9629(C)+0.05 X=1.0177(C)-0.55
................ S=0.0136(X)+0.95 S=0.0359(X)+0.90
................ SR=0.0203(X)-0.07 SR=0.0445(X)-0.10
Boron......................................... 19-5189 X=0.8807(C)+9.0 X=0.9676(C)+18.7
................ S=0.1150(X)+14.1 S=0.1320(X)+16.0
................ SR=0.0742(X)+23.2 SR=0.0743(X)+21.1
Cadmium....................................... 9-1943 X=0.9874(C)-0.18 X=1.0137(C)-0.65
................ S=0.557(X)+2.02 S=0.0585(X)+1.15
................ SR=0.0300(X)+0.94 SR=0.332(X)+0.90
Calcium....................................... 17-47170 X=0.9182(C)-2.6 X=0.9658(C)+0.8
................ S=0.1228(X)+10.1 S=0.0917(X)+6.9
................ SR=0.0189(X)+3.7 SR=0.0327(X)+10.1
Chromium...................................... 13-1406 X=0.9544(C)+3.1 X=1.0049(C)-1.2
................ S=0.0499(X)+4.4 S=0.0698(X)+2.8
................ SR=0.0009(X)+7.9 SR=0.0571(X)+1.0
Cobalt........................................ 17-2340 X=0.9209(C)-4.5 X=0.9278(C)-1.5
................ S=0.0436(X)+3.8 S=0.0498(X)+2.6
................ SR=0.0428(X)+0.5 SR=0.0407(X)+0.4
Copper........................................ 8-1887 X=0.9297(C)-0.30 X=0.9647(C)-3.64
................ S=0.0442(X)+2.85 S=0.0497(X)+2.28
................ SR=0.0128(X)+2.53 SR=0.0406(X)+0.96
Iron.......................................... 13-9359 X=0.8829(C)+7.0 X=0.9830(C)+5.7
................ S=0.0683(X)+11.5 S=0.1024(X)+13.0
................ SR=0.0046(X)+10.0 SR=0.0790(X)+11.5
Lead.......................................... 42-4717 X=0.9699(C)-2.2 X=1.0056(C)+4.1
................ S=0.0558(X)+7.0 S=0.0779(X)+4.6
................ SR=0.0353(X)+3.6 SR=0.0448(X)+3.5
Magnesium..................................... 34-13868 X=0.9881(C)-1.1 X=0.9879(C)+2.2
................ S=0.0607(C)+11.6 S=0.0564(X)+13.2
................ SR=0.0298(X)+0.6 SR=0.0268(X)+8.1
Manganese..................................... 4-1887 X=0.9417(C)+0.13 X=0.9725(C)+0.07
................ S=0.0324(X)+0.88 S=0.0557(X)+0.76
................ SR=0.0153(X)+0.91 SR=0.0400(X)+0.82
Molybdenum.................................... 17-1830 X=0.9682(C)+0.1 X=0.9707(C)-2.3
................ S=0.0618(X)+1.6 S=0.0811(X)+3.8
................ SR=0.0371(X)+2.2 SR=0.0529(X)+2.1
Nickel........................................ 17-47170 X=0.9508(C)+0.4 X=0.9869(C)+1.5
................ S=0.0604(X)+4.4 S=0.0526(X)+5.5
................ SR=0.0425(X)+3.6 SR=0.0393(X)+2.2
Potassium..................................... 347-14151 X=0.8669(C)-36.4 X=0.9355(C)-183.1
................ S=0.0934(X)+77.8 S=0.0481(X)+177.2
................ SR=0.0099(X)+144.2 SR=0.0329(X)+60.9
Selenium...................................... 69-1415 X=0.9363(C)-2.5 X=0.9737(C)-1.0
................ S=0.0855(X)+17.8 S=0.1523(X)+7.8
................ SR=0.0284(X)+9.3 SR=0.0443(X)+6.6
Silicon....................................... 189-9434 X=0.5742(C)-35.6 X=0.9737(C)-60.8
................ S=0.4160(X)+37.8 S=0.3288(X)+46.0
................ SR=0.1987(X)+8.4 SR=0.2133(X)+22.6
Silver........................................ 8-189 X=0.4466(C)+5.07 X=0.3987(C)+8.25
................ S=0.5055(X)-3.05 S=0.5478(X)-3.93
................ SR=0.2086(X)-1.74 SR=0.1836(X)-0.27
Sodium........................................ 35-47170 X=0.9581(C)+39.6 X=1.0526(C)+26.7
................ S=0.2097(X)+33.0 S=0.1473(X)+27.4
................ SR=0.0280(X)+105.8 SR=0.0884(X)+50.5
Thallium...................................... 79-1434 X=0.9020(C)-7.3 X=0.9238(C)+5.5
................ S=0.1004(X)+18.3 S=0.2156(X)+5.7
................ SR=0.0364(X)+11.5 SR=0.0106(X)+48.0
Vanadium...................................... 13-4698 X=0.9615(C)-2.0 X=0.9551(C)+0.4
................ S=0.0618(X)+1.7 S=0.0927(X)+1.6
................ SR=0.0220(X)+0.7 SR=0.0472(X)+0.5
Zinc.......................................... 7-7076 X=0.9356(C)-0.30 X=0.9500(C)+1.82
................ S=0.0914(X)+3.75 S=0.0597(X)+6.50
................ SR=0.0130(X)+10.7 SR=0.0153(X)+7.78
----------------------------------------------------------------------------------------------------------------
AAAAAX=Mean Recovery, [micro]g/L
AAAAAC=True Value for the Concentration, [micro]g/L
AAAAAS=Multi-laboratory Standard Deviation, [micro]g/L
SR=Single-analyst Standard Deviation, [micro]g/L
[[Page 332]]
[49 FR 43431, Oct. 26, 1984; 50 FR 695, 696, Jan. 4, 1985, as amended at
51 FR 23703, June 30, 1986; 55 FR 33440, Aug. 15, 1990]
Appendix D to Part 136--Precision and Recovery Statements for Methods
for Measuring Metals
Twenty-eight selected methods from ``Methods for Chemical Analysis
of Water and Wastes,'' EPA-600/4-79-020 (1979) have been subjected to
interlaboratory method validation studies. The following precision and
recovery statements are presented in this appendix and incorporated into
part 136:
Method 202.1
For Aluminum, Method 202.1 (Atomic Absorption, Direct Aspiration)
replace the Precision and Accuracy Section with the following:
Precision and Accuracy
An interlaboratory study on metal analyses by this method was
conducted by the Quality Assurance Branch (QAB) of the En vi ronmental
Monitoring Systems Labora tory--Cincinnati (EMSL-CI). Synthetic concen
trates containing various levels of this element were added to reagent
water and a natural water or effluent of the analyst's choice. The
digestion procedure was not specified. Results for the reagent water are
given below. Results for other water types and study details are found
in ``USEPA Method Study 7, Analyses for Trace Methods in water by Atomic
Absorption Spectroscopy (Direction Aspiration) and Colorimetry'',
National Technical Information Service, 5285 Port Royal Road,
Springfield, VA 22161, Order No. PB86-208709/AS, Winter, J.A. and
Britton, P.W., June, 1986.
For a concentration range of 500-1200 [micro]g/L
X=0.979(C)+6.16
S=0.066(X)+125
SR=0.086(X)+40.5
where:
C=True Value for the Concentration, [micro]g/L
X=Mean Recovery, [micro]g/L
S=Multi-laboratory Standard Deviation, [micro]g/L
SR=Single-analyst Standard Deviation, [micro]g/L
Method 206.4
For Arsenic, Method 206.4 (Spectrophotometric- SDDC) add the
following to the Precision and Accuracy Section:
Precision and Accuracy
An interlaboratory study on metal anal yses by this method was
conducted by the Quality Assurance Branch (QAB) of the Environmental
Monitoring Systems Labor a tory--Cincinnati (EMSL-CI). Synthetic
concentrates containing various levels of this element were added to
reagent water and a natural water or effluent of the analyst's choice.
Results for the reagent water are given below. Results for other water
types and study details are found in ``USEPA Method Study 7, Analyses
for Trace Methods in Water by Atomic Absorption Spectroscopy (Direct
Aspiration) and Colorimetry'', National Technical Information Service,
5285 Port Royal Road, Springfield, VA 22161, Order No. PB86-208709/AS,
Winter, J.A. and Britton, P.W., June, 1986.
For a concentration range of 20-292 [micro]g/L
X=0.850(C)-0.25
S=0.198(X)+5.93
SR=0.122(X)+3.10
where:
C=True Value for the Concentration, [micro]g/L
X=Mean Recovery, [micro]g/L
S=Multi-laboratory Standard Deviation, [micro]g/L
SR=Single-analyst Standard Deviation, [micro]g/L
Method 213.1
For Cadmium, Method 213.1 (Atomic Absorption, Direct Aspiration)
replace the Precision and Accuracy Section with the following:
Precision and Accuracy
An interlaboratory study on metal analyses by this method was
conducted by the Quality Assurance Branch (QAB) of the Environmental
Monitoring Systems Laboratory--Cincinnati (EMSL-CI). Synthetic
concentrates containing various levels of this element were added to
reagent water and a natural water or effluent of the analyst's choice.
The digestion procedure was not specified. Results for the reagent water
are given below. Results for other water types and study details are
found in ``USEPA Method Study 7, Analyses for Trace Methods in Water by
Atomic Absorption Spectroscopy (Direct Aspiration) and Colorimetry'',
National Technical Information Service, 5285 Port Royal Road,
Springfield, VA 22161, Order No. PB86-208709/AS, Winter, J.A. and
Britton, P.W., June, 1986.
For a concentration range of 14-78 [micro]g/L
X=0.919(C)+2.97
S=0.108(X)+5.08
SR=0.120(X)+0.89
where:
C=True Value for the Concentration, [micro]g/L
X=Mean Recovery, [micro]g/L
S=Multi-laboratory Standard Deviation, [micro]g/L
SR=Single-analyst Standard Deviation, [micro]g/L
[[Page 333]]
Method 218.1
For Chromium, Method 218.1 (Atomic Absorption, Direct Aspiration)
replace the Precision and Accuracy Section with the following:
Precision and Accuracy
An interlaboratory study on metal analyses by this method was
conducted by the Quality Assurance Branch (QAB) of the Environmental
Monitoring Systems Laboratory--Cincinnati (EMSL-CI). Synthetic
concentrates containing various levels of this element were added to
reagent water and a natural water or effluent of the analyst's choice.
The digestion procedure was not specified. Results for the reagent water
are given below. Results for other water types and study details are
found in ``USEPA Method Study 7, Analyses for Trace Methods in Water by
Atomic Absorption Spectroscopy (Direct Aspiration) and Colorimetry'',
National Technical Information Service, 5285 Port Royal Road,
Springfield, VA 22161, Order No. PB86-208709/AS, Winter, J.A. and
Britton, P.W., June 1986.
For a concentration range of 74-407 [micro]g/L
X=0.976(C)+3.94
S=0.131(X)+4.26
SR=0.052(X)+3.01
where:
C=True Value for the Concentration, [micro]g/L
X=Mean Recovery, [micro]g/L
S=Multi-laboratory Standard Deviation, [micro]g/L
SR=Single-analyst Standard Deviation, [micro]g/L
Method 220.1
For Copper, Method 220.1 (Atomic Absorption, Direct Aspiration)
replace the Precision and Accuracy Section with the following:
Precision and Accuracy
An interlaboratory study on metal analyses by this method was
conducted by the Quality Assurance Branch (QAB) of the Environmental
Monitoring Systems Laboratory--Cincinnati (EMSL-CI). Synthetic
concentrates containing various levels of this element were added to
reagent water and a natural water or effluent of the analyst's choice.
The digestion procedure was not specified. Results for the reagent water
are given below. Results for other water types and study details are
found in ``USEPA Method Study 7, Analyses for Trace Methods in Water by
Atomic Absorption Spectroscopy (Direct Aspiration) and Colorimetry'',
National Technical Information Service, 5285 Port Royal Road,
Springfield, VA 22161, Order No. PB86-208709/AS, Winter, J.A. and
Britton, P.W., June, 1986.
For concentration range 60-332 [micro]g/L
X=0.963(C)+3.49
S=0.047(X)+12.3
SR=0.042(X)+4.60
where:
C=True Value for the Concentration, [micro]g/L
X=Mean Recovery, [micro]g/L
S=Multi-laboratory Standard Deviation, [micro]g/L
SR=Single-analyst Standard Deviation, [micro]g/L
Method 236.1
For Iron, Method 236.1 (Atomic Absorption, Direct Aspiration)
replace the Precision and Accuracy Section with the following:
Precision and Accuracy
An interlaboratory study on metal analyses by this method was
conducted by the Quality Assurance Branch (QAB) of the Environmental
Monitoring Systems Laboratory--Cincinnati (EMSL-CI). Synthetic
concentrates containing various levels of this element were added to
reagent water and a natural water or effluent of the analyst's choice.
The digestion procedure was not specified. Results for the reagent water
are given below. Results for other water types and study details are
found in ``USEPA Method Study 7, Analyses for Trade Methods in Water by
Atomic Absorption Spectroscopy (Direct Aspiration) and Colorimetry'',
National Technical Information Service, 5285 Port Royal Road,
Springfield, VA 22161, Order No. PB86-208709/AS, Winter, J.A. and
Britton, P.W., June, 1986.
For concentration range 350-840 [micro]g/L
X=0.999(C)-2.21
S=0.022(X)+41.0
SR=0.019(X)+21.2
where:
C=True Value for the Concentration, [micro]g/L
X=Mean Recovery, [micro]g/L
S=Multi-Laboratory Standard Deviation, [micro]g/L
SR=Single-analyst Standard Deviation, [micro]g/L
Method 239.1
For Lead, Method 239.1 (Atomic Absorption, Direct Aspiration)
replace Precision and Accuracy Section with the following:
Precision and Accuracy
An interlaboratory study on metal analyses by this method was
conducted by the Quality Assurance Branch (QAB) of the Environmental
Monitoring Systems Laboratory--Cincinnati (EMSL-CI). Synthetic
concentrates containing various levels of this element were added to
reagent water and a natural water or effluent of the analyst's choice.
The digestion procedure was not specified. Results for the reagent water
are given below. Results for other water types and study details are
found in ``USEPA Method Study 7 Analyses for Trace Methods in Water by
Atomic Absorption Spectroscopy
[[Page 334]]
(Direct Aspiration) and Colorimetry''; National Technical Information
Service, 5285 Port Royal Road, Springfield, VA 22161, Order No. PB86-
208709/AS, Winter, J.A. and Britton, P.W., June, 1986.
For concentration range of 84-367 [micro]g/L
X=0.961(C)+13.8
S=0.028(C)+33.9
SR=0.011(X)+16.1
where:
C=True Value for the Concentration, [micro]g/L
X=Mean Recovery, [micro]g/L
S=Multi-laboratory Standard Deviation, [micro]g/L
SR=Single-analyst Standard Deviation, [micro]g/L
Method 243.1
For Manganese, Method 243.1 (Atomic Absorption, Direct Aspiration)
replace Precision and Accuracy Section with the following:
Precision and Accuracy
An interlaboratory study on metal analyses by this method was
conducted by the Quality Assurance Branch (QAB) of the Environmental
Monitoring Systems Laboratory--Cincinnati (EMSL-CI). Synthetic
concentrates containing various levels of this element were added to
reagent water and a natural water or effluent of the analyst's choice.
The digestion procedure was not specified. Results for the reagent water
are given below. Results for other water types and study details are
found in ``USEPA Method Study 7, Analyses for Trace Methods in Water by
Atomic Absorption Spectroscopy (Direct Aspiration) and Colorimetry'',
National Technical Information Service, 5285 Port Royal Road,
Springfield, VA 22161, Order No. PB86-208709/AS, Winter, J.A. and
Britton, P.W., June, 1986.
For concentration range 84-469 [micro]g/L
X=0.987(C)-1.27
S=0.042(X)+8.95
SR=0.023(X)+4.90
where:
C=True Value for the Concentration, [micro]g/L
X=Mean Recovery, [micro]g/L
S=Multi-laboratory Standard Deviation, [micro]g/L
SR=Single-analyst Standard Deviation, [micro]g/L
Method 289.1
For Zinc, Method 289.1 (Atomic Absorption, Direct Aspiration)
replace the Precision and Accuracy Section with the following:
Precision and Accuracy
An interlaboratory study on metal analyses by this method was
conducted by the Quality Assurance Branch (QAB) of the Environmental
Monitoring Systems Laboratory-Cincinnati (EMSL-CI). Synthetic
concentrates containing various levels of this element were added to
reagent water and a natural water or effluent of the analyst's choice.
The digestion procedure was not specified. Results for the reagent water
are given below. Results for other water types and study details are
found in ``USEPA Method Study 7, Analyses for Trace Methods in Water by
Atomic Absorption Spectroscopy (Direct Aspiration) and Colorimetry'',
National Technical Information Service, 5285 Port Royal Road,
Springfield, VA 22161, Order No. PB86-208709/AS, Winter, J. A. and
Britton, P. W., June, 1986.
For concentration range 56-310 [micro]g/L
X=0.999(C)+0.033
S=0.078(X)+10.8
SR=0.049(X)+1.10
where:
C=True Value for the Concentration, [micro]g/L
X=Mean Recovery, [micro]g/L
S=Multi-laboratory Standard Deviation, [micro]g/L
SR=Single-analyst Standard Deviation, [micro]g/L
Method 202.2
For Aluminum, Method 202.2 (Atomic Absorption, Furnace Technique)
replace the Precision and Accuracy Section statement with the following:
Precision and Accuracy
An interlaboratory study on metal analyses by this method was
conducted by the Quality Assurance Branch (QAB) of the Environmental
Monitoring Systems Laboratory-Cincinnati (EMSL-CI). Synthetic
concentrates containing various levels of this element were added to
reagent water, surface water, drinking water and three effluents. These
samples were digested by the total digestion procedure, 4.1.3 in this
manual. Results for the reagent water are given below. Results for other
water types and study details are found in ``EPA Method Study 31, Trace
Metals by Atomic Absorption (Furnace Techniques), ``National Technical
Information Service, 5285 Port Royal Road, Springfield, VA 22161, Order
No. PB 86-121 704/AS, by Copeland, F.R. and Maney, J.P., January 1986.
For a concentration range of 0.46-125 [micro]g/L
X=1.1579(C)-0.121
S=0.4286(X)-0.124
SR=0.2908(X)-0.082
where:
C=True Value for the Concentration, [micro]g/L
X=Mean Recovery, [micro]g/L
S=Multi-laboratory Standard Deviation, [micro]g/L
SR=Single-analyst Standard Deviation, [micro]g/L
[[Page 335]]
Method 204.2
For Antimony, Method 204.2 (Atomic Absorption, Furnace Technique)
replace the Precision and Accuracy Section statement with the following:
Precision and Accuracy
An interlaboratory study on metal analyses by this method was
conducted by the Quality Assurance Branch (QAB) of the Environmental
Monitoring Systems Laboratory-Cincinnati (EMSL-CI). Synthetic
concentrates containing various levels of this element were added to
reagent water, surface water, drinking water and three effluents. These
samples were digested by the total digestion procedure, 4.1.3 in this
manual as modified by this method. Results for the reagent water are
given below. Results for other water types and study details are found
in ``EPA Method Study 31, Trace Metals by Atomic Absorption (Furnace
Techniques),'' National Technical Information Service, 5285 Port Royal
Road, Springfield, VA 22161, Order No. PB 86-121 704/AS, by Copeland,
F.R. and Maney, J.P., January 1986.
For a concentration range of 10.50-240 [micro]g/L
X=0.7219(C)-0.986
S=0.3732(X)+0.854
SR=0.1874(X)-0.461
where:
C=True Value for the Concentration, [micro]g/L
X=Mean Recovery, [micro]g/L
S=Multi-laboratory Standard Deviation, [micro]g/L
SR=Single-analyst Standard Deviation, [micro]g/L
Method 206.2
For Arsenic, Method 206.2 (Atomic Absorption, Furnace Technique) add
the following to the existing Precision and Accuracy statement:
Precision and Accuracy
An interlaboratory study on metal analyses by this method was
conducted by the Quality Assurance Branch (QAB) of the Environmental
Monitoring Systems Laboratory-Cincinnati (EMSL-CI). Synthetic
concentrates containing various levels of this element were added to
reagent water, surface water, drinking water and three effluents.
Results for the reagent water are given below. Results for other water
types and study details are found in ``EPA Method Study 31, Trace Metals
by Atomic Absorption (Furnace Techniques),'' National Technical
Information Service, 5285 Port Royal Road, Springfield, VA 22161, Order
No. PB 86-121 704/AS, by Copeland, F.R. and Maney, J.P., January 1986.
For a concentration range of 9.78-237 [micro]g/L
X=0.9652(C)+2.112
S=0.1411(X)+1.873
SR=0.0464(X)+2.109
where:
C=True Value for the Concentration, [micro]g/L
X=Mean Recovery, [micro]g/L
S=Multi-laboratory Standard Deviation, [micro]g/L
SR=Single-analyst Standard Deviation, [micro]g/L
Method 208.2
For Barium, Method 208.2 (Atomic Absorption, Furnace Technique) add
the following to the existing Precision and Accuracy information:
Precision and Accuracy
An interlaboratory study on metal analyses by this method was
conducted by the Quality Assurance Branch (QAB) of the Environmental
Monitoring Systems Laboratory--Cincinnati (EMSL-CI). Synthetic
concentrates containing various levels of this element were added to
reagent water, surface water, drinking water and three effluents. These
samples were digested by the total digestion procedure, 4.1.3 in this
manual. Results for the reagent water are given below. Results for other
water types and study details are found in ``EPA Method Study 31, Trace
Metals by Atomic Absorption (Furnace Techniques),'' National Technical
Information Service, 5285 Port Royal Road, Springfield, VA 22161, Order
No. PB 86-121 704/AS, by Copeland, F.R. and Maney, J.P., January 1986.
For a concentration range of 56.50-437 [micro]g/L
X=0.8268(C)+59.459
S=0.2466(X)+6.436
SR=0.1393(X)-0.428
where:
C=True Value for the Concentration, [micro]g/L
X=Mean Recovery, [micro]g/L
S=Multi-laboratory Standard Deviation, [micro]g/L
SR=Single-analyst Standard Deviation, [micro]g/L
Method 210.2
For Beryllium, Method 210.2 (Atomic Absorption, Furnace Technique)
replace the existing Precision and Accuracy statement with the
following:
Precision and Accuracy
An interlaboratory study on metal analyses by this method was
conducted by the Quality Assurance Branch (QAB) of the Environmental
Monitoring Systems Laboratory--Cincinnati (EMSL-CI). Synthetic
concentrates containing various levels of this element were added to
reagent water, surface water, drinking water and three effluents. These
samples were digested by the total digestion procedure, 4.1.3 in this
manual. Results for the reagent water are given below. Results for other
water types and study details are found in ``EPA Method Study 31,
[[Page 336]]
Trace Metals by Atomic Absorption (Furnace Techniques),'' National
Technical Information Service, 5285 Port Royal Road, Springfield, VA
22161, Order No. PB 86-121 704/AS, by Copeland, F.R. and Maney, J.P.,
January 1986.
For a concentration range of 0.45-11.4 [micro]g/L
X=1.0682(C)-0.158
S=0.2167(X)+0.090
SR=0.1096(X)+0.061
where:
C=True Value for the Concentration, [micro]g/L
X=Mean Recovery, [micro]g/L
S=Multi-laboratory Standard Deviation, [micro]g/L
SR=Single-analyst Standard Deviation, [micro]g/L
Method 213.2
For Cadmium, Method 213.2 (Atomic Absorption, Furnace Technique) add
the following to the existing Precision and Accuracy information:
Precision and Accuracy
An interlaboratory study on metal analyses by this method was
conducted by the Quality Assurance Branch (QAB) of the Environmental
Monitoring System Laboratory--Cincinnati (EMSL-CI). Synthetic
concentrates containing various levels of this element were added to
reagent water, surface water, drinking water and three effluents. These
samples were digested by the total digestion procedure, 4.1.3 in this
manual. Results for the reagent water are given below. Results for other
water types and study details are found in ``EPA Method Study 31, Trace
Metals by Atomic Absorption (Furnace Techniques),'' National Technical
Information Service, 5285 Port Royal Road, Springfield, VA 22161, Order
No. PB 86-121 704/AS, by Copeland, F.R. and Maney, J.P., January 1986.
For a concentration range of 0.43-12.5 [micro]g/L
X=0.9826(C)+0.171
S=0.2300(X)+0.045
SR=0.1031(X)+0.116
where:
C=True Value for the Concentration, [micro]g/L
X=Mean Recovery, [micro]g/L
S=Multi-laboratory Standard Deviation, [micro]g/L
SR=Single-analyst Standard Devision, [micro]g/L
Method 218.2
For Chromium, Method 218.2 (Atomic Absorption, Furnace Technique)
add the following to the existing Precision and Accuracy Section:
Precision and Accuracy
An interlaboratory study on metal analyses by this method was
conducted by the Quality Assurance Branch (QAB) of the Environmental
Monitoring Systems Laboratory--Cincinnati (EMSL-CI). Synthetic
concentrates containing various levels of this element were added to
reagent water, surface water, drinking water and three effluents. These
samples were digested by the total digestion procedure, 4.1.3 in this
manual. Results for the reagent water are given below. Results for other
water types and study details are found in ``EPA Method Study 31, Trace
Metals by Atomic Absorption (Furnace Techniques),'' National Technical
Information Service, 5285 Port Royal Road, Springfield, VA 22161, Order
No. PB 86-121 704/AS, by Copeland, F.R. and Maney, J.P., January 1986.
For a concentration range of 9.87-246 [micro]g/L
X=0.9120(C)+0.234
S=0.1684(X)+0.852
SR=0.1469(X)+0.315
where:
C=True Value for the Concentration, [micro]g/L
X=Mean Recovery, [micro]g/L
S=Multi-laboratory Standard Deviation, [micro]g/L
SR=Single-analyst Standard Devision, [micro]g/L
Method 219.2
For Cobalt, Method 219.2 (Atomic Absorption, Furnace Technique),
replace the Precision and Accuracy Section statement with the following:
Precision and Accuracy
An interlaboratory study on metal analyses by this method was
conducted by the Quality Assurance Branch (QAB) of the Environmental
Monitoring Systems Laboratory--Cincinnati (EMSL-CI). Synthetic
concentrates containing various levels of this element were added to
reagent water, surface water, drinking water and three effluents. These
samples were digested by the total digestion procedure, 4.1.3 in this
manual. Results for the reagent water are given below. Results for other
water types and study details are found in ``EPA Method Study 31, Trace
Metals by Atomic Absorption (Furnace Techniques),'' National Technical
Information Service, 5285 Port Royal Road, Springfield, VA 22161 Order
No. PB 86-121 704/AS, by Copeland, F.R. and Maney, J.P., January 1986.
For a concentration range of 21.10-461 [micro]g/L
X=0.8875(C)+0.859
S=0.2481(X)-2.541
SR=0.0969(X)+0.134
where:
C=True Value for the Concentration, [micro]g/L
X=Mean Recovery, [micro]g/L
S=Multi-laboratory Standard Deviation, [micro]g/L
SR=Single-analyst Standard Deviation, [micro]g/L
[[Page 337]]
Method 220.2
For Copper, Method 220.2 (Atomic Absorption, Furnace Technique)
replace the Precision and Accuracy Section statement with the following:
Precision and Accuracy
An interlaboratory study on metal analyses by this method was
conducted by the Quality Assurance Branch (QAB) of the Environmental
Monitoring Systems Laboratory--Cincinnati (EMSL-CI). Synthetic
concentrates containing various levels of this element were added to
reagent water, surface water, drinking water and three effluents. These
samples were digested by the total digestion procedure, 4.1.3 in this
manual. Results for the reagent water are given below. Results for other
water types and study details are found in ``EPA Method Study 31, Trace
Metals by Atomic Absorption (Furnace Techniques),'' National Technical
Information Service, 5285 Port Royal Road, Springfield, VA 22161 Order
No. PB 86-121 704/AS, by Copeland, F.R. and Maney, J.P., January 1986.
For a concentration range of 0.30-245 [micro]g/L
X=0.9253(C)+0.010
S=0.2735(X)-0.058
SR=0.2197(X)-0.050
where:
C=True Value for the Concentration, [micro]g/L
X=Mean Recovery, [micro]g/L
S=Multi-laboratory Standard Deviation, [micro]g/L
SR=Single-analyst Standard Deviation, [micro]g/L
Method 236.2
For Iron, Method 236.2 (Atomic Absorption, Furnace Technique)
replace the Precision and Accuracy Section statement with the following:
Precision and Accuracy
An interlaboratory study on metal analyses by this method was
conducted by the Quality Assurance Branch (QAB) of the Environmental
Monitoring Systems Laboratory--Cincinnati (EMSL-CI). Synthetic
concentrates containing various levels of this element were added to
reagent water, surface water, drinking water and three effluents. These
samples were digested by the total digestion procedure, 4.1.3 in this
manual. Results for the reagent water are given below. Results for other
water types and study details are found in ``EPA Method Study 31, Trace
Metals by Atomic Absorption (Furnace Techniques),'' National Technical
Information Service, 5285 Port Royal Road, Springfield, VA 22161 Order
No. PB 86-121 704/AS, by Copeland, F.R. and Maney, J.P., January 1986.
For a concentration range of 0.37-455 [micro]g/L
X=1.4494(C)-0.229
S=0.3611(X)-0.079
SR=0.3715(X)-0.161
where:
C=True Value for the Concentration, [micro]g/L
X=Mean Recovery, [micro]g/L
S=Multi-laboratory Standard Deviation, [micro]g/L
SR=Single-analyst Standard Deviation, [micro]g/L
Method 239.2
For Lead, Method 239.2 (Atomic Absorption, Furnace Technique) add
the following to the existing Precisions and Accuracy Section:
Precision and Accuracy
An interlaboratory study on metal analyses by this method was
conducted by the Quality Assurance Branch (QAB) of the Environmental
Monitoring Systems Laboratory--Cincinnati (EMSL-CI). Synthetic
concentrates containing various levels of this element were added to
reagent water, surface water, drinking water and three effluents. These
samples were digested by the total digestion procedure, 4.1.3 in this
manual. Results for the reagent water are given below. Results for other
water types and study details are found in ``EPA Method Study 31, Trace
Metals by Atomic Absorption (Furnace Techniques),'' National Technical
Information Service, 5285 Port Royal Road, Springfield, VA 22161 Order
No. PB 86-121 704/AS, by Copeland, F.R. and Maney, J.P., January 1986.
For a concentration range of 10.40-254 [micro]g/L
X=0.9430(C)-0.504
S=0.2224(X)+0.507
SR=0.1931(X)-0.378
where:
C=True Value for the Concentration, [micro]g/L
X=Mean Recovery, [micro]g/L
S=Multi-laboratory Standard Deviation, [micro]g/L
SR=Single-analyst Standard Deviation, [micro]g/L
Method 243.2
For Manganese, Method 243.2 (Atomic Absorption, Furnace Technique)
replace the Precision and Accuracy Section statement with the following:
Precision and Accuracy
An interlaboratory study on metal analyses by this method was
conducted by the Quality Assurance Branch (QAB) of the Environmental
Monitoring Systems Laboratory--Cincinnati (EMSL--CI). Synthetic
concentrates containing various levels of this element were added to
reagent water, surface water, drinking water and three effluents.
[[Page 338]]
These samples were digested by the total digestion procedure, 4.1.3 in
this manual. Results for the reagent water are given below. Results for
other water types and study details are found in ``EPA Method Study 31,
Trace Metals by Atomic Absorption (Furnace Techniques),'' National
Technical Information Service, 5285 Port Royal Road, Springfield, VA
22161. Order No. PB 86-121 704/AS, by Copeland, F.R. and Maney, J.P.,
January 1986.
For a concentration range of 0.42-666 [micro]g/L
X=1.0480(C)+1.404
S=0.2001(X)+1.042
SR=0.1333(X)+0.680
where:
C=True Value for the Concentration, [micro]g/L
X=Mean Recovery, [micro]g/L
S=Multi-laboratory Standard Deviation, [micro]g/L
SR=Single-analyst Standard Deviation, [micro]g/L
Method 249.2
For Nickel, Method 249.2 (Atomic Absorption, Furnace Technique)
replace the Precision and Accuracy Section statement with the following:
Precision and Accuracy
An interlaboratory study on metal analyses by this method was
conducted by the Quality Assurance Branch (QAB) of the Environmental
Monitoring Systems Laboratory--Cincinnati (EMSL--CI). Synthetic
concentrates containing various levels of this element were added to
reagent water, surface water, drinking water and three effluents. These
samples were digested by the total digestion procedure, 4.1.3 in this
manual. Results for the reagent water are given below. Results for other
water types and study details are found in ``EPA Method Study 31, Trace
Metals by Atomic Absorption (Furnace Techniques),'' National Technical
Information Service, 5285 Port Royal Road, Springfield, VA 22161. Order
No. PB 86-121 704/AS, by Copeland, F.R. and Maney, J.P., January 1986.
For a concentration range of 26.20-482 [micro]g/L
X=0.8812(C)+2.426
S=0.2475(X)+1.896
SR=0.1935(X)+1.315
where:
C=True Value for the Concentration, [micro]g/L
X=Mean Recovery, [micro]g/L
S=Multi-laboratory Standard Deviation, [micro]g/L
SR=Single-analyst Standard Deviation, [micro]g/L
Method 270.2
For Selenium, Method 270.2 (Atomic Absorption, Furnace Technique)
add the following to the existing Precision and Accuracy Section:
Precision and Accuracy
An interlaboratory study on metal analyses by this method was
conducted by the Quality Assurance Branch (QAB) of the Environmental
Monitoring Systems Laboratory--Cincinnati (EMSL--CI). Synthetic
concentrates containing various levels of this element were added to
reagent water, surface water, drinking water and three effluents.
Results for the reagent water are given below. Results for other water
types and study details are found in ``EPA Method Study 31, Trace Metals
by Atomic Absorption (Furnace Techniques),'' National Technical
Information Service, 5285 Port Royal Road, Springfield, VA 22161. Order
No. PB 86-121 704/AS, by Copeland, F.R. and Maney, J.P., January 1986.
For a concentration range of 10.00-246 [micro]g/L
X=0.9564(C)+0.476
S=0.1584(X)+0.878
SR=0.0772(X)+0.547
where:
C=True Value for the Concentration, [micro]g/L
X=Mean Recovery, [micro]g/L
S=Multi-laboratory Standard Deviation, [micro]g/L
SR=Single-analyst Standard Deviation, [micro]g/L
Method 272.2
For Silver, Method 272.2 (Atomic Absorption, Furnace Technique) add
the following to the existing Precision and Accuracy Section:
Precision and Accuracy
An interlaboratory study on metal analyses by this method was
conducted by the Quality Assurance Branch (QAB) of the Environmental
Monitoring Systems Laboratory--Cincinnati (EMSL--CI). Synthetic
concentrates containing various levels of this element were added to
reagent water, surface water, drinking water and three effluents. These
samples were digested by the total digestion procedure, 4.1.3 in this
manual. Results for the reagent water are given below. Results for other
water types and study details are found in ``EPA Method Study 31, Trace
Metals by Atomic Absorption (Furnace Techniques),'' National Technical
Information Service, 5285 Port Royal Road, Springfield, VA 22161. Order
No. PB 86-121 704/AS, by Copeland, F.R. and Maney, J.P., January 1986.
For a concentration range of 0.45-56.5 [micro]g/L
X=0.9470(C)+0.181
S=0.1805(X)+0.153
SR=0.1417(X)+0.039
where:
C=True Value for the Concentration, [micro]g/L
X=Mean Recovery, [micro]g/L
S=Multi-laboratory Standard Deviation, [micro]g/L
[[Page 339]]
SR=Single-analyst Standard Deviation, [micro]g/L
Method 279.2
For Thalliu, Method 279.2 (Atomic Absorption, Furnace Technique)
replace the Precision and Accuracy Section statement with the following:
Precision and Accuracy
An interlaboratory study on metal analyses by this method was
conducted by the Quality Assurance Branch (QAB) of the Environmental
Monitoring Systems Laboratory--Cincinnati (EMSL-CI). Synthetic
concentrates containing various levels of this element were added to
reagent water, surface water, drinking water and three effluents. These
samples were digested by the total digestion procedure, 4.1.3 in this
manual. Results for the reagent water are given below. Results for other
water types and study details are found in ``EPA Method Study 31, Trace
Metals by Atomic Absorption (Furnace Techniques),'' National Technical
Information Service, 5285 Port Royal Road, Springfield, VA 22161 Order
No. PB 86-121 704/AS, by Copeland, F.R. and Maney, J.P., January 1986.
For a concentration range of 10.00-252 [micro]g/L.
X=0.8781(C)-0.715
S=0.1112(X)+0.669
SR=0.1005(X)+0.241
where:
C=True Value for the Concentration, [micro]g/L
X=Mean Recovery, [micro]g/L
S=Multi-laboratory Standard Deviation, [micro]g/L
SR=Single-analyst Standard Deviation, [micro]g/L
Method 286.2
For Vanadium, Method 286.2 (Atomic Absorption, Furnace Technique)
replace the Precision and Accuracy Section statement with the following:
Precision and Accuracy
An interlaboratory study on metal analyses by this method was
conducted by the Quality Assurance Branch (QAB) of the Environmental
Monitoring Systems Laboratory--Cincinnati (EMSL-CI). Synthetic
concentrates containing various levels of this element were added to
reagent water, surface water, drinking water and three effluents. These
samples were digested by the total digestion procedure, 4.1.3 in this
manual. Results for the reagent water are given below. Results for other
water types and study details are found in ``EPA Method Study 31, Trace
Metals by Atomic Absorption (Furnace Techniques),'' National Technical
Information Service, 5285 Port Royal Road, Springfield, VA 22161 Order
No. PB 86-121 704/AS, by Copeland, F.R. and Maney, J.P., January 1986.
For a concentration range of 1.36-982 [micro]g/L.
X=0.8486(C)+0.252
S=0.3323(X)-0.428
SR=0.1195(X)-0.121
where:
C=True Value for the Concentration, [micro]g/L
X=Mean Recovery, [micro]g/L
S=Multi-laboratory Standard Deviation, [micro]g/L
SR=Single-analyst Standard Deviation, [micro]g/L
Method 289.2
For Zinc, Method 289.2 (Atomic Absorption, Furnace Technique)
replace the Precision and Accuracy Section statement with the following:
Precision and Accuracy
An interlaboratory study on metal analyses by this method was
conducted by the Quality Assurance Branch (QAB) of the Environmental
Monitoring Systems Laboratory--Cincinnati (EMSL-CI). Synthetic
concentrates containing various levels of this element were added to
reagent water, surface water, drinking water and three effluents. These
samples were digested by the total digestion procedure, 4.1.3 in this
manual. Results for the reagent water are given below. Results for other
water types and study details are found in ``EPA Method Study 31, Trace
Metals by Atomic Absorption (Furnace Techniques),'' National Technical
Information Service, 5285 Port Royal Road, Springfield, VA 22161 Order
No. PB 86-121 704/AS, by Copeland, F.R. and Maney, J.P., January 1986.
For a concentration range of 0.51-189 [micro]g/L.
X=1.6710(C)+1.485
S=0.6740(X)-0.342
SR=0.3895(X)-0.384
where:
C=True Value for the Concentration, [micro]g/L
X=Mean Recovery, [micro]g/L
S=Multi-laboratory Standard Deviation, [micro]g/L
SR=Single-analyst Standard Deviation, [micro]g/L
[55 FR 33442, Aug. 15, 1990]
PART 140_MARINE SANITATION DEVICE STANDARD--Table of Contents
Sec.
140.1 Definitions.
140.2 Scope of standard.
140.3 Standard.
140.4 Complete prohibition.
140.5 Analytical procedures.
Authority: 33 U.S.C. 1322, as amended.
[[Page 340]]
Source: 41 FR 4453, Jan. 29, 1976, unless otherwise noted.
Sec. 140.1 Definitions.
For the purpose of these standards the following definitions shall
apply:
(a) Sewage means human body wastes and the wastes from toilets and
other receptacles intended to receive or retain body wastes;
(b) Discharge includes, but is not limited to, any spilling,
leaking, pumping, pouring, emitting, emptying, or dumping;
(c) Marine sanitation device includes any equipment for installation
onboard a vessel and which is designed to receive, retain, treat, or
discharge sewage and any process to treat such sewage;
(d) Vessel includes every description of watercraft or other
artificial contrivance used, or capable of being used, as a means of
transportation on waters of the United States;
(e) New vessel refers to any vessel on which construction was
initiated on or after January 30, 1975;
(f) Existing vessel refers to any vessel on which construction was
initiated before January 30, 1975;
(g) Fecal coliform bacteria are those organisms associated with the
intestines of warm-blooded animals that are commonly used to indicate
the presence of fecal material and the potential presence of organisms
capable of causing human disease.
Sec. 140.2 Scope of standard.
The standard adopted herein applies only to vessels on which a
marine sanitation device has been installed. The standard does not
require the installation of a marine sanitation device on any vessel
that is not so equipped. The standard applies to vessels owned and
operated by the United States unless the Secretary of Defense finds that
compliance would not be in the interest of national security.
Sec. 140.3 Standard.
(a) (1) In freshwater lakes, freshwater reservoirs or other
freshwater impoundments whose inlets or outlets are such as to prevent
the ingress or egress by vessel traffic subject to this regulation, or
in rivers not capable of navigation by interstate vessel traffic subject
to this regulation, marine sanitation devices certified by the U.S.
Coast Guard (see 33 CFR part 159, published in 40 FR 4622, January 30,
1975), installed on all vessels shall be designed and operated to
prevent the overboard discharge of sewage, treated or untreated, or of
any waste derived from sewage. This shall not be construed to prohibit
the carriage of Coast Guard-certified flow-through treatment devices
which have been secured so as to prevent such discharges.
(2) In all other waters, Coast Guard-certified marine sanitation
devices installed on all vessels shall be designed and operated to
either retain, dispose of, or discharge sewage. If the device has a
discharge, subject to paragraph (d) of this section, the effluent shall
not have a fecal coliform bacterial count of greater than 1,000 per 100
milliliters nor visible floating solids. Waters where a Coast Guard-
certified marine sanitation device permitting discharge is allowed
include coastal waters and estuaries, the Great Lakes and inter-
connected waterways, fresh-water lakes and impoundments accessible
through locks, and other flowing waters that are navigable interstate by
vessels subject to this regulation.
(b) This standard shall become effective on January 30, 1977 for new
vessels and on January 30, 1980 for existing vessels (or, in the case of
vessels owned and operated by the Department of Defense, two years and
five years, for new and existing vessels, respectively, after
promulgation of implementing regulations by the Secretary of Defense
under section 312(d) of the Act).
(c) Any vessel which is equipped as of the date of promulgation of
this regulation with a Coast Guard-certified flow-through marine
sanitation device meeting the requirements of paragraph (a)(2) of this
section, shall not be required to comply with the provisions designed to
prevent the overboard discharge of sewage, treated or untreated, in
paragraph (a)(1) of this section, for the operable life of that device.
(d) After January 30, 1980, subject to paragraphs (e) and (f) of
this section, marine sanitation devices on all vessels on waters that
are not subject to a prohibition of the overboard discharge
[[Page 341]]
of sewage, treated or untreated, as specified in paragraph (a)(1) of
this section, shall be designed and operated to either retain, dispose
of, or discharge sewage, and shall be certified by the U.S. Coast Guard.
If the device has a discharge, the effluent shall not have a fecal
coliform bacterial count of greater than 200 per 100 milliliters, nor
suspended solids greater than 150 mg/1.
(e) Any existing vessel on waters not subject to a prohibition of
the overboard discharge of sewage in paragraph (a)(1) of this section,
and which is equipped with a certified device on or before January 30,
1978, shall not be required to comply with paragraph (d) of this
section, for the operable life of that device.
(f) Any new vessel on waters not subject to the prohibition of the
overboard discharge of sewage in paragraph (a)(1) of this section, and
on which construction is initiated before January 31, 1980, which is
equipped with a marine sanitation device before January 31, 1980,
certified under paragraph (a)(2) of this section, shall not be required
to comply with paragraph (d) of this section, for the operable life of
that device.
(g) The degrees of treatment described in paragraphs (a) and (d) of
this section are ``appropriate standards'' for purposes of Coast Guard
and Department of Defense certification pursuant to section 312(g)(2) of
the Act.
[41 FR 4453, Jan. 29, 1976, as amended at 60 FR 33932, June 29, 1995]
Sec. 140.4 Complete prohibition.
(a) Prohibition pursuant to CWA section 312(f)(3): a State may
completely prohibit the discharge from all vessels of any sewage,
whether treated or not, into some or all of the waters within such State
by making a written application to the Administrator, Environmental
Protection Agency, and by receiving the Administrator's affirmative
determination pursuant to section 312(f)(3) of the Act. Upon receipt of
an application under section 312(f)(3) of the Act, the Administrator
will determine within 90 days whether adequate facilities for the safe
and sanitary removal and treatment of sewage from all vessels using such
waters are reasonably available. Applications made by States pursuant to
section 312(f)(3) of the Act shall include:
(1) A certification that the protection and enhancement of the
waters described in the petition require greater environmental
protection than the applicable Federal standard;
(2) A map showing the location of commercial and recreational pump-
out facilities;
(3) A description of the location of pump-out facilities within
waters designated for no discharge;
(4) The general schedule of operating hours of the pump-out
facilities;
(5) The draught requirements on vessels that may be excluded because
of insufficient water depth adjacent to the facility;
(6) Information indicating that treatment of wastes from such pump-
out facilities is in conformance with Federal law; and
(7) Information on vessel population and vessel usage of the subject
waters.
(b) Prohibition pursuant to CWA section 312(f)(4)(A): a State may
make a written application to the Administrator, Environmental
Protection Agency, under section 312(f)(4)(A) of the Act, for the
issuance of a regulation completely prohibiting discharge from a vessel
of any sewage, whether treated or not, into particular waters of the
United States or specified portions thereof, which waters are located
within the boundaries of such State. Such application shall specify with
particularly the waters, or portions thereof, for which a complete
prohibition is desired. The application shall include identification of
water recreational areas, drinking water intakes, aquatic sanctuaries,
identifiable fish-spawning and nursery areas, and areas of intensive
boating activities. If, on the basis of the State's application and any
other information available to him, the Administrator is unable to make
a finding that the waters listed in the application require a complete
prohibition of any discharge in the waters or portions thereof covered
by the application, he shall state the reasons why he cannot make such a
finding, and shall deny the application. If the Administrator makes a
finding that the waters listed in the application require a complete
prohibition of any
[[Page 342]]
discharge in all or any part of the waters or portions thereof covered
by the State's application, he shall publish notice of such findings
together with a notice of proposed rule making, and then shall proceed
in accordance with 5 U.S.C. 553. If the Administrator's finding is that
applicable water quality standards require a complete prohibition
covering a more restricted or more expanded area than that applied for
by the State, he shall state the reasons why his finding differs in
scope from that requested in the State's application.
(1) For the following waters the discharge from a vessel of any
sewage (whether treated or not) is completely prohibited pursuant to CWA
section 312(f)(4)(A):
(i) Boundary Waters Canoe Area, formerly designated as the Superior,
Little Indian Sioux, and Caribou Roadless Areas, in the Superior
National Forest, Minnesota, as described in 16 U.S.C. 577-577d1.
(ii) Waters of the State of Florida within the boundaries of the
Florida Keys National Marine Sanctuary as delineated on a map of the
Sanctuary at http://www.fknms.nos.noaa.gov/.
(c)(1) Prohibition pursuant to CWA section 312(f)(4)(B): A State may
make written application to the Administrator of the Environmental
Protection Agency under section 312(f)(4)(B) of the Act for the issuance
of a regulation establishing a drinking water intake no discharge zone
which completely prohibits discharge from a vessel of any sewage,
whether treated or untreated, into that zone in particular waters, or
portions thereof, within such State. Such application shall:
(i) Identify and describe exactly and in detail the location of the
drinking water supply intake(s) and the community served by the
intake(s), including average and maximum expected amounts of inflow;
(ii) Specify and describe exactly and in detail, the waters, or
portions thereof, for which a complete prohibition is desired, and where
appropriate, average, maximum and low flows in million gallons per day
(MGD) or the metric equivalent;
(iii) Include a map, either a USGS topographic quadrant map or a
NOAA nautical chart, as applicable, clearly marking by latitude and
longitude the waters or portions thereof to be designated a drinking
water intake zone; and
(iv) Include a statement of basis justifying the size of the
requested drinking water intake zone, for example, identifying areas of
intensive boating activities.
(2) If the Administrator finds that a complete prohibition is
appropriate under this paragraph, he or she shall publish notice of such
finding together with a notice of proposed rulemaking, and then shall
proceed in accordance with 5 U.S.C. 553. If the Administrator's finding
is that a complete prohibition covering a more restricted or more
expanded area than that applied for by the State is appropriate, he or
she shall also include a statement of the reasons why the finding
differs in scope from that requested in the State's application.
(3) If the Administrator finds that a complete prohibition is
inappropriate under this paragraph, he or she shall deny the application
and state the reasons for such denial.
(4) For the following waters the discharge from a vessel of any
sewage, whether treated or not, is completely prohibited pursuant to CWA
section 312(f)(4)(B):
(i) Two portions of the Hudson River in New York State, the first is
bounded by an east-west line through the most northern confluence of the
Mohawk River which will be designated by the Troy-Waterford Bridge
(126th Street Bridge) on the south and Lock 2 on the north, and the
second of which is bounded on the north by the southern end of
Houghtaling Island and on the south by a line between the Village of
Roseton on the western shore and Low Point on the eastern shore in the
vicinity of Chelsea, as described in Items 2 and 3 of 6 NYCRR Part
858.4.
(ii) [Reserved]
[41 FR 4453, Jan. 29, 1976, as amended at 42 FR 43837, Aug. 31, 1977; 60
FR 63945, Dec. 13, 1995; 63 FR 1320, Jan. 8, 1998; 67 FR 35743, May 21,
2002]
[[Page 343]]
Sec. 140.5 Analytical procedures.
In determining the composition and quality of effluent discharge
from marine sanitation devices, the procedures contained in 40 CFR part
136, ``Guidelines Establishing Test Procedures for the Analysis of
Pollutants,'' or subsequent revisions or amendments thereto, shall be
employed.
PART 141_NATIONAL PRIMARY DRINKING WATER REGULATIONS--Table of Contents
Subpart A_General
Sec.
141.1 Applicability.
141.2 Definitions.
141.3 Coverage.
141.4 Variances and exemptions.
141.5 Siting requirements.
141.6 Effective dates.
Subpart B_Maximum Contaminant Levels
141.11 Maximum contaminant levels for inorganic chemicals.
141.12 Maximum contaminant levels for total trihalomethanes.
141.13 Maximum contaminant levels for turbidity.
Subpart C_Monitoring and Analytical Requirements
141.21 Coliform sampling.
141.22 Turbidity sampling and analytical requirements.
141.23 Inorganic chemical sampling and analytical requirements.
141.24 Organic chemicals, sampling and analytical requirements.
141.25 Analytical methods for radioactivity.
141.26 Monitoring frequency and compliance requirements for
radionuclides in community water systems
141.27 Alternate analytical techniques.
141.28 Certified laboratories.
141.29 Monitoring of consecutive public water systems.
141.30 Total trihalomethanes sampling, analytical and other
requirements.
Subpart D_Reporting and Recordkeeping
141.31 Reporting requirements.
141.32 Public notification.
141.33 Record maintenance.
141.34 [Reserved]
141.35 Reporting of unregulated contaminant monitoring results.
Subpart E_Special Regulations, Including Monitoring Regulations and
Prohibition on Lead Use
141.40 Monitoring requirements for unregulated contaminants.
141.41 Special monitoring for sodium.
141.42 Special monitoring for corrosivity characteristics.
141.43 Prohibition on use of lead pipes, solder, and flux.
Subpart F_Maximum Contaminant Level Goals and Maximum Residual
Disinfectant Level Goals
141.50 Maximum contaminant level goals for organic contaminants.
141.51 Maximum contaminant level goals for inorganic contaminants.
141.52 Maximum contaminant level goals for microbiological contaminants.
141.53 Maximum contaminant level goals for disinfection byproducts.
141.54 Maximum residual disinfectant level goals for disinfectants.
141.55 Maximum contaminant level goals for radionuclides.
Subpart G_National Primary Drinking Water Regulations: Maximum
Contaminant Levels and Maximum Residual Disinfectant Levels
141.60 Effective dates.
141.61 Maximum contaminant levels for organic contaminants.
141.62 Maximum contaminant levels for inorganic contaminants.
141.63 Maximum contaminant levels (MCLs) for microbiological
contaminants.
141.64 Maximum contaminant levels for disinfection byproducts.
141.65 Maximum residual disinfectant levels.
141.66 Maximum contaminant levels for radionuclides.
Subpart H_Filtration and Disinfection
141.70 General requirements.
141.71 Criteria for avoiding filtration.
141.72 Disinfection.
141.73 Filtration.
141.74 Analytical and monitoring requirements.
141.75 Reporting and recordkeeping requirements.
141.76 Recycle provisions.
Subpart I_Control of Lead and Copper
141.80 General requirements.
[[Page 344]]
141.81 Applicability of corrosion control treatment steps to small,
medium-size and large water systems.
141.82 Description of corrosion control treatment requirements.
141.83 Source water treatment requirements.
141.84 Lead service line replacement requirements.
141.85 Public education and supplemental monitoring requirements.
141.86 Monitoring requirements for lead and copper in tap water.
141.87 Monitoring requirements for water quality parameters.
141.88 Monitoring requirements for lead and copper in source water.
141.89 Analytical methods.
141.90 Reporting requirements.
141.91 Recordkeeping requirements.
Subpart J_Use of Non-Centralized Treatment Devices
141.100 Criteria and procedures for public water systems using point-of-
entry devices.
141.101 Use of bottled water.
Subpart K_Treatment Techniques
141.110 General requirements.
141.111 Treatment techniques for acrylamide and epichlorohydrin.
Subpart L_Disinfectant Residuals, Disinfection Byproducts, and
Disinfection Byproduct Precursors
141.130 General requirements.
141.131 Analytical requirements.
141.132 Monitoring requirements.
141.133 Compliance requirements.
141.134 Reporting and recordkeeping requirements.
141.135 Treatment technique for control of disinfection byproduct (DBP)
precursors.
Subparts M-N [Reserved]
Subpart O_Consumer Confidence Reports
141.151 Purpose and applicability of this subpart.
141.152 Effective dates.
141.153 Content of the reports.
141.154 Required additional health information.
141.155 Report delivery and recordkeeping.
Appendix A to Subpart O of Part 141--Regulated Contaminants
Subpart P_Enhanced Filtration and Disinfection_Systems Serving 10,000 or
More People
141.170 General requirements.
141.171 Criteria for avoiding filtration.
141.172 Disinfection profiling and benchmarking.
141.173 Filtration.
141.174 Filtration sampling requirements.
141.175 Reporting and recordkeeping requirements.
Subpart Q_Public Notification of Drinking Water Violations
141.201 General public notification requirements.
141.202 Tier 1 Public Notice--Form, manner, and frequency of notice.
141.203 Tier 2 Public Notice--Form, manner, and frequency of notice.
141.204 Tier 3 Public Notice--Form, manner, and frequency of notice.
141.205 Content of the public notice.
141.206 Notice to new billing units or new customers.
141.207 Special notice of the availability of unregulated contaminant
monitoring results.
141.208 Special notice for exceedance of the SMCL for fluoride.
141.209 Special notice for nitrate exceedances above MCL by non-
community water systems (NCWS), where granted permission by
the primacy agency under Sec. 141.11(d).
141.210 Notice by primacy agency on behalf of the public water system.
Appendix A to Subpart Q of Part 141--NPDWR Violations and Situations
Requiring Public Notice
Appendix B to Subpart Q of Part 141--Standard Health Effects Language
for Public Notification
Appendix C to Subpart Q of Part 141--List of Acronyms Used in Public
Notification Regulation
Subparts R-S [Reserved]
Subpart T_Enhanced Filtration and Disinfection_Systems Serving Fewer
Than 10,000 People
General Requirements
141.500 General requirements.
141.501 Who is subject to the requirements of subpart T?
141.502 When must my system comply with these requirements?
141.503 What does subpart T require?
Finished Water Reservoirs
141.510 Is my system subject to the new finished water reservoir
requirements?
141.511 What is required of new finished water reservoirs?
[[Page 345]]
Additional Watershed Control Requirements for Unfiltered Systems
141.520 Is my system subject to the updated watershed control
requirements?
141.521 What updated watershed control requirements must my unfiltered
system implement to continue to avoid filtration?
141.522 How does the State determine whether my system's watershed
control requirements are adequate?
Disinfection Profile
141.530 What is a disinfection profile and who must develop one?
141.531 What criteria must a State use to determine that a profile is
unnecessary?
141.532 How does my system develop a disinfection profile and when must
it begin?
141.533 What data must my system collect to calculate a disinfection
profile?
141.534 How does my system use this data to calculate an inactivation
ratio?
141.535 What if my system uses chloramines, ozone, or chlorine dioxide
for primary disinfection?
141.536 My system has developed an inactivation ratio; what must we do
now?
Disinfection Benchmark
141.540 Who has to develop a disinfection benchmark?
141.541 What are significant changes to disinfection practice?
141.542 What must my system do if we are considering a significant
change to disinfection practices?
141.543 How is the disinfection benchmark calculated?
141.544 What if my system uses chloramines, ozone, or chlorine dioxide
for primary disinfection?
Combined Filter Effluent Requirements
141.550 Is my system required to meet subpart T combined filter effluent
turbidity limits?
141.551 What strengthened combined filter effluent turbidity limits must
my system meet?
141.552 My system consists of ``alternative filtration'' and is required
to conduct a demonstration--what is required of my system and
how does the State establish my turbidity limits?
141.553 My system practices lime softening--is there any special
provision regarding my combined filter effluent?
Individual Filter Turbidity Requirements
141.560 Is my system subject to individual filter turbidity
requirements?
141.561 What happens if my system's turbidity monitoring equipment
fails?
141.562 My system only has two or fewer filters--is there any special
provision regarding individual filter turbidity monitoring?
141.563 What follow-up action is my system required to take based on
continuous turbidity monitoring?
141.564 My system practices lime softening--is there any special
provision regarding my individual filter turbidity monitoring?
Reporting and Recordkeeping Requirements
141.570 What does subpart T require that my system report to the State?
141.571 What records does subpart T require my system to keep?
Authority: 42 U.S.C. 300f, 300g-1, 300g-2, 300g-3, 300g-4, 300g-5,
300g-6, 300j-4, 300j-9, and 300j-11.
Source: 40 FR 59570, Dec. 24, 1975, unless otherwise noted.
Editorial Note: Nomenclature changes to part 141 appear at 69 FR
18803, Apr. 9, 2004.
Note: For community water systems serving 75,000 or more
persons,monitoring must begin 1 year following promulation and the
effective date of the MCL is 2 years following promulgation. For
community water systems serving 10,000 to 75,000 persons, monitoring
must begin within 3 years from the date of promulgation and the
effective date of the MCL is 4 years from the date of promulgation.
Effective immediately, systems that plan to make significant
modifications to their treatment processes for the purpose of complying
with the TTHM MCL are required to seek and obtain State approval of
their treatment modification plans. This note affects Sec. Sec. 141.2,
141.6, 141.12, 141.24 and 141.30. For additional information see 44 FR
68641, Nov. 29, 1979.
Subpart A_General
Sec. 141.1 Applicability.
This part establishes primary drinking water regulations pursuant to
section 1412 of the Public Health Service Act, as amended by the Safe
Drinking Water Act (Pub. L. 93-523); and related regulations applicable
to public water systems.
Sec. 141.2 Definitions.
As used in this part, the term:
Act means the Public Health Service Act, as amended by the Safe
Drinking Water Act, Public Law 93-523.
Action level, is the concentration of lead or copper in water
specified in
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Sec. 141.80(c) which determines, in some cases, the treatment
requirements contained in subpart I of this part that a water system is
required to complete.
Best available technology or BAT means the best technology,
treatment techniques, or other means which the Administrator finds,
after examination for efficacy under field conditions and not solely
under laboratory conditions, are available (taking cost into
consideration). For the purposes of setting MCLs for synthetic organic
chemicals, any BAT must be at least as effective as granular activated
carbon.
Coagulation means a process using coagulant chemicals and mixing by
which colloidal and suspended materials are destabilized and
agglomerated into flocs.
Community water system means a public water system which serves at
least 15 service connections used by year-round residents or regularly
serves at least 25 year-round residents.
Compliance cycle means the nine-year calendar year cycle during
which public water systems must monitor. Each compliance cycle consists
of three three-year compliance periods. The first calendar year cycle
begins January 1, 1993 and ends December 31, 2001; the second begins
January 1, 2002 and ends December 31, 2010; the third begins January 1,
2011 and ends December 31, 2019.
Compliance period means a three-year calendar year period within a
compliance cycle. Each compliance cycle has three three-year compliance
periods. Within the first compliance cycle, the first compliance period
runs from January 1, 1993 to December 31, 1995; the second from January
1, 1996 to December 31, 1998; the third from January 1, 1999 to December
31, 2001.
Comprehensive performance evaluation (CPE) is a thorough review and
analysis of a treatment plant's performance-based capabilities and
associated administrative, operation and maintenance practices. It is
conducted to identify factors that may be adversely impacting a plant's
capability to achieve compliance and emphasizes approaches that can be
implemented without significant capital improvements. For purpose of
compliance with subparts P and T of this part, the comprehensive
performance evaluation must consist of at least the following
components: Assessment of plant performance; evaluation of major unit
processes; identification and prioritization of performance limiting
factors; assessment of the applicability of comprehensive technical
assistance; and preparation of a CPE report.
Confluent growth means a continuous bacterial growth covering the
entire filtration area of a membrane filter, or a portion thereof, in
which bacterial colonies are not discrete.
Contaminant means any physical, chemical, biological, or
radiological substance or matter in water.
Conventional filtration treatment means a series of processes
including coagulation, flocculation, sedimentation, and filtration
resulting in substantial particulate removal.
Corrosion inhibitor means a substance capable of reducing the
corrosivity of water toward metal plumbing materials, especially lead
and copper, by forming a protective film on the interior surface of
those materials.
CT or CTcalc is the product of ``residual disinfectant
concentration'' (C) in mg/1 determined before or at the first customer,
and the corresponding ``disinfectant contact time'' (T) in minutes,
i.e., ``C'' x ``T''. If a public water system applies disinfectants at
more than one point prior to the first customer, it must determine the
CT of each disinfectant sequence before or at the first customer to
determine the total percent inactivation or ``total inactivation
ratio.'' In determining the total inactivation ratio, the public water
system must determine the residual disinfectant concentration of each
disinfection sequence and corresponding contact time before any
subsequent disinfection application point(s). ``CT99.9'' is
the CT value required for 99.9 percent (3-log) inactivation of Giardia
lamblia cysts. CT99.9 for a variety of disinfectants and
conditions appear in tables 1.1-1.6, 2.1, and 3.1 of Sec. 141.74(b)(3).
[GRAPHIC] [TIFF OMITTED] TC15NO91.129
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is the inactivation ratio. The sum of the inactivation ratios, or total
inactivation ratio shown as
[GRAPHIC] [TIFF OMITTED] TC15NO91.130
is calculated by adding together the inactivation ratio for each
disinfection sequence. A total inactivation ratio equal to or greater
than 1.0 is assumed to provide a 3-log inactivation of Giardia lamblia
cysts.
Diatomaceous earth filtration means a process resulting in
substantial particulate removal in which (1) a precoat cake of
diatomaceous earth filter media is deposited on a support membrance
(septum), and (2) while the water is filtered by passing through the
cake on the septum, additional filter media known as body feed is
continuously added to the feed water to maintain the permeability of the
filter cake.
Direct filtration means a series of processes including coagulation
and filtration but excluding sedimentation resulting in substantial
particulate removal.
Disinfectant means any oxidant, including but not limited to
chlorine, chlorine dioxide, chloramines, and ozone added to water in any
part of the treatment or distribution process, that is intended to kill
or inactivate pathogenic microorganisms.
Disinfectant contact time (``T'' in CT calculations) means the time
in minutes that it takes for water to move from the point of
disinfectant application or the previous point of disinfectant residual
measurement to a point before or at the point where residual
disinfectant concentration (``C'') is measured. Where only one ``C'' is
measured, ``T'' is the time in minutes that it takes for water to move
from the point of disinfectant application to a point before or at where
residual disinfectant concentration (``C'') is measured. Where more than
one ``C'' is measured, ``T'' is (a) for the first measurement of ``C'',
the time in minutes that it takes for water to move from the first or
only point of disinfectant application to a point before or at the point
where the first ``C'' is measured and (b) for subsequent measurements of
``C'', the time in minutes that it takes for water to move from the
previous ``C'' measurement point to the ``C'' measurement point for
which the particular ``T'' is being calculated. Disinfectant contact
time in pipelines must be calculated based on ``plug flow'' by dividing
the internal volume of the pipe by the maximum hourly flow rate through
that pipe. Disinfectant contact time within mixing basins and storage
reservoirs must be determined by tracer studies or an equivalent
demonstration.
Disinfection means a process which inactivates pathogenic organisms
in water by chemical oxidants or equivalent agents.
Disinfection profile is a summary of Giardia lamblia inactivation
through the treatment plant. The procedure for developing a disinfection
profile is contained in Sec. 141.172 (Disinfection profiling and
benchmarking) in subpart P and Sec. Sec. 141.530-141.536 (Disinfection
profile) in subpart T of this part.
Domestic or other non-distribution system plumbing problem means a
coliform contamination problem in a public water system with more than
one service connection that is limited to the specific service
connection from which the coliform-positive sample was taken.
Dose equivalent means the product of the absorbed dose from ionizing
radiation and such factors as account for differences in biological
effective ness due to the type of radiation and its distribution in the
body as speci fied by the International Commission on Radiological Units
and Measurements (ICRU).
Effective corrosion inhibitor residual, for the purpose of subpart I
of this part only, means a concentration sufficient to form a
passivating film on the interior walls of a pipe.
Enhanced coagulation means the addition of sufficient coagulant for
improved removal of disinfection byproduct precursors by conventional
filtration treatment.
Enhanced softening means the improved removal of disinfection
byproduct precursors by precipitative softening.
Filter profile is a graphical representation of individual filter
performance,
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based on continuous turbidity measurements or total particle counts
versus time for an entire filter run, from startup to backwash
inclusively, that includes an assessment of filter performance while
another filter is being backwashed.
Filtration means a process for removing particulate matter from
water by passage through porous media.
First draw sample means a one-liter sample of tap water, collected
in accordance with Sec. 141.86(b)(2), that has been standing in
plumbing pipes at least 6 hours and is collected without flushing the
tap.
Flocculation means a process to enhance agglomeration or collection
of smaller floc particles into larger, more easily settleable particles
through gentle stirring by hydraulic or mechanical means.
GAC10 means granular activated carbon filter beds with an empty-bed
contact time of 10 minutes based on average daily flow and a carbon
reactivation frequency of every 180 days.
Ground water under the direct influence of surface water (GWUDI)
means any water beneath the surface of the ground with significant
occurrence of insects or other macroorganisms, algae, or large-diameter
pathogens such as Giardia lamblia or Cryptosporidium, or significant and
relatively rapid shifts in water characteristics such as turbidity,
temperature, conductivity, or pH which closely correlate to
climatological or surface water conditions. Direct influence must be
determined for individual sources in accordance with criteria
established by the State. The State determination of direct influence
may be based on site-specific measurements of water quality and/or
documentation of well construction characteristics and geology with
field evaluation.
Gross alpha particle activity means the total radioactivity due to
alpha particle emission as inferred from measurements on a dry sample.
Gross beta particle activity means the total radioactivity due to
beta particle emission as inferred from measurements on a dry sample.
Haloacetic acids (five) (HAA5) mean the sum of the concentrations in
milligrams per liter of the haloacetic acid compounds (monochloroacetic
acid, dichloroacetic acid, trichloroacetic acid, monobromoacetic acid,
and dibromoacetic acid), rounded to two significant figures after
addition.
Halogen means one of the chemical elements chlorine, bromine or
iodine.
Initial compliance period means the first full three-year compliance
period which begins at least 18 months after promulgation, except for
contaminants listed at Sec. 141.61(a) (19)-(21), (c) (19)-(33), and
Sec. 141.62(b) (11)-(15), initial compliance period means the first
full three-year compliance period after promulgation for systems with
150 or more service connections (January 1993-December 1995), and first
full three-year compliance period after the effective date of the
regulation (January 1996-December 1998) for systems having fewer than
150 service connections.
Large water system, for the purpose of subpart I of this part only,
means a water system that serves more than 50,000 persons.
Lead service line means a service line made of lead which connects
the water main to the building inlet and any lead pigtail, gooseneck or
other fitting which is connected to such lead line.
Legionella means a genus of bacteria, some species of which have
caused a type of pneumonia called Legionnaires Disease.
Man-made beta particle and photon emitters means all radionuclides
emitting beta particles and/or photons listed in Maximum Permissible
Body Burdens and Maximum Permissible Concentration of Radionuclides in
Air or Water for Occupational Exposure, NBS Handbook 69, except the
daughter products of thorium-232, uranium-235 and uranium-238.
Maximum contaminant level means the maximum permissable level of a
contaminant in water which is delivered to any user of a public water
system.
Maximum contaminant level goal or MCLG means the maximum level of a
contaminant in drinking water at which no known or anticipated adverse
effect on the health of persons would occur, and which allows an
adequate margin of safety. Maximum contaminant level goals are
nonenforceable health goals.
[[Page 349]]
Maximum residual disinfectant level (MRDL) means a level of a
disinfectant added for water treatment that may not be exceeded at the
consumer's tap without an unacceptable possibility of adverse health
effects. For chlorine and chloramines, a PWS is in compliance with the
MRDL when the running annual average of monthly averages of samples
taken in the distribution system, computed quarterly, is less than or
equal to the MRDL. For chlorine dioxide, a PWS is in compliance with the
MRDL when daily samples are taken at the entrance to the distribution
system and no two consecutive daily samples exceed the MRDL. MRDLs are
enforceable in the same manner as maximum contaminant levels under
Section 1412 of the Safe Drinking Water Act. There is convincing
evidence that addition of a disinfectant is necessary for control of
waterborne microbial contaminants. Notwithstanding the MRDLs listed in
Sec. 141.65, operators may increase residual disinfectant levels of
chlorine or chloramines (but not chlorine dioxide) in the distribution
system to a level and for a time necessary to protect public health to
address specific microbiological contamination problems caused by
circumstances such as distribution line breaks, storm runoff events,
source water contamination, or cross-connections.
Maximum residual disinfectant level goal (MRDLG) means the maximum
level of a disinfectant added for water treatment at which no known or
anticipated adverse effect on the health of persons would occur, and
which allows an adequate margin of safety. MRDLGs are nonenforceable
health goals and do not reflect the benefit of the addition of the
chemical for control of waterborne microbial contaminants.
Maximum Total Trihalomethane Potential (MTP) means the maximum
concentration of total trihalomethanes produced in a given water
containing a disinfectant residual after 7 days at a temperature of 25
[deg]C or above.
Medium-size water system, for the purpose of subpart I of this part
only, means a water system that serves greater than 3,300 and less than
or equal to 50,000 persons.
Near the first service connection means at one of the 20 percent of
all service connections in the entire system that are nearest the water
supply treatment facility, as measured by water transport time within
the distribution system.
Non-community water system means a public water system that is not a
community water system. A non-community water system is either a
``transient non-community water system (TWS)'' or a ``non-transient non-
community water system (NTNCWS).''
Non-transient non-community water system or NTNCWS means a public
water system that is not a community water system and that regularly
serves at least 25 of the same persons over 6 months per year.
Optimal corrosion control treatment, for the purpose of subpart I of
this part only, means the corrosion control treatment that minimizes the
lead and copper concentrations at users' taps while insuring that the
treatment does not cause the water system to violate any national
primary drinking water regulations.
Performance evaluation sample means a reference sample provided to a
laboratory for the purpose of demonstrating that the laboratory can
successfully analyze the sample within limits of performance specified
by the Agency. The true value of the concentration of the reference
material is unknown to the laboratory at the time of the analysis.
Person means an individual; corporation; company; association;
partnership; municipality; or State, Federal, or tribal agency.
Picocurie (pCi) means the quantity of radioactive material producing
2.22 nuclear transformations per minute.
Point of disinfectant application is the point where the
disinfectant is applied and water downstream of that point is not
subject to recontamination by surface water runoff.
Point-of-entry treatment device (POE) is a treatment device applied
to the drinking water entering a house or building for the purpose of
reducing contaminants in the drinking water distributed throughout the
house or building.
[[Page 350]]
Point-of-use treatment device (POU) is a treat ment device applied
to a single tap used for the purpose of reducing con tam i nants in
drinking water at that one tap.
Public water system means a system for the provision to the public
of water for human consumption through pipes or, after August 5, 1998,
other constructed conveyances, if such system has at least fifteen
service connections or regularly serves an average of at least twenty-
five individuals daily at least 60 days out of the year. Such term
includes: any collection, treatment, storage, and distribution
facilities under control of the operator of such system and used
primarily in connection with such system; and any collection or
pretreatment storage facilities not under such control which are used
primarily in connection with such system. Such term does not include any
``special irrigation district.'' A public water system is either a
``community water system'' or a ``noncommunity water system.''
Rem means the unit of dose equivalent from ionizing radiation to the
total body or any internal organ or organ system. A ``millirem (mrem)''
is 1/1000 of a rem.
Repeat compliance period means any subsequent compliance period
after the initial compliance period.
Residual disinfectant concentration (``C'' in CT calculations) means
the concentration of disinfectant measured in mg/l in a representative
sample of water.
Sanitary survey means an onsite review of the water source,
facilities, equipment, operation and maintenance of a public water
system for the purpose of evaluating the adequacy of such source,
facilities, equipment, operation and maintenance for producing and
distributing safe drinking water.
Sedimentation means a process for removal of solids before
filtration by gravity or separation.
Service connection, as used in the definition of public water
system, does not include a connection to a system that delivers water by
a constructed conveyance other than a pipe if:
(1) The water is used exclusively for purposes other than
residential uses (consisting of drinking, bathing, and cooking, or other
similar uses);
(2) The State determines that alternative water to achieve the
equivalent level of public health protection provided by the applicable
national primary drinking water regulation is provided for residential
or similar uses for drinking and cooking; or
(3) The State determines that the water provided for residential or
similar uses for drinking, cooking, and bathing is centrally treated or
treated at the point of entry by the provider, a pass-through entity, or
the user to achieve the equivalent level of protection provided by the
applicable national primary drinking water regulations.
Service line sample means a one-liter sample of water collected in
accordance with Sec. 141.86(b)(3), that has been standing for at least
6 hours in a service line.
Single family structure, for the purpose of subpart I of this part
only, means a building constructed as a single-family residence that is
currently used as either a residence or a place of business.
Slow sand filtration means a process involving passage of raw water
through a bed of sand at low velocity (generally less than 0.4 m/h)
resulting in substantial particulate removal by physical and biological
mechanisms.
Small water system, for the purpose of subpart I of this part only,
means a water system that serves 3,300 persons or fewer.
Special irrigation district means an irrigation district in
existence prior to May 18, 1994 that provides primarily agricultural
service through a piped water system with only incidental residential or
similar use where the system or the residential or similar users of the
system comply with the exclusion provisions in section 1401(4)(B)(i)(II)
or (III).
Standard sample means the aliquot of finished drinking water that is
examined for the presence of coliform bacteria.
State means the agency of the State or Tribal government which has
jurisdiction over public water systems. During any period when a State
or Tribal government does not have primary enforcement responsibility
pursuant to
[[Page 351]]
section 1413 of the Act, the term ``State'' means the Regional
Administrator, U.S. Environmental Protection Agency.
Subpart H systems means public water systems using surface water or
ground water under the direct influence of surface water as a source
that are subject to the requirements of subpart H of this part.
Supplier of water means any person who owns or operates a public
water system.
Surface water means all water which is open to the atmosphere and
subject to surface runoff.
SUVA means Specific Ultraviolet Absorption at 254 nanometers (nm),
an indicator of the humic content of water. It is a calculated parameter
obtained by dividing a sample's ultraviolet absorption at a wavelength
of 254 nm (UV 254) (in m =1) by its concentration
of dissolved organic carbon (DOC) (in mg/L).
System with a single service connection means a system which
supplies drinking water to consumers via a single service line.
Too numerous to count means that the total number of bacterial
colonies exceeds 200 on a 47-mm diameter membrane filter used for
coliform detection.
Total Organic Carbon (TOC) means total organic carbon in mg/L
measured using heat, oxygen, ultraviolet irradiation, chemical oxidants,
or combinations of these oxidants that convert organic carbon to carbon
dioxide, rounded to two significant figures.
Total trihalomethanes (TTHM) means the sum of the concentration in
milligrams per liter of the trihalo methane compounds (trichloromethane
[chloro form], dibromochloromethane, bromodichloro methane and
tribromomethane [bromoform]), rounded to two significant figures.
Transient non-community water system or TWS means a non-community
water system that does not regularly serve at least 25 of the same
persons over six months per year.
Trihalomethane (THM) means one of the family of organic compounds,
named as derivatives of methane, wherein three of the four hydrogen
atoms in methane are each sub stituted by a halogen atom in the
molecular struc ture.
Uncovered finished water storage facility is a tank, reservoir, or
other facility used to store water that will undergo no further
treatment except residual disinfection and is open to the atmosphere.
Virus means a virus of fecal origin which is infectious to humans by
waterborne transmission.
Waterborne disease outbreak means the significant occurrence of
acute infectious illness, epidemiologically associated with the
ingestion of water from a public water system which is deficient in
treatment, as determined by the appropriate local or State agency.
[40 FR 59570, Dec. 24, 1975, as amended at 41 FR 28403, July 9, 1976; 44
FR 68641, Nov. 29, 1979; 51 FR 11410, Apr. 2, 1986; 52 FR 20674, June 2,
1987; 52 FR 25712, July 8, 1987; 53 FR 37410, Sept. 26, 1988; 54 FR
27526, 27562, June 29, 1989; 56 FR 3578, Jan. 30, 1991; 56 FR 26547,
June 7, 1991; 57 FR 31838, July 17, 1992; 59 FR 34322, July 1, 1994; 61
FR 24368, May 14, 1996; 63 FR 23366, Apr. 28, 1998; 63 FR 69463, 69515,
Dec. 16, 1998; 66 FR 7061, Jan. 22, 2001; 67 FR 1835, Jan. 14, 2002]
Sec. 141.3 Coverage.
This part shall apply to each public water system, unless the public
water system meets all of the following conditions:
(a) Consists only of distribution and storage facilities (and does
not have any collection and treatment facilities);
(b) Obtains all of its water from, but is not owned or operated by,
a public water system to which such regulations apply:
(c) Does not sell water to any person; and
(d) Is not a carrier which conveys passengers in interstate
commerce.
Sec. 141.4 Variances and exemptions.
(a) Variances or exemptions from certain provisions of these
regulations may be granted pursuant to sections 1415 and 1416 of the Act
and subpart K of part 142 of this chapter (for small system variances)
by the entity with primary enforcement responsibility, except that
variances or exemptions from the MCL for total coliforms and variances
from any of the treatment
[[Page 352]]
technique requirements of subpart H of this part may not be granted.
(b) EPA has stayed the effective date of this section relating to
the total coliform MCL of Sec. 141.63(a) for systems that demonstrate
to the State that the violation of the total coliform MCL is due to a
persistent growth of total coliforms in the distribution system rather
than fecal or pathogenic contamination, a treatment lapse or deficiency,
or a problem in the operation or maintenance of the distribution system.
[54 FR 27562, June 29, 1989, as amended at 56 FR 1557, Jan. 15, 1991; 63
FR 43846, Aug. 14, 1998]
Sec. 141.5 Siting requirements.
Before a person may enter into a financial commitment for or
initiate construction of a new public water system or increase the
capacity of an existing public water system, he shall notify the State
and, to the extent practicable, avoid locating part or all of the new or
expanded facility at a site which:
(a) Is subject to a significant risk from earthquakes, floods, fires
or other disasters which could cause a breakdown of the public water
system or a portion thereof; or
(b) Except for intake structures, is within the floodplain of a 100-
year flood or is lower than any recorded high tide where appropriate
records exist. The U.S. Environmental Protection Agency will not seek to
override land use decisions affecting public water systems siting which
are made at the State or local government levels.
Sec. 141.6 Effective dates.
(a) Except as provided in paragraphs (b) through (k) of this
section, and in Sec. 141.80(a)(2), the regulations set forth in this
part shall take effect on June 24, 1977.
(b) The regulations for total tri hal o methanes set forth in Sec.
141.12(c) shall take effect 2 years after the date of pro mul gation of
these regulations for community water systems serving 75,000 or more
individuals, and 4 years after the date of promulgation for communities
serving 10,000 to 74,999 individuals.
(c) The regulations set forth in Sec. Sec. 141.11(d); 141.21(a),
(c) and (i); 141.22(a) and (e); 141.23(a)(3) and (a)(4); 141.23(f);
141.24(e) and (f); 141.25(e); 141.27(a); 141.28(a) and (b); 141.31(a),
(d) and (e); 141.32(b)(3); and 141.32(d) shall take effect immediately
upon promulgation.
(d) The regulations set forth in Sec. 141.41 shall take effect 18
months from the date of promulgation. Suppliers must complete the first
round of sampling and reporting within 12 months following the effective
date.
(e) The regulations set forth in Sec. 141.42 shall take effect 18
months from the date of promulgation. All requirements in Sec. 141.42
must be completed within 12 months following the effective date.
(f) The regulations set forth in Sec. 141.11(c) and Sec. 141.23(g)
are effective May 2, 1986. Section 141.23(g)(4) is effective October 2,
1987.
(g) The regulations contained in Sec. 141.6, paragraph (c) of the
table in 141.12, and 141.62(b)(1) are effective July 1, 1991. The
regulations contained in Sec. Sec. 141.11(b), 141.23, 141.24,
142.57(b), 143.4(b)(12) and (b)(13), are effective July 30, 1992. The
regulations contained in the revisions to Sec. Sec. 141.32(e) (16),
(25) through (27) and (46); 141.61(c)(16); and 141.62(b)(3) are
effective January 1, 1993. The effective date of regulations contained
in Sec. 141.61(c) (2), (3), and (4) is postponed.
(h) Regulations for the analytic methods listed at Sec.
141.23(k)(4) for measuring antimony, beryllium, cyanide, nickel, and
thallium are ef fective August 17, 1992. Regulations for the analytic
methods listed at Sec. 141.24(f)(16) for dichloromethane, 1,2,4-tri
chlor o benzene, and 1,1,2-tri chlor o ethane are effective August 17,
1992. Regulations for the analytic methods listed at Sec. 141.24(h)(12)
for measuring dalapon, dinoseb, diquat, endothall, endrin, glyphosate,
oxamyl, picloram, simazine, benzo(a)pyrene, di(2-ethylhexyl)adipate,
di(2-ethylhexyl)ph thalate, hex a chlor o ben zene,
hexachlorocyclopentadiene, and 2,3,7,8-TCDD are effective August 17,
1992. The revision to Sec. 141.12(a) promulgated on July 17, 1992 is
effective on August 17, 1992.
(i) [Reserved]
[[Page 353]]
(j) The arsenic maximum contaminant levels (MCL) listed in Sec.
141.62 is effective for the purpose of compliance on January 23, 2006.
Requirements relating to arsenic set forth in Sec. Sec. 141.23(i)(4),
141.23(k)(3) introductory text, 141.23(k)(3)(ii), 141.51(b), 141.62(b),
141.62(b)(16), 141.62(c), 141.62(d), and 142.62(b) revisions in Appendix
A of subpart O for the consumer confidence rule, and Appendices A and B
of subpart Q for the public notification rule are effective for the
purpose of compliance on January 23, 2006. However, the consumer
confidence rule reporting requirements relating to arsenic listed in
Sec. 141.154(b) and (f) are effective for the purpose of compliance on
February 22, 2002.
(k) Regulations set forth in Sec. Sec. 141.23(i)(1), 141.23(i)(2),
141.24(f)(15), 141.24(f)(22), 141.24(h)(11), 141.24(h)(20), 142.16(e),
142.16(j), and 142.16(k) are effective for the purpose of compliance on
January 22, 2004.
[44 FR 68641, Nov. 29, 1979, as amended at 45 FR 57342, Aug. 27, 1980;
47 FR 10998, Mar. 12, 1982; 51 FR 11410, Apr. 2, 1986; 56 FR 30274, July
1, 1991; 57 FR 22178, May 27, 1992; 57 FR 31838, July 17, 1992; 59 FR
34322, July 1, 1994; 61 FR 24368, May 14, 1996; 66 FR 7061, Jan. 22,
2001; 66 FR 28350, May 22, 2001]
Subpart B_Maximum Contaminant Levels
Sec. 141.11 Maximum contaminant levels for inorganic chemicals.
(a) The maximum contaminant level for arsenic applies only to
community water systems. The analyses and determination of compliance
with the 0.05 milligrams per liter maximum contaminant level for arsenic
use the requirements of Sec. 141.23.
(b) The maximum contaminant level for arsenic is 0.05 milligrams per
liter for community water systems until January 23, 2006.
(c) [Reserved]
(d) At the discretion of the State, nitrate levels not to exceed 20
mg/l may be allowed in a non-community water system if the supplier of
water demonstrates to the satisfaction of the State that:
(1) Such water will not be available to children under 6 months of
age; and
(2) The non-community water system is meeting the public
notification requirements under Sec. 141.209, including continuous
posting of the fact that nitrate levels exceed 10 mg/l and the potential
health effects of exposure; and
(3) Local and State public health authorities will be notified
annually of nitrate levels that exceed 10 mg/l; and
(4) No adverse health effects shall result.
[40 FR 59570, Dec. 24, 1975, as amended at 45 FR 57342, Aug. 27, 1980;
47 FR 10998, Mar. 12, 1982; 51 FR 11410, Apr. 2, 1986; 56 FR 3578, Jan.
30, 1991; 56 FR 26548, June 7, 1991; 56 FR 30274, July 1, 1991; 56 FR
32113, July 15, 1991; 60 FR 33932, June 29, 1995; 65 FR 26022, May 4,
2000; 66 FR 7061, Jan. 22, 2001]
Sec. 141.12 Maximum contaminant levels for total trihalomethanes.
The maximum contaminant level of 0.10 mg/L for total trihalomethanes
(the sum of the concentrations of bromodichloromethane,
dibromochloromethane, tribromomethane (bromoform), and trichloromethane
(chloroform)) applies to subpart H community water systems which serve a
population of 10,000 people or more until December 31, 2001. This level
applies to community water systems that use only ground water not under
the direct influence of surface water and serve a population of 10,000
people or more until December 31, 2003. Compliance with the maximum
contaminant level for total trihalomethanes is calculated pursuant to
Sec. 141.30. After December 31, 2003, this section is no longer
applicable.
[63 FR 69463, Dec. 16, 1998, as amended at 66 FR 3776, Jan. 16, 2001]
Sec. 141.13 Maximum contaminant levels for turbidity.
The maximum contaminant levels for turbidity are applicable to both
community water systems and non-community water systems using surface
water sources in whole or in part. The maximum contaminant levels for
turbidity in drinking water, measured at a representative entry point(s)
to the distribution system, are:
Editorial Note: At 54 FR 27527, June 29, 1989, Sec. 141.13 was
amended by adding introductory text, effective December 31, 1990.
[[Page 354]]
However, introductory text already exists. The added text follows.
The requirements in this section apply to unfiltered systems until
December 30, 1991, unless the State has determined prior to that date,
in writing pursuant to Sec. 1412(b)(7)(C)(iii), that filtration is
required. The requirements in this section apply to filtered systems
until June 29, 1993. The requirements in this section apply to
unfiltered systems that the State has determined, in writing pursuant to
Sec. 1412(b)(7)(C)(iii), must install filtration, until June 29, 1993,
or until filtration is installed, whichever is later.
(a) One turbidity unit (TU), as determined by a monthly average
pursuant to Sec. 141.22, except that five or fewer turbidity units may
be allowed if the supplier of water can demonstrate to the State that
the higher turbidity does not do any of the following:
(1) Interfere with disinfection;
(2) Prevent maintenance of an effective disinfectant agent
throughout the distribution system; or
(3) Interfere with microbiological determinations.
(b) Five turbidity units based on an average for two consecutive
days pursuant to Sec. 141.22.
[40 FR 59570, Dec. 24, 1975]
Subpart C_Monitoring and Analytical Requirements
Sec. 141.21 Coliform sampling.
(a) Routine monitoring. (1) Public water systems must collect total
coliform samples at sites which are representative of water throughout
the distribution system according to a written sample siting plan. These
plans are subject to State review and revision.
(2) The monitoring frequency for total coliforms for community water
systems is based on the population served by the system, as follows:
Total Coliform Monitoring Frequency for Community Water Systems
------------------------------------------------------------------------
Minimum
number of
Population served samples
per month
------------------------------------------------------------------------
25 to 1,000 \1\.............................................. 1
1,001 to 2,500............................................... 2
2,501 to 3,300............................................... 3
3,301 to 4,100............................................... 4
4,101 to 4,900............................................... 5
4,901 to 5,800............................................... 6
5,801 to 6,700............................................... 7
6,701 to 7,600............................................... 8
7,601 to 8,500............................................... 9
8,501 to 12,900.............................................. 10
12,901 to 17,200............................................. 15
17,201 to 21,500............................................. 20
21,501 to 25,000............................................. 25
25,001 to 33,000............................................. 30
33,001 to 41,000............................................. 40
41,001 to 50,000............................................. 50
50,001 to 59,000............................................. 60
59,001 to 70,000............................................. 70
70,001 to 83,000............................................. 80
83,001 to 96,000............................................. 90
96,001 to 130,000............................................ 100
130,001 to 220,000........................................... 120
220,001 to 320,000........................................... 150
320,001 to 450,000........................................... 180
450,001 to 600,000........................................... 210
600,001 to 780,000........................................... 240
780,001 to 970,000........................................... 270
970,001 to 1,230,000......................................... 300
1,230,001 to 1,520,000....................................... 330
1,520,001 to 1,850,000....................................... 360
1,850,001 to 2,270,000....................................... 390
2,270,001 to 3,020,000....................................... 420
3,020,001 to 3,960,000....................................... 450
3,960,001 or more............................................ 480
------------------------------------------------------------------------
\1\ Includes public water systems which have at least 15 service
connections, but serve fewer than 25 persons.
If a community water system serving 25 to 1,000 persons has no history
of total coliform contamination in its current configuration and a
sanitary survey conducted in the past five years shows that the system
is supplied solely by a protected groundwater source and is free of
sanitary defects, the State may reduce the monitoring frequency
specified above, except that in no case may the State reduce the
monitoring frequency to less than one sample per quarter. The State must
approve the reduced monitoring frequency in writing.
(3) The monitoring frequency for total coliforms for non-community
water systems is as follows:
(i) A non-community water system using only ground water (except
ground water under the direct influence of surface water, as defined in
Sec. 141.2) and serving 1,000 persons or fewer must monitor each
calendar
[[Page 355]]
quarter that the system provides water to the public, except that the
State may reduce this monitoring frequency, in writing, if a sanitary
survey shows that the system is free of sanitary defects. Beginning June
29, 1994, the State cannot reduce the monitoring frequency for a non-
community water system using only ground water (except ground water
under the direct influence of surface water, as defined in Sec. 141.2)
and serving 1,000 persons or fewer to less than once/year.
(ii) A non-community water system using only ground water (except
ground water under the direct influence of surface water, as defined in
Sec. 141.2) and serving more than 1,000 persons during any month must
monitor at the same frequency as a like-sized community water system, as
specified in paragraph (a)(2) of this section, except the State may
reduce this monitoring frequency, in writing, for any month the system
serves 1,000 persons or fewer. The State cannot reduce the monitoring
frequency to less than once/year. For systems using ground water under
the direct influence of surface water, paragraph (a)(3)(iv) of this
section applies.
(iii) A non-community water system using surface water, in total or
in part, must monitor at the same frequency as a like-sized community
water system, as specified in paragraph (a)(2) of this section,
regardless of the number of persons it serves.
(iv) A non-community water system using ground water under the
direct influence of surface water, as defined in Sec. 141.2, must
monitor at the same frequency as a like-sized community water system, as
specified in paragraph (a)(2) of this section. The system must begin
monitoring at this frequency beginning six months after the State
determines that the ground water is under the direct influence of
surface water.
(4) The public water system must collect samples at regular time
intervals throughout the month, except that a system which uses only
ground water (except ground water under the direct influence of surface
water, as defined in Sec. 141.2), and serves 4,900 persons or fewer,
may collect all required samples on a single day if they are taken from
different sites.
(5) A public water system that uses surface water or ground water
under the direct influence of surface water, as defined in Sec. 141.2,
and does not practice filtration in compliance with Subpart H must
collect at least one sample near the first service connection each day
the turbidity level of the source water, measured as specified in Sec.
141.74(b)(2), exceeds 1 NTU. This sample must be analyzed for the
presence of total coliforms. When one or more turbidity measurements in
any day exceed 1 NTU, the system must collect this coliform sample
within 24 hours of the first exceedance, unless the State determines
that the system, for logistical reasons outside the system's control,
cannot have the sample analyzed within 30 hours of collection. Sample
results from this coliform monitoring must be included in determining
compliance with the MCL for total coliforms in Sec. 141.63.
(6) Special purpose samples, such as those taken to determine
whether disinfection practices are sufficient following pipe placement,
replacement, or repair, shall not be used to determine compliance with
the MCL for total coliforms in Sec. 141.63. Repeat samples taken
pursuant to paragraph (b) of this section are not considered special
purpose samples, and must be used to determine compliance with the MCL
for total coliforms in Sec. 141.63.
(b) Repeat monitoring. (1) If a routine sample is total coliform-
positive, the public water system must collect a set of repeat samples
within 24 hours of being notified of the positive result. A system which
collects more than one routine sample/month must collect no fewer than
three repeat samples for each total coliform-positive sample found. A
system which collects one routine sample/month or fewer must collect no
fewer than four repeat samples for each total coliform-positive sample
found. The State may extend the 24-hour limit on a case-by-case basis if
the system has a logistical problem in collecting the repeat samples
within 24 hours that is beyond its control. In the case of an extension,
the State must specify how much time
[[Page 356]]
the system has to collect the repeat samples.
(2) The system must collect at least one repeat sample from the
sampling tap where the original total coliform-positive sample was
taken, and at least one repeat sample at a tap within five service
connections upstream and at least one repeat sample at a tap within five
service connections downstream of the original sampling site. If a total
coliform-positive sample is at the end of the distribution system, or
one away from the end of the distribution system, the State may waive
the requirement to collect at least one repeat sample upstream or
downstream of the original sampling site.
(3) The system must collect all repeat samples on the same day,
except that the State may allow a system with a single service
connection to collect the required set of repeat samples over a four-day
period or to collect a larger volume repeat sample(s) in one or more
sample containers of any size, as long as the total volume collected is
at least 400 ml (300 ml for systems which collect more than one routine
sample/month).
(4) If one or more repeat samples in the set is total coliform-
positive, the public water system must collect an additional set of
repeat samples in the manner specified in paragraphs (b) (1)-(3) of this
section. The additional samples must be collected within 24 hours of
being notified of the positive result, unless the State extends the
limit as provided in paragraph (b)(1) of this section. The system must
repeat this process until either total coliforms are not detected in one
complete set of repeat samples or the system determines that the MCL for
total coliforms in Sec. 141.63 has been exceeded and notifies the
State.
(5) If a system collecting fewer than five routine samples/month has
one or more total coliform-positive samples and the State does not
invalidate the sample(s) under paragraph (c) of this section, it must
collect at least five routine samples during the next month the system
provides water to the public, except that the State may waive this
requirement if the conditions of paragraph (b)(5) (i) or (ii) of this
section are met. The State cannot waive the requirement for a system to
collect repeat samples in paragraphs (b) (1)-(4) of this section.
(i) The State may waive the requirement to collect five routine
samples the next month the system provides water to the public if the
State, or an agent approved by the State, performs a site visit before
the end of the next month the system provides water to the public.
Although a sanitary survey need not be performed, the site visit must be
sufficiently detailed to allow the State to determine whether additional
monitoring and/or any corrective action is needed. The State cannot
approve an employee of the system to perform this site visit, even if
the employee is an agent approved by the State to perform sanitary
surveys.
(ii) The State may waive the requirement to collect five routine
samples the next month the system provides water to the public if the
State has determined why the sample was total coliform-positive and
establishes that the system has corrected the problem or will correct
the problem before the end of the next month the system serves water to
the public. In this case, the State must document this decision to waive
the following month's additional monitoring requirement in writing, have
it approved and signed by the supervisor of the State official who
recommends such a decision, and make this document available to the EPA
and public. The written documentation must describe the specific cause
of the total coliform-positive sample and what action the system has
taken and/or will take to correct this problem. The State cannot waive
the requirement to collect five routine samples the next month the
system provides water to the public solely on the grounds that all
repeat samples are total coliform-negative. Under this paragraph, a
system must still take at least one routine sample before the end of the
next month it serves water to the public and use it to determine
compliance with the MCL for total coliforms in Sec. 141.63, unless the
State has determined that the system has corrected the contamination
problem before the system took the set of repeat samples required in
paragraphs (b) (1)-
[[Page 357]]
(4) of this section, and all repeat samples were total coliform-
negative.
(6) After a system collects a routine sample and before it learns
the results of the analysis of that sample, if it collects another
routine sample(s) from within five adjacent service connections of the
initial sample, and the initial sample, after analysis, is found to
contain total coliforms, then the system may count the subsequent
sample(s) as a repeat sample instead of as a routine sample.
(7) Results of all routine and repeat samples not invalidated by the
State must be included in determining compliance with the MCL for total
coliforms in Sec. 141.63.
(c) Invalidation of total coliform samples. A total coliform-
positive sample invalidated under this paragraph (c) does not count
towards meeting the minimum monitoring requirements of this section.
(1) The State may invalidate a total coliform-positive sample only
if the conditions of paragraph (c)(1) (i), (ii), or (iii) of this
section are met.
(i) The laboratory establishes that improper sample analysis caused
the total coliform-positive result.
(ii) The State, on the basis of the results of repeat samples
collected as required by paragraphs (b) (1) through (4) of this section,
determines that the total coliform-positive sample resulted from a
domestic or other non-distribution system plumbing problem. The State
cannot invalidate a sample on the basis of repeat sample results unless
all repeat sample(s) collected at the same tap as the original total
coliform-positive sample are also total coliform-positive, and all
repeat samples collected within five service connections of the original
tap are total coliform-negative (e.g., a State cannot invalidate a total
coliform-positive sample on the basis of repeat samples if all the
repeat samples are total coliform-negative, or if the public water
system has only one service connection).
(iii) The State has substantial grounds to believe that a total
coliform-positive result is due to a circumstance or condition which
does not reflect water quality in the distribution system. In this case,
the system must still collect all repeat samples required under
paragraphs (b) (1)-(4) of this section, and use them to determine
compliance with the MCL for total coliforms in Sec. 141.63. To
invalidate a total coliform-positive sample under this paragraph, the
decision with the rationale for the decision must be documented in
writing, and approved and signed by the supervisor of the State official
who recommended the decision. The State must make this document
available to EPA and the public. The written documentation must state
the specific cause of the total coliform-positive sample, and what
action the system has taken, or will take, to correct this problem. The
State may not invalidate a total coliform-positive sample solely on the
grounds that all repeat samples are total coliform-negative.
(2) A laboratory must invalidate a total coliform sample (unless
total coliforms are detected) if the sample produces a turbid culture in
the absence of gas production using an analytical method where gas
formation is examined (e.g., the Multiple-Tube Fermentation Technique),
produces a turbid culture in the absence of an acid reaction in the
Presence-Absence (P-A) Coliform Test, or exhibits confluent growth or
produces colonies too numerous to count with an analytical method using
a membrane filter (e.g., Membrane Filter Technique). If a laboratory
invalidates a sample because of such interference, the system must
collect another sample from the same location as the original sample
within 24 hours of being notified of the interference problem, and have
it analyzed for the presence of total coliforms. The system must
continue to re-sample within 24 hours and have the samples analyzed
until it obtains a valid result. The State may waive the 24-hour time
limit on a case-by-case basis.
(d) Sanitary surveys. (1)(i) Public water systems which do not
collect five or more routine samples/month must undergo an initial
sanitary survey by June 29, 1994, for community public water systems and
June 29, 1999, for non-community water systems. Thereafter, systems must
undergo another
[[Page 358]]
sanitary survey every five years, except that non-community water
systems using only protected and disinfected ground water, as defined by
the State, must undergo subsequent sanitary surveys at least every ten
years after the initial sanitary survey. The State must review the
results of each sanitary survey to determine whether the existing
monitoring frequency is adequate and what additional measures, if any,
the system needs to undertake to improve drinking water quality.
(ii) In conducting a sanitary survey of a system using ground water
in a State having an EPA-approved wellhead protection program under
section 1428 of the Safe Drinking Water Act, information on sources of
contamination within the delineated wellhead protection area that was
collected in the course of developing and implementing the program
should be considered instead of collecting new information, if the
information was collected since the last time the system was subject to
a sanitary survey.
(2) Sanitary surveys must be performed by the State or an agent
approved by the State. The system is responsible for ensuring the survey
takes place.
(e) Fecal coliforms/Escherichia coli (E. coli) testing. (1) If any
routine or repeat sample is total coliform-positive, the system must
analyze that total coliform-positive culture medium to determine if
fecal coliforms are present, except that the system may test for E. coli
in lieu of fecal coliforms. If fecal coliforms or E. coli are present,
the system must notify the State by the end of the day when the system
is notified of the test result, unless the system is notified of the
result after the State office is closed, in which case the system must
notify the State before the end of the next business day.
(2) The State has the discretion to allow a public water system, on
a case-by-case basis, to forgo fecal coliform or E. coli testing on a
total coliform-positive sample if that system assumes that the total
coliform-positive sample is fecal coliform-positive or E. coli-positive.
Accordingly, the system must notify the State as specified in paragraph
(e)(1) of this section and the provisions of Sec. 141.63(b) apply.
(f) Analytical methodology. (1) The standard sample volume required
for total coliform analysis, regardless of analytical method used, is
100 ml.
(2) Public water systems need only determine the presence or absence
of total coliforms; a determination of total coliform density is not
required.
(3) Public water systems must conduct total coliform analyses in
accordance with one of the analytical methods in the following table.
----------------------------------------------------------------------------------------------------------------
Organism Methodology\12\ Citation\1\
----------------------------------------------------------------------------------------------------------------
Total Coliforms \2\................... Total Coliform Fermentation Technique 3, 9221A, B.
4, 5.
Total Coliform Membrane Filter Technique 9222A, B, C.
\6\.
Presence-Absence (P-A) Coliform Test 5, 9221D.
7.
ONPG-MUG Test \8\....................... 9223.
Colisure Test \9\. ..............................
E*Colite [reg] Test \10\. ..............................
m-ColiBlue24 [reg] Test \11\. ..............................
Readycult [reg] Coliforms 100 Presence/ ..............................
Absence Test \13\.
Membrane Filter Technique using ..............................
Chromocult [reg] Coliform Agar\14\.
Colitag [reg] Test \15\. ..............................
----------------------------------------------------------------------------------------------------------------
The procedures shall be done in accordance with the documents listed below. The incorporation by reference of
the following documents listed in footnotes 1, 6, 8, 9, 10 , 11, 13, 14 and 15 was approved by the Director of
the Federal Register in accordance with 5 U.S.C. 552(a) and 1 CFR Part 51. Copies of the documents may be
obtained from the sources listed below. Information regarding obtaining these documents can be obtained from
the Safe Drinking Water Hotline at 800-426-4791. Documents may be inspected at EPA's Drinking Water Docket,
EPA West, 1301 Constitution Avenue, NW., EPA West, Room B102, Washington DC 20460 (Telephone: 202-566-2426);
or at the National Archives and Records Administration (NARA). For information on the availability of this
material at NARA, call 202-741-6030, or go to: http://www.archives.gov/federal--register/code--of--federal--
regulations/ibr--locations.html.
\1\ Standard Methods for the Examination of Water and Wastewater, 18th edition (1992), 19th edition (1995), or
20th edition (1998). American Public Health Association, 1015 Fifteenth Street, NW., Washington, DC 20005. The
cited methods published in any of these three editions may be used.
\2\ The time from sample collection to initiation of analysis may not exceed 30 hours. Systems are encouraged
but not required to hold samples below 10 deg. C during transit.
\3\ Lactose broth, as commercially available, may be used in lieu of lauryl tryptose broth, if the system
conducts at least 25 parallel tests between this medium and lauryl tryptose broth using the water normally
tested, and this comparison demonstrates that the false-positive rate and false-negative rate for total
coliform, using lactose broth, is less than 10 percent.
\4\ If inverted tubes are used to detect gas production, the media should cover these tubes at least one-half to
two-thirds after the sample is added.
\5\ No requirement exists to run the completed phase on 10 percent of all total coliform-positive confirmed
tubes.
[[Page 359]]
\6\ MI agar also may be used. Preparation and use of MI agar is set forth in the article, ``New medium for the
simultaneous detection of total coliform and Escherichia coli in water'' by Brenner, K.P., et. al., 1993,
Appl. Environ. Microbiol. 59:3534-3544. Also available from the Office of Water Resource Center (RC-4100T),
1200 Pennsylvania Avenue, NW., Washington, DC 20460, EPA/600/J-99/225. Verification of colonies is not
required.
\7\ Six-times formulation strength may be used if the medium is filter-sterilized rather than autoclaved.
\8\ The ONPG-MUG Test is also known as the Autoanalysis Collect System.
\9\ A description of the Colisure Test, Feb 28, 1994, may be obtained from IDEXX Laboratories, Inc., One IDEXX
Drive, Westbrook, Maine 04092. The Colisure Test may be read after an incubation time of 24 hours.
\10\ A description of the E*Colite [reg] Test, ``Presence/Absence for Coliforms and E. Coli in Water,'' Dec 21,
1997, is available from Charm Sciences, Inc., 36 Franklin Street, Malden, MA 02148-4120.
\11\ A description of the m-ColiBlue24 [reg] Test, Aug 17, 1999, is available from the Hach Company, 100 Dayton
Avenue, Ames, IA 50010.
\12\ EPA strongly recommends that laboratories evaluate the false-positive and negative rates for the method(s)
they use for monitoring total coliforms. EPA also encourages laboratories to establish false-positive and
false-negative rates within their own laboratory and sample matrix (drinking water or source water) with the
intent that if the method they choose has an unacceptable false-positive or negative rate, another method can
be used. The Agency suggests that laboratories perform these studies on a minimum of 5% of all total coliform-
positive samples, except for those methods where verification/confirmation is already required, e.g., the M-
Endo and LES Endo Membrane Filter Tests, Standard Total Coliform Fermentation Technique, and Presence-Absence
Coliform Test. Methods for establishing false-positive and negative-rates may be based on lactose
fermentation, the rapid test for [beta]-galactosidase and cytochrome oxidase, multi-test identification
systems, or equivalent confirmation tests. False-positive and false-negative information is often available in
published studies and/or from the manufacturer(s).
\13\ The Readycult [reg] Coliforms 100 Presence/Absence Test is described in the document, ``Readycult [reg]
Coliforms 100 Presence/Absence Test for Detection and Identification of Coliform Bacteria and Escherichla coli
in Finished Waters'', November 2000, Version 1.0, available from EM Science (an affiliate of Merck KGgA,
Darmstadt Germany), 480 S. Democrat Road, Gibbstown, NJ 08027-1297. Telephone number is (800) 222-0342, e-mail
address is: [email protected].
\14\ Membrane Filter Technique using Chromocult [reg] Coliform Agar is described in the document, ``Chromocult
[reg] Coliform Agar Presence/Absence Membrane Filter Test Method for Detection and Identification of Coliform
Bacteria and Escherichla coli in Finished Waters'', November 2000, Version 1.0, available from EM Science (an
affiliate of Merck KGgA, Darmstadt Germany), 480 S. Democrat Road, Gibbstown, NJ 08027-1297. Telephone number
is (800) 222-0342, e-mail address is: [email protected].
\15\ Colitag [reg] product for the determination of the presence/absence of total coliforms and E. coli is
described in ``Colitag [reg] Product as a Test for Detection and Identification of Coliforms and E. coli
Bacteria in Drinking Water and Source Water as Required in National Primary Drinking Water Regulations,''
August 2001, available from CPI International, Inc., 5580 Skylane Blvd., Santa Rosa, CA, 95403, telephone
(800) 878-7654, Fax (707) 545-7901, Internet address http://www.cpiinternational.com.
(4) [Reserved]
(5) Public water systems must conduct fecal coliform analysis in
accordance with the following procedure. When the MTF Technique or
Presence-Absence (PA) Coliform Test is used to test for total coliforms,
shake the lactose-positive presumptive tube or P-A vigorously and
transfer the growth with a sterile 3-mm loop or sterile applicator stick
into brilliant green lactose bile broth and EC medium to determine the
presence of total and fecal coliforms, respectively. For EPA-approved
analytical methods which use a membrane filter, transfer the total
coliform-positive culture by one of the following methods: remove the
membrane containing the total coliform colonies from the substrate with
a sterile forceps and carefully curl and insert the membrane into a tube
of EC medium (the laboratory may first remove a small portion of
selected colonies for verification), swab the entire membrane filter
surface with a sterile cotton swab and transfer the inoculum to EC
medium (do not leave the cotton swab in the EC medium), or inoculate
individual total coliform-positive colonies into EC Medium. Gently shake
the inoculated tubes of EC medium to insure adequate mixing and incubate
in a waterbath at 44.5 0.2 [deg]C for 24 2 hours. Gas production of any amount in the inner
fermentation tube of the EC medium indicates a positive fecal coliform
test. The preparation of EC medium is described in Method 9221E
(paragraph 1a) in Standard Methods for the Examination of Water and
Wastewater, 18th edition (1992), 19th edition (1995), and 20th edition
(1998); the cited method in any one of these three editions may be used.
Public water systems need only determine the presence or absence of
fecal coliforms; a determination of fecal coliform density is not
required.
(6) Public water systems must conduct analysis of Escherichia coli
in accordance with one of the following analytical methods:
(i) EC medium supplemented with 50 [micro]g/mL of 4-
methylumbelliferyl-beta-D-glucuronide (MUG) (final concentration), as
described in Method 9222G in Standard Methods for the Examination of
Water and Wastewater, 19th edition (1995) and 20th edition (1998).
Either edition may be used. Alternatively, the 18th edition (1992) may
be used if at least 10 mL of EC medium, as described in paragraph (f)(5)
of this section, is supplemented with 50 [micro]g/mL of MUG before
autoclaving. The inner inverted fermentation tube may be omitted. If
[[Page 360]]
the 18th edition is used, apply the procedure in paragraph (f)(5) of
this section for transferring a total coliform-positive culture to EC
medium supplemented with MUG, incubate the tube at 44.5 0.2 [deg]C for 24 2 hours, and
then observe fluorescence with an ultraviolet light (366 nm) in the
dark. If fluorescence is visible, E. coli are present.
(ii) Nutrient agar supplemented with 100 [micro]g/mL of 4-
methylumbelliferyl-beta-D-glucuronide (MUG) (final concentration), as
described in Method 9222G in Standard Methods for the Examination of
Water and Wastewater, 19th edition (1995) and 20th edition (1998).
Either edition may be used for determining if a total coliform-positive
sample, as determined by a membrane filter technique, contains E. coli.
Alternatively, the 18th edition (1992) may be used if the membrane
filter containing a total coliform-positive colony(ies) is transferred
to nutrient agar, as described in Method 9221B (paragraph 3) of Standard
Methods (18th edition), supplemented with 100 [micro]g/mL of MUG. If the
18th edition is used, incubate the agar plate at 35 [deg]C for 4 hours
and then observe the colony(ies) under ultraviolet light (366 nm) in the
dark for fluorescence. If fluorescence is visible, E. coli are present.
(iii) Minimal Medium ONPG-MUG (MMO-MUG) Test, as set forth in the
article ``National Field Evaluation of a Defined Substrate Method for
the Simultaneous Detection of Total Coliforms and Escherichia coli from
Drinking Water: Comparison with Presence-Absence Techniques'' (Edberg et
al.), Applied and Environmental Microbiology, Volume 55, pp. 1003-1008,
April 1989. (Note: The Autoanalysis Colilert System is an MMO-MUG test).
If the MMO-MUG test is total coliform-positive after a 24-hour
incubation, test the medium for fluorescence with a 366-nm ultraviolet
light (preferably with a 6-watt lamp) in the dark. If fluorescence is
observed, the sample is E. coli-positive. If fluorescence is
questionable (cannot be definitively read) after 24 hours incubation,
incubate the culture for an additional four hours (but not to exceed 28
hours total), and again test the medium for fluorescence. The MMO-MUG
Test with hepes buffer in lieu of phosphate buffer is the only approved
formulation for the detection of E. coli.
(iv) The Colisure Test. A description of the Colisure Test may be
obtained from the Millipore Corporation, Technical Services Department,
80 Ashby Road, Bedford, MA 01730.
(v) The membrane filter method with MI agar, a description of which
is cited in footnote 6 to the table in paragraph (f)(3) of this section.
(vi) E*Colite [reg] Test, a description of which is cited
in footnote 10 to the table at paragraph (f)(3) of this section.
(vii) m-ColiBlue24 [reg] Test, a description of which is
cited in footnote 11 to the table in paragraph (f)(3) of this section.
(viii) Readycult [reg] Coliforms 100 Presence/Absence
Test, a description of which is cited in footnote 13 to the table at
paragraph (f)(3) of this section.
(ix) Membrane Filter Technique using Chromocult [reg]
Coliform Agar, a description of which is cited in footnote 14 to the
table at paragraph (f)(3) of this section.
(x) Colitag [reg], a description of which is cited in
footnote 15 to the table at paragraph (f)(3) of this section.
(7) As an option to paragraph (f)(6)(iii) of this section, a system
with a total coliform-pos i tive, MUG-negative, MMO-MUG test may further
analyze the culture for the presence of E. coli by transferring a 0.1
ml, 28-hour MMO-MUG culture to EC Medium + MUG with a pipet. The
formulation and incubation conditions of EC Medium + MUG, and
observation of the results are described in paragraph (f)(6)(i) of this
section.
(8) The following materials are incorporated by reference in this
section with the approval of the Director of the Federal Register in
accordance with 5 U.S.C. 552(a) and 1 CFR part 51. Copies of the
analytical methods cited in Standard Methods for the Examination of
Water and Wastewater (18th, 19th, and 20th editions) may be obtained
from the American Public Health Association et al.; 1015 Fifteenth
Street, NW., Washington, DC 20005-2605. Copies of the MMO-MUG Test, as
set forth in the article ``National Field Evaluation of a Defined
Substrate Method for the Simultaneous Enumeration of Total Coliforms and
Escherichia coli from
[[Page 361]]
Drinking Water: Comparison with the Standard Multiple Tube Fermentation
Method'' (Edberg et al.) may be obtained from the American Water Works
Association Research Foundation, 6666 West Quincy Avenue, Denver, CO
80235. Copies of the MMO-MUG Test as set forth in the article ``National
Field Evaluation of a Defined Substrate Method for the Simultaneous
Enumeration of Total Coliforms and Escherichia coli from Drinking Water:
Comparison with the Standard Multiple Tube Fermentation Method'' (Edberg
et al.) may be obtained from the American Water Works Association
Research Foundation, 6666 West Quincy Avenue, Denver, CO 80235. A
description of the Colisure Test may be obtained from the Millipore
Corp., Technical Services Department, 80 Ashby Road, Bedford, MA 01730.
Copies may be inspected at EPA's Drinking Water Docket; 401 M St., SW.;
Washington, DC 20460, or at the National Archives and Records
Administration (NARA). For information on the availability of this
material at NARA, call 202-741-6030, or go to: http://www.archives.gov/
federal--register/code--of--federal--regulations/ibr--locations.html.
(g) Response to violation. (1) A pub lic water system which has
exceeded the MCL for total coliforms in Sec. 141.63 must report the
violation to the State no later than the end of the next busi ness day
after it learns of the violation, and notify the public in accordance
with subpart Q.
(2) A public water system which has failed to comply with a coliform
monitoring requirement, including the sanitary survey requirement, must
report the monitoring violation to the State within ten days after the
system discovers the violation, and notify the public in accordance with
subpart Q.
[54 FR 27562, June 29, 1989, as amended at 54 FR 30001, July 17, 1989;
55 FR 25064, June 19, 1990; 56 FR 642, Jan. 8, 1991; 57 FR 1852, Jan.
15, 1992; 57 FR 24747, June 10, 1992; 59 FR 62466, Dec. 5, 1994; 60 FR
34085, June 29, 1995; 64 FR 67461, Dec. 1, 1999; 65 FR 26022, May 4,
2000; 67 FR 65246, Oct. 23, 2002; 67 FR 65896, Oct. 29, 2002; 69 FR
7160, Feb. 13, 2004]
Sec. 141.22 Turbidity sampling and analytical requirements.
The requirements in this section apply to unfiltered systems until
December 30, 1991, unless the State has determined prior to that date,
in writing pursuant to section 1412(b)(7)(iii), that filtration is
required. The requirements in this section apply to filtered systems
until June 29, 1993. The requirements in this section apply to
unfiltered systems that the State has determined, in writing pursuant to
section 1412(b)(7)(C)(iii), must install filtration, until June 29,
1993, or until filtration is installed, whichever is later.
(a) Samples shall be taken by suppliers of water for both community
and non-community water systems at a representative entry point(s) to
the water distribution system at least once per day, for the purposes of
making turbidity measurements to determine compliance with Sec. 141.13.
If the State determines that a reduced sampling frequency in a non-
community will not pose a risk to public health, it can reduce the
required sampling frequency. The option of reducing the turbidity
frequency shall be permitted only in those public water systems that
practice disinfection and which maintain an active residual disinfectant
in the distribution system, and in those cases where the State has
indicated in writing that no unreasonable risk to health existed under
the circumstances of this option. Turbidity measurements shall be made
as directed in Sec. 141.74(a)(1).
(b) If the result of a turbidity analysis indicates that the maximum
allowable limit has been exceeded, the sampling and measurement shall be
confirmed by resampling as soon as practicable and preferably within one
hour. If the repeat sample confirms that the maximum allowable limit has
been exceeded, the supplier of water shall report to the State within 48
hours. The repeat sample shall be the sample used for the purpose of
calculating the monthly average. If the monthly average of the daily
samples exceeds the maximum allowable limit, or if the average of two
samples taken on consecutive days exceeds 5 TU, the supplier of water
shall report to the State and notify the public as directed in
Sec. Sec. 141.31 and subpart Q.
[[Page 362]]
(c) Sampling for non-community water systems shall begin within two
years after the effective date of this part.
(d) The requirements of this Sec. 141.22 shall apply only to public
water systems which use water obtained in whole or in part from surface
sources.
(e) The State has the authority to determine compliance or initiate
enforcement action based upon analytical results or other information
compiled by their sanctioned representatives and agencies.
[40 FR 59570, Dec. 24, 1975, as amended at 45 FR 57344, Aug. 27, 1980;
47 FR 8998, Mar. 3, 1982; 47 FR 10998, Mar. 12, 1982; 54 FR 27527, June
29, 1989; 59 FR 62466, Dec. 5, 1994; 65 FR 26022, May 4, 2000]
Sec. 141.23 Inorganic chemical sampling and analytical requirements.
Community water systems shall conduct monitoring to determine
compliance with the maximum contaminant levels specified in Sec. 141.62
in accordance with this section. Non-transient, non-community water
systems shall conduct monitoring to determine compliance with the
maximum contaminant levels specified in Sec. 141.62 in accordance with
this section. Transient, non-community water systems shall conduct
monitoring to determine compliance with the nitrate and nitrite maximum
contaminant levels in Sec. Sec. 141.11 and 141.62 (as appropriate) in
accordance with this section.
(a) Monitoring shall be conducted as follows:
(1) Groundwater systems shall take a minimum of one sample at every
entry point to the distribution system which is representative of each
well after treatment (hereafter called a sampling point) beginning in
the initial compliance period. The system shall take each sample at the
same sampling point unless conditions make another sampling point more
representative of each source or treatment plant.
(2) Surface water systems shall take a minimum of one sample at
every entry point to the distribution system after any application of
treatment or in the distribution system at a point which is
representative of each source after treatment (hereafter called a
sampling point) beginning in the initial compliance period. The system
shall take each sample at the same sampling point unless conditions make
another sampling point more representative of each source or treatment
plant.
Note: For purposes of this paragraph, surface water systems include
systems with a combination of surface and ground sources.
(3) If a system draws water from more than one source and the
sources are combined before distribution, the system must sample at an
entry point to the distribution system during periods of normal
operating conditions (i.e., when water is representative of all sources
being used).
(4) The State may reduce the total number of samples which must be
analyzed by allowing the use of compositing. Composite samples from a
maximum of five samples are allowed, provided that the detection limit
of the method used for analysis is less than one-fifth of the MCL.
Compositing of samples must be done in the laboratory.
(i) If the concentration in the composite sample is greater than or
equal to one-fifth of the MCL of any inorganic chemical, then a follow-
up sample must be taken within 14 days at each sampling point included
in the composite. These samples must be analyzed for the contaminants
which exceeded one-fifth of the MCL in the composite sample. Detection
limits for each analytical method and MCLs for each inorganic
contaminant are the following:
Detection Limits for Inorganic Contaminants
------------------------------------------------------------------------
Detection
Contaminant MCL (mg/l) Methodology limit (mg/l)
------------------------------------------------------------------------
Antimony.................. 0.006...... Atomic 0.003
Absorption;
Furnace.
Atomic 0.0008 \5\
Absorption;
Platform.
ICP-Mass 0.0004
Spectrometry.
Hydride-Atomic 0.001
Absorption.
Arsenic................... 0.010 \6\.. Atomic 0.001
Absorption;
Furnace.
Atomic 0.0005 \7\
Absorption;
Platform--Stabi
lized
Temperature.
[[Page 363]]
Atomic 0.001
Absorption;
Gaseous Hydride.
ICP-Mass 0.0014 \8\
Spectrometry.
Asbestos.................. 7 MFL \1\.. Transmission 0.01 MFL
Electron
Microscopy.
Barium.................... 2.......... Atomic 0.002
Absorption;
furnace
technique.
Atomic 0.1
Absorption;
direct
aspiration.
Inductively 0.002 (0.001)
Coupled Plasma.
Beryllium................. 0.004...... Atomic 0.0002
Absorption;
Furnace.
Atomic 0.00002 \5\
Absorption;
Platform.
Inductively 0.0003
Coupled Plasma
\2\.
ICP-Mass 0.0003
Spectrometry.
Cadmium................... 0.005...... Atomic 0.0001
Absorption;
furnace
technique.
Inductively 0.001
Coupled Plasma.
Chromium.................. 0.1........ Atomic 0.001
Absorption;
furnace
technique.
Inductively 0.007 (0.001)
Coupled Plasma.
Cyanide................... 0.2........ Distillation, 0.02
Spectrophotomet
ric \3\.
........... Distillation, 0.005
Automated,
Spectrophotomet
ric \3\.
........... Distillation, 0.02
Amenable,
Spectrophotomet
ric \4\.
........... Distillation, 0.05
Selective
Electrode \3\.
........... UV, 0.0005
Distillation,
Spectrophotomet
ric.
........... Distillation, 0.0006
Spectrophotomet
ric.
Mercury................... 0.002...... Manual Cold 0.0002
Vapor Technique.
Automated Cold 0.0002
Vapor Technique.
Nickel.................... xl......... Atomic 0.001
Absorption;
Furnace.
Atomic 0.0006 \5\
Absorption;
Platform.
Inductively 0.005
Coupled Plasma
\2\.
ICP-Mass 0.0005
Spectrometry.
Nitrate................... 10 (as N).. Manual Cadmium 0.01
Reduction.
Automated 0.01
Hydrazine
Reduction.
Automated 0.05
Cadmium
Reduction.
Ion Selective 1
Electrode.
Ion 0.01
Chromatography.
Nitrite................... 1 (as N)... Spectrophotometr 0.01
ic.
Automated 0.05
Cadmium
Reduction.
Manual Cadmium 0.01
Reduction.
Ion 0.004
Chromatography.
Selenium.................. 0.05....... Atomic 0.002
Absorption;
furnace.
Atomic 0.002
Absorption;
gaseous hydride.
Thallium.................. 0.002...... Atomic 0.001
Absorption;
Furnace.
Atomic 0.0007 \5\
Absorption;
Platform.
ICP-Mass 0.0003
Spectrometry.
------------------------------------------------------------------------
\1\ MFL = million fibers per liter 10 [micro]m.
\2\ Using a 2X preconcentration step as noted in Method 200.7. Lower
MDLs may be achieved when using a 4X preconcentration.
\3\ Screening method for total cyanides.
\4\ Measures ``free'' cyanides.
\5\ Lower MDLs are reported using stabilized temperature graphite
furnace atomic absorption.
\6\ The value for arsenic is effective January 23, 2006. Unit then, the
MCL is 0.05 mg/L.
\7\ The MDL reported for EPA method 200.9 (Atomic Absorption; Platform--
Stablized Temperature) was determined using a 2x concentration step
during sample digestion. The MDL determined for samples analyzed using
direct analyses (i.e., no sample digestion) will be higher. Using
multiple depositions, EPA 200.9 is capable of obtaining MDL of 0.0001
mg/L.
\8\ Using selective ion monitoring, EPA Method 200.8 (ICP-MS) is capable
of obtaining a MDL of 0.0001 mg/L.
(ii) If the population served by the system is 3,300
persons, then composit ing may only be permitted by the State at
sampling points within a single system. In systems serving <=3,300
persons, the State may permit compositing among different systems
provided the 5-sample limit is maintained.
(iii) If duplicates of the original sample taken from each sampling
point used in the composite sample are available, the system may use
these instead of resampling. The duplicates must be analyzed and the
results reported to the State within 14 days after completing analysis
of the composite sample, provided the holding time of the sample is not
exceeded.
(5) The frequency of monitoring for asbestos shall be in accordance
with paragraph (b) of this section: the frequency of monitoring for
antimony, arsenic, barium, beryllium, cadmium, chromium, cyanide,
fluoride, mercury, nickel, selenium and thallium shall be in accordance
with paragraph (c) of
[[Page 364]]
this section; the frequency of monitoring for nitrate shall be in
accordance with paragraph (d) of this section; and the frequency of
monitoring for nitrite shall be in accordance with paragraph (e) of this
section.
(b) The frequency of monitoring conducted to determine compliance
with the maximum contaminant level for asbestos specified in Sec.
141.62(b) shall be conducted as follows:
(1) Each community and non-transient, non-community water system is
required to monitor for asbestos during the first three-year compliance
period of each nine-year compliance cycle beginning in the compliance
period starting January 1, 1993.
(2) If the system believes it is not vulnerable to either asbestos
contamination in its source water or due to corrosion of asbestos-cement
pipe, or both, it may apply to the State for a waiver of the monitoring
requirement in paragraph (b)(1) of this section. If the State grants the
waiver, the system is not required to monitor.
(3) The State may grant a waiver based on a consideration of the
following factors:
(i) Potential asbestos contamination of the water source, and
(ii) The use of asbestos-cement pipe for finished water distribution
and the corrosive nature of the water.
(4) A waiver remains in effect until the completion of the three-
year compliance period. Systems not receiving a waiver must monitor in
accordance with the provisions of paragraph (b)(1) of this section.
(5) A system vulnerable to asbestos contamination due solely to
corrosion of asbestos-cement pipe shall take one sample at a tap served
by asbestos-cement pipe and under conditions where asbestos
contamination is most likely to occur.
(6) A system vulnerable to asbestos contamination due solely to
source water shall monitor in accordance with the provision of paragraph
(a) of this section.
(7) A system vulnerable to asbestos contamination due both to its
source water supply and corrosion of asbestos-cement pipe shall take one
sample at a tap served by asbestos-cement pipe and under conditions
where asbestos contamination is most likely to occur.
(8) A system which exceeds the maximum contaminant levels as
determined in Sec. 141.23(i) of this section shall monitor quarterly
beginning in the next quarter after the violation occurred.
(9) The State may decrease the quarterly monitoring requirement to
the frequency specified in paragraph (b)(1) of this section pro vided
the State has determined that the sys tem is reliably and consistently
below the maximum contaminant level. In no case can a State make this de
term i na tion unless a groundwater system takes a minimum of two
quarterly samples and a surface (or combined surface/ground) water
system takes a minimum of four quarterly samples.
(10) If monitoring data collected after January 1, 1990 are
generally consistent with the requirements of Sec. 141.23(b), then the
State may allow systems to use that data to satisfy the monitoring
requirement for the initial compliance period beginning January 1, 1993.
(c) The frequency of monitoring conducted to determine compliance
with the maximum contaminant levels in Sec. 141.62 for antimony,
arsenic, barium, beryllium, cadmium, chromium, cyanide, fluoride,
mercury, nickel, selenium and thallium shall be as follows:
(1) Groundwater systems shall take one sample at each sampling point
during each compliance period. Surface water systems (or combined
surface/ground) shall take one sample annually at each sampling point.
(2) The system may apply to the State for a waiver from the
monitoring frequencies specified in paragraph (c)(1) of this section.
States may grant a public water system a waiver for monitoring of
cyanide, provided that the State determines that the system is not
vulnerable due to lack of any industrial source of cyanide.
(3) A condition of the waiver shall require that a system shall take
a minimum of one sample while the waiver is effective. The term during
which the waiver is effective shall not exceed one compliance cycle
(i.e., nine years).
[[Page 365]]
(4) The State may grant a waiver provided surface water systems have
monitored annually for at least three years and groundwater systems have
conducted a minimum of three rounds of monitoring. (At least one sample
shall have been taken since January 1, 1990). Both surface and
groundwater systems shall demonstrate that all previous analytical
results were less than the maximum contaminant level. Systems that use a
new water source are not eligible for a waiver until three rounds of
monitoring from the new source have been completed.
(5) In determining the appropriate reduced monitoring frequency, the
State shall consider:
(i) Reported concentrations from all previous monitoring;
(ii) The degree of variation in reported concentrations; and
(iii) Other factors which may affect contaminant concentrations such
as changes in groundwater pumping rates, changes in the system's
configuration, changes in the system's operating procedures, or changes
in stream flows or characteristics.
(6) A decision by the State to grant a waiver shall be made in
writing and shall set forth the basis for the determination. The
determination may be initiated by the State or upon an application by
the public water system. The public water system shall specify the basis
for its request. The State shall review and, where appropriate, revise
its determination of the appropriate monitoring frequency when the
system submits new monitoring data or when other data relevant to the
system's appropriate monitoring frequency become available.
(7) Systems which exceed the maximum contaminant levels as
calculated in Sec. 141.23(i) of this section shall monitor quarterly
beginning in the next quarter after the violation occurred.
(8) The State may decrease the quarterly monitoring requirement to
the frequencies specified in paragraphs (c)(1) and (c)(2) of this
section provided it has determined that the system is reliably and
consistently below the maximum contaminant level. In no case can a State
make this determination unless a groundwater system takes a minimum of
two quarterly samples and a surface water system takes a minimum of four
quarterly samples.
(9) All new systems or systems that use a new source of water that
begin operation after January 22, 2004 must demonstrate compliance with
the MCL within a period of time specified by the State. The system must
also comply with the initial sampling frequencies specified by the State
to ensure a system can demonstrate compliance with the MCL. Routine and
increased monitoring frequencies shall be conducted in accordance with
the requirements in this section.
(d) All public water systems (community; non-transient, non-
community; and transient, non-community systems) shall monitor to
determine compliance with the maximum contaminant level for nitrate in
Sec. 141.62.
(1) Community and non-transient, non-community water systems served
by groundwater systems shall monitor annually beginning January 1, 1993;
systems served by surface water shall monitor quarterly beginning
January 1, 1993.
(2) For community and non-transient, non-community water systems,
the repeat monitoring frequency for groundwater systems shall be
quarterly for at least one year following any one sample in which the
concentration is =50 percent of the MCL. The State may allow
a groundwater system to reduce the sampling frequency to annually after
four consecutive quarterly samples are reliably and consistently less
than the MCL.
(3) For community and non-transient, non-community water systems,
the State may allow a surface water system to reduce the sampling
frequency to annually if all analytical results from four consecutive
quarters are <50 percent of the MCL. A surface water system shall return
to quarterly monitoring if any one sample is =50 percent of
the MCL.
(4) Each transient non-community water system shall monitor annually
beginning January 1, 1993.
[[Page 366]]
(5) After the initial round of quarterly sampling is completed, each
community and non-transient non-community system which is monitoring
annually shall take subsequent samples during the quarter(s) which
previously resulted in the highest analytical result.
(e) All public water systems (community; non-transient, non-
community; and transient, non-community systems) shall monitor to
determine compliance with the maximum contaminant level for nitrite in
Sec. 141.62(b).
(1) All public water systems shall take one sample at each sampling
point in the compliance period beginning January 1, 1993 and ending
December 31, 1995.
(2) After the initial sample, systems where an analytical result for
nitrite is <50 percent of the MCL shall monitor at the frequency
specified by the State.
(3) For community, non-transient, non-community, and transient non-
community water systems, the repeat monitoring frequency for any water
system shall be quarterly for at least one year following any one sample
in which the concentration is [gteqt]50 percent of the MCL. The State
may allow a system to reduce the sampling frequency to annually after
determining the system is reliably and consistently less than the MCL.
(4) Systems which are monitoring annually shall take each subsequent
sample during the quarter(s) which previously resulted in the highest
analytical result.
(f) Confirmation samples:
(1) Where the results of sampling for antimony, arsenic, asbestos,
barium, beryllium, cadmium, chromium, cyanide, fluoride, mercury,
nickel, selenium or thallium indicate an exceedance of the maximum
contaminant level, the State may require that one additional sample be
collected as soon as possible after the initial sample was taken (but
not to exceed two weeks) at the same sampling point.
(2) Where nitrate or nitrite sampling results indicate an exceedance
of the maximum contaminant level, the system shall take a confirmation
sample within 24 hours of the system's receipt of notification of the
analytical results of the first sample. Systems unable to comply with
the 24-hour sampling requirement must immediately notify persons served
by the public water system in accordance with Sec. 141.202 and meet
other Tier 1 public notification requirements under Subpart Q of this
part. Systems exercising this option must take and analyze a
confirmation sample within two weeks of notification of the analytical
results of the first sample.
(3) If a State-required confirmation sample is taken for any
contaminant, then the results of the initial and confirmation sample
shall be aver aged. The resulting average shall be used to determine the
system's compliance in accordance with paragraph (i) of this section.
States have the discretion to delete results of obvious sampling errors.
(g) The State may require more frequent monitoring than specified in
paragraphs (b), (c), (d) and (e) of this section or may require
confirmation samples for positive and negative results at its
discretion.
(h) Systems may apply to the State to conduct more frequent
monitoring than the minimum monitoring frequencies specified in this
section.
(i) Compliance with Sec. Sec. 141.11 or 141.62(b) (as appropriate)
shall be determined based on the analytical result(s) obtained at each
sampling point.
(1) For systems which are conducting monitoring at a frequency
greater than annual, compliance with the maximum contaminant levels for
antimony, arsenic, asbestos, barium, beryllium, cadmium, chromium,
cyanide, fluoride, mercury, nickel, selenium or thallium is determined
by a running annual average at any sampling point. If the average at any
sampling point is greater than the MCL, then the system is out of
compliance. If any one sample would cause the annual average to be
exceeded, then the system is out of compliance immediately. Any sample
below the method detection limit shall be calculated at zero for the
purpose of determining the annual average. If a system fails to collect
the required number of samples, compliance (average concentration) will
be based on the total number of samples collected.
[[Page 367]]
(2) For systems which are monitoring annually, or less frequently,
the system is out of compliance with the maximum contaminant levels for
antimony, arsenic, asbestos, barium, beryllium, cadmium, chromium,
cyanide, fluoride, mercury, nickel, selenium or thallium if the level of
a contaminant is greater than the MCL. If confirmation samples are
required by the State, the determination of compliance will be based on
the annual average of the initial MCL exceedance and any State-required
confirmation samples. If a system fails to collect the required number
of samples, compliance (average concentration) will be based on the
total number of samples collected.
(3) Compliance with the maximum contaminant levels for nitrate and
nitrate is determined based on one sample if the levels of these
contaminants are below the MCLs. If the levels of nitrate and/or nitrite
exceed the MCLs in the initial sample, a confirmation sample is required
in accordance with paragraph (f)(2) of this section, and compliance
shall be determined based on the average of the initial and confirmation
samples.
(4) Arsenic sampling results will be reported to the nearest 0.001
mg/L.
(j) Each public water system shall monitor at the time designated by
the State during each compliance period.
(k) Inorganic analysis:
(1) Analysis for the following contaminants shall be conducted in
accordance with the methods in the following table, or their equivalent
as determined by EPA. Criteria for analyzing arsenic, barium, beryllium,
cadmium, calcium, chromium, copper, lead, nickel, selenium, sodium, and
thallium with digestion or directly without digestion, and other
analytical test procedures are contained in Technical Notes on Drinking
Water Methods, EPA-600/R-94-173, October 1994. This document also
contains approved analytical test methods which remain available for
compliance monitoring until July 1, 1996. These methods will not be
available for use after July 1, 1996. This document is available from
the National Technical Information Service, NTIS PB95-104766, U.S.
Department of Commerce, 5285 Port Royal Road, Springfield, Virginia
22161. The toll-free number is 800-553-6847.
----------------------------------------------------------------------------------------------------------------
Contaminant and methodology SM \4\ (18th, SM \4\ (20th
\13\ EPA ASTM \3\ 19th ed.) ed.) Other
----------------------------------------------------------------------------------------------------------------
1. Alkalinity:
Titrimetric................. .............. D1067--92B.... 2320 B........ 2320 B
Electrometric titration..... .............. .............. .............. .............. I-1030-85 \5\
2. Antimony:
Inductively Coupled Plasma 200.8 \2\.....
(ICP)--Mass Spectrometry.
Hydride-Atomic Absorption... .............. D3697-92
Atomic Absorption; Platform. 200.9 \2\
Atomic Absorption; Furnace.. .............. .............. 3113 B
3. Arsenic: \14\
Inductively Coupled Plasma 200.7 \2\..... .............. 3120 B........ 3120 B
\15\.
ICP-Mass Spectrometry....... 200.8 \2\.....
Atomic Absorption; Platform. 200.9 \2\.....
Atomic Absorption; Furnace.. .............. D2972-97C..... 3113 B
Hydride Atomic Absorption... .............. D2972-97B..... 3114 B
4. Asbestos:
Transmission Electron 100.1 \9\.....
Microscopy.
Transmission Electron 100.2 \10\....
Microscopy.
5. Barium:
Inductively Coupled Plasma.. 200.7 \2\..... .............. 3120 B........ 3120 B
ICP-Mass Spectrometry....... 200.8 \2\.....
Atomic Absorption; Direct... .............. .............. 3111 D
Atomic Absorption; Furnace.. .............. .............. 3113 B
6. Beryllium:
Inductively Coupled Plasma.. 200.7 \2\..... .............. 3120 B........ 3120 B
ICP-Mass Spectrometry....... 200.8 \2\.....
Atomic Absorption; Platform. 200.9 \2\.....
Atomic Absorption; Furnace.. .............. D3645--97B.... 3113 B
[[Page 368]]
7. Cadmium:
Inductively Coupled Plasma.. 200.7 \2\
ICP-Mass Spectrometry....... 200.8 \2\
Atomic Absorption; Platform. 200.9 \2\
Atomic Absorption; Furnace.. .............. .............. 3113 B........
8. Calcium:
EDTA titrimetric............ .............. D511--93A..... 3500-Ca D..... 3500-Ca B.....
Atomic Absorption; Direct .............. D511--93B..... 3111 B........
Aspiration.
Inductively Coupled Plasma.. 200.7 \2\..... .............. 3120 B........ 3120 B........
9. Chromium:
Inductively Coupled Plasma.. 200.7 \2\..... .............. 3120 B........ 3120 B........
ICP-Mass Spectrometry....... 200.8 \2\.....
Atomic Absorption; Platform. 200.9 \2\.....
Atomic Absorption; Furnace.. .............. .............. 3113 B........
10. Copper:
Atomic Absorption; Furnace.. .............. D1688-95C..... 3113 B........
Atomic Absorption; Direct .............. D1688-95A..... 3111 B........
Aspiration.
Inductively Coupled Plasma.. 200.7 \2\..... .............. 3120 B........ 3120 B........
ICP-Mass spectrometry....... 200.8 \2\.....
Atomic Absorption; Platform. 200.9 \2\.....
11. Conductivity:
Conductance................. .............. D1125-95A..... 2510 B........ 2510 B........
12. Cyanide:
Manual Distillation followed .............. D2036-98A..... 4500-CN- C.... 4500-CN- C....
by.
Spectrophotometric .............. D2036-98A..... 4500-CN- E.... 4500-CN- E.... I-3300-85 \5\
Manual.
Spectrophotometric Semi- 335.4 \6\.....
automated.
Spectrophotometric, .............. D2036-98B..... 4500-CN- G.... 4500-CN- G....
Amenable.
Selective Electrode......... .............. .............. 4500-CN- F.... 4500-CN- F....
UV/Distillation/ .............. .............. .............. .............. Kelada 01 \17\
Spectrophotometric.
Distillation/ .............. .............. .............. .............. QuikChem 10-
Spectrophotometric. 204-00-1-X
\18\
13. Fluoride:
Ion Chromatography.......... 300.0 \6\..... D4327-97...... 4110 B........ 4110 B........
Manual Distill.; Color. .............. .............. 4500-F- B,D... 4500-F- B,D... ..............
SPADNS.
Manual Electrode............ .............. D1179-93B..... 4500-F- C..... 4500-F- C..... ..............
Automated Electrode......... .............. .............. .............. .............. 380-75WE \11\
Automated Alizarin.......... .............. .............. 4500-F- E..... 4500-F- E..... 29-71W \11\
14. Lead:
Atomic Absorption; Furnace.. .............. D3559-96D..... 3113 B........
ICP-Mass spectrometry....... 200.8 \2\.....
Atomic Absorption; Platform. 200.9 \2\.....
Differential Pulse Anodic .............. .............. .............. .............. Method 1001
Stripping Voltammetry. \16\
15. Magnesium:
Atomic Absorption........... .............. D511-93 B..... 3111 B........
ICP......................... 200.7 \2\..... .............. 3120 B........ 3120 B........
Complexation Titrimetric .............. D511-93 A..... 3500-Mg E..... 3500-Mg B.....
Methods.
16. Mercury:
Manual, Cold Vapor.......... 245.1 \2\..... D3223-97...... 3112 B........
Automated, Cold Vapor....... 245.2 \1\.....
ICP-Mass Spectrometry....... 200.8 \2\.....
17. Nickel:
Inductively Coupled Plasma.. 200.7 \2\..... .............. 3120 B........ 3120 B........
ICP-Mass Spectrometry....... 200.8 \2\.....
[[Page 369]]
Atomic Absorption; Platform. 200.9 \2\.....
Atomic Absorption; Direct... .............. .............. 3111 B........
Atomic Absorption; Furnace.. .............. .............. 3113 B........
18. Nitrate:
Ion Chromatography.......... 300.0 \6\..... D4327-97...... 4110 B........ 4110 B........ B-1011 \8\
Automated Cadmium Reduction. 353.2 \6\..... D3867-90A..... 4500-NO3- F... 4500-NO3- F...
Ion Selective Electrode..... .............. .............. 4500-NO3- D... 4500-NO3- D... 601 \7\
Manual Cadmium Reduction.... .............. D3867-90B..... 4500-NO3- E... 4500-NO3- E...
19. Nitrite:
Ion Chromatography.......... 300.0 \6\..... D4327-97...... 4110 B........ 4110 B........ B-1011 \8\
Automated Cadmium Reduction. 353.2 \6\..... D3867-90A..... 4500-NO3-..... 4500-NO3- F...
Manual Cadmium Reduction.... .............. D3867-90B..... 4500-NO3- E... 4500-NO3- E... ..............
Spectrophotometric.......... .............. .............. 4500-NO2- B... 4500- NO2- B..
20. Ortho-phosphate: \12\
Colorimetric, Automated, 365.1 \6\..... .............. 4500-P F...... 4500-P F......
Ascorbic Acid.
Colorimetric, ascorbic acid, .............. D515-88A...... 4500-P E...... 4500-P E......
single reagent.
Colorimetric .............. .............. .............. .............. I-1601-85 \5\
Phosphomolybdate;.
Automated-segmented .............. .............. .............. .............. I-2601-90 \5\
Flow;.
Automated Discrete...... .............. .............. .............. .............. I-2598-85 \5\
Ion Chromatography.......... 300.0 \6\..... D4327-97...... 4110 B........ 4110 B........
21. pH:
Electrometric............... 150.1 \1\..... D1293-95...... 4500-H+ B..... 4500-H+ B.....
150.2 \1\.....
22. Selenium:
Hydride-Atomic Absorption... .............. D3859-98A..... 3114 B........
ICP-Mass Spectrometry....... 200.8 \2\.....
Atomic Absorption; Platform. 200.9 \2\.....
Atomic Absorption; Furnace.. .............. D3859-98B..... 3113 B........
23. Silica:
Colorimetric, Molybdate .............. .............. .............. .............. I-1700-85 \5\
Blue;.
Automated-segmented Flow .............. .............. .............. .............. I-2700-85 \5\
Colorimetric................ .............. D859-95.......
Molybdosilicate............. .............. .............. 4500-Si D..... 4500-SiO2 C...
Heteropoly Blue............. .............. .............. 4500-Si E..... 4500-SiO2 D...
Automated for Molybdate- .............. .............. 4500-Si F..... 4500-SiO2 E...
reactive Silica.
Inductively Coupled Plasma.. 200.7 \2\..... .............. 3120 B........ 3120 B........
24. Sodium:
Inductively Coupled Plasma.. 200.7 \2\.....
Atomic Absorption; Direct .............. .............. 3111 B........
Aspiration.
25. Temperature:
Thermometric................ .............. .............. 2550.......... 2550..........
26. Thallium:
ICP-Mass Spectrometry....... 200.8 \2\.....
Atomic Absorption; Platform. 200.9 \2\.....
----------------------------------------------------------------------------------------------------------------
The procedures shall be done in accordance with the documents listed below. The incorporation by reference of
the following documents listed in footnotes 1-11 and 16 was approved by the Director of the Federal Register
in accordance with 5 U.S.C. 552(a) and 1 CFR part 51. Copies of the documents may be obtained from the sources
listed below. Information regarding obtaining these documents can be obtained from the Safe Drinking Water
Hotline at 800-426-4791. Documents may be inspected at EPA'sDrinking Water Docket, EPA West, 1301 Constitution
Avenue, NW, Room B135, Washington, DC (Telephone: 202-566-2426); or at the National Archives and Records
Administration (NARA). For information on the availability of this material at NARA, call 202-741-6030, or go
to: http://www.archives.gov/federal--register/code--of--federal--regulations/ibr--locations.html.
\1\ ``Methods for Chemical Analysis of Water and Wastes'', EPA/600/4-79/020, March 1983. Available at NTIS, PB84-
128677.
\2\ ``Methods for the Determination of Metals in Environmental Samples--Supplement I'', EPA/600/R-94/111, May
1994. Available at NTIS, PB95-125472.
[[Page 370]]
\3\ Annual Book of ASTM Standards, 1994, 1996, or 1999, Vols. 11.01 and 11.02, ASTM International; any year
containing the cited version of the method may be used. The previous versions of D1688-95A, D1688-95C
(copper), D3559-95D (lead), D1293-95 (pH), D1125-91A (conductivity) and D859-94 (silica) are also approved.
These previous versions D1688-90A, C; D3559-90D, D1293-84, D1125-91A and D859-88, respectively are located in
the Annual Book of ASTM Standards, 1994, Vol. 11.01. Copies may be obtained from ASTM International, 100 Barr
Harbor Drive, West Conshohocken, PA 19428.
\4\ Standard Methods for the Examination of Water and Wastewater, 18th edition (1992), 19th edition (1995), or
20th edition (1998). American Public Health Association, 1015 Fifteenth Street, NW, Washington, DC 20005. The
cited methods published in any of these three editions may be used, except that the versions of 3111 B, 3111
D, 3113 B and 3114 B in the 20th edition may not be used.
\5\ Method I-2601-90, Methods for Analysis by the U.S. Geological Survey National Water Quality Laboratory--
Determination of Inorganic and Organic Constituents in Water and Fluvial Sediment, Open File Report 93-125,
1993; For Methods I-1030-85; I-1601-85; I-1700-85; I-2598-85; I-2700-85; and I-3300-85 See Techniques of Water
Resources Investigation of the U.S. Geological Survey, Book 5, Chapter A-1, 3rd ed., 1989; Available from
Information Services, U.S. Geological Survey, Federal Center, Box 25286, Denver, CO 80225-0425.
\6\ ``Methods for the Determination of Inorganic Substances in Environmental Samples'', EPA/600/R-93/100, August
1993. Available at NTIS, PB94-120821.
\7\ The procedure shall be done in accordance with the Technical Bulletin 601 ``Standard Method of Test for
Nitrate in Drinking Water'', July 1994, PN 221890-001, Analytical Technology, Inc. Copies may be obtained from
ATI Orion, 529 Main Street, Boston, MA 02129.
\8\ Method B-1011, ``Waters Test Method for Determination of Nitrite/Nitrate in Water Using Single Column Ion
Chromatography,'' August 1987. Copies may be obtained from Waters Corporation, Technical Services Division, 34
Maple Street, Milford, MA 01757.
\9\ Method 100.1, ``Analytical Method For Determination of Asbestos Fibers in Water'', EPA/600/4-83/043, EPA,
September 1983. Available at NTIS, PB83-260471.
\10\ Method 100.2, ``Determination of Asbestos Structure Over 10 [micro]m In Length In Drinking Water'', EPA/600/
R-94/134, June 1994. Available at NTIS, PB94-201902.
\11\ Industrial Method No. 129-71W, ``Fluoride in Water and Wastewater'', December 1972, and Method No. 380-
75WE, ``Fluoride in Water and Wastewater'', February 1976, Technicon Industrial Systems. Copies may be
obtained from Bran & Luebbe, 1025 Busch Parkway, Buffalo Grove, IL 60089.
\12\ Unfiltered, no digestion or hydrolysis.
\13\ Because MDLs reported in EPA Methods 200.7 and 200.9 were determined using a 2X preconcentration step
during sample digestion, MDLs determined when samples are analyzed by direct analysis (i.e., no sample
digestion) will be higher. For direct analysis of cadmium and arsenic by Method 200.7, and arsenic by Method
3120 B sample preconcentration using pneumatic nebulization may be required to achieve lower detection limits.
Preconcentration may also be required for direct analysis of antimony, lead, and thallium by Method 200.9;
antimony and lead by Method 3113 B; and lead by Method D3559-90D unless multiple in-furnace depositions are
made.
\14\ If ultrasonic nebulization is used in the determination of arsenic by Methods 200.7, 200.8, or SM 3120 B,
the arsenic must be in the pentavalent state to provide uniform signal response. For methods 200.7 and 3120 B,
both samples and standards must be diluted in the same mixed acid matrix concentration of nitric and
hydrochloric acid with the addition of 100 [micro]L of 30% hydrogen peroxide per 100ml of solution. For direct
analysis of arsenic with method 200.8 using ultrasonic nebulization, samples and standards must contain one mg/
L of sodium hypochlorite.
\15\ Starting January 23, 2006, analytical methods using the ICP-AES technology, may not be used because the
detection limits for these methods are 0.008 mg/L or higher. This restriction means that the two ICP-AES
methods (EPA Method 200.7 and SM 3120 B) approved for use for the MCL of 0.05 mg/L may not be used for
compliance determinations for the revised MCL of 0.010 mg/L. However, prior to January 23, 2006, systems may
have compliance samples analyzed with these less sensitive methods.
\16\ The description for Method Number 1001 for lead is available from Palintest, LTD, 21 Kenton Lands Road,
P.O. Box 18395, Erlanger, KY 41018. Or from the Hach Company, P.O. Box 389, Loveland, CO 80539.
\17\ The description for the Kelada 01 Method, ``Kelada Automated Test Methods for Total Cyanide, Acid
Dissociable Cyanide, And Thiocyanate'', Revision 1.2, August 2001, EPA 821-B-01-009 for cyanide is
available from the National Technical Information Service (NTIS), PB 2001-108275, 5285 Port Royal Road,
Springfield, VA 22161. The toll free telephone number is 800-553-6847.
\18\ The description for the QuikChem Method 10-204-00-1-X, ``Digestion and distillation of total cyanide in
drinking and wastewaters using MICRO DIST and determination of cyanide by flow injection analysis'', Revision
2.1, November 30, 2000 for cyanide is available from Lachat Instruments, 6645 W. Mill Rd., Milwaukee, WI
53218, USA. Phone: 414-358-4200.
(2) Sample collection for antimony, arsenic, asbestos, barium,
beryllium, cadmium, chromium, cyanide, fluoride, mercury, nickel,
nitrate, nitrite, selenium, and thallium under this section shall be
conducted using the sample preservation, container, and maximum holding
time procedures specified in the table below:
------------------------------------------------------------------------
Container
Contaminant Preservative \1\ \2\ Time \3\
------------------------------------------------------------------------
Antimony..................... HNO\3\.......... P or G.... 6 months
Arsenic...................... Conc HNO3 to pH P or G.... 6 months
<2.
Asbestos..................... 4 [deg]C........ P or G.... 48 hours
\4\
Barium....................... HNO\3\.......... P or G.... 6 months
Beryllium.................... HNO\3\.......... P or G.... 6 months
Cadmium...................... HNO\3\.......... P or G.... 6 months
Chromium..................... HNO\3\.......... P or G.... 6 months
Cyanide...................... 4 [deg]C, NaOH.. P or G.... 14 days
Fluoride..................... None............ P or G.... 1 month
Mercury...................... HNO\3\.......... P or G.... 28 days
Nickel....................... HNO\3\.......... P or G.... 6 months
Nitrate...................... 4 [deg]C........ P or G.... 48 hours
\5\
Nitrate-Nitrite \6\.......... H\2\SO\4\....... P or G.... 28 days
Nitrite...................... 4[deg]C......... P or G.... 48 hours
Selenium..................... HNO\3\.......... P or G.... 6 months
Thallium..................... HNO\3\.......... P or G.... 6 months
------------------------------------------------------------------------
\1\ For cyanide determinations samples must be adjusted with sodium
hydroxide to pH 12 at the time off collection. When chilling is
indicated the sample must be shipped and stored at 4 [deg]C or less.
Acidification of nitrate or metals samples may be with a concentrated
acid or a dilute (50% by volume) solution of the applicable
concentrated acid. Acidification of samples for metals analysis is
encouraged and allowed at the laboratory rather than at the time of
sampling provided the shipping time and other instructions in Section
8.3 of EPA Methods 200.7 or 200.8 or 200.9 are followed.
\2\ P=plastic, hard or soft; G=glass, hard or soft.
\3\ In all cases samples should be analyzed as soon after collection as
possible. Follow additional (if any) information on preservation,
containers or holding times that is specified in method.
\4\ Instructions for containers, preservation procedures and holding
times as specified in Method 100.2 must be adhered to for all
compliance analyses including those conducted with Method 100.1.
[[Page 371]]
\5\ If the sample is chlorinated, the holding time for an unacidified
sample kept at 4 [deg]C is extended to 14 days.
\6\ Nitrate-Nitrite refers to a measurement of total nitrate.
(3) Analysis under this section shall only be conducted by
laboratories that have been certified by EPA or the State. Laboratories
may conduct sample analysis under provisional certification until
January 1, 1996. To receive certification to conduct analyses for
antimony, arsenic, asbestos, barium, beryllium, cadmium, chromium,
cyanide, fluoride, mercury, nickel, nitrate, nitrite and selenium and
thallium, the laboratory must:
(i) Analyze Performance Evaluation (PE) samples provided by EPA, the
State or by a third party (with the approval of the State or EPA) at
least once a year.
(ii) For each contaminant that has been included in the PE sample
and for each method for which the laboratory desires certification
achieve quantitative results on the analyses that are within the
following acceptance limits:
------------------------------------------------------------------------
Contaminant Acceptance limit
------------------------------------------------------------------------
Antimony............................ 30 at =0.006 mg/1
Arsenic............................. 30 at =0.003 mg/L
Asbestos............................ 2 standard deviations based on
study statistics.
Barium.............................. 15% at =0.15 mg/1
Beryllium........................... 15% at =0.001 mg/1
Cadmium............................. 20% at =0.002 mg/1
Chromium............................ 15% at =0.01 mg/1
Cyanide............................. 25% at =0.1 mg/1
Fluoride............................ 10% at =1 to 10 mg/1
Mercury............................. 30% at =0.0005 mg/1
Nickel.............................. 15% at =0.01 mg/1
Nitrate............................. 10% at =0.4 mg/1
Nitrite............................. 15% at =0.4 mg/1
Selenium............................ 20% at =0.01 mg/1
Thallium............................ 30% at =0.002 mg/1
------------------------------------------------------------------------
(l) Analyses for the purpose of determining compliance with Sec.
141.11 shall be conducted using the requirements specified in paragraphs
(l) through (q) of this section.
(1) Analyses for all community water systems utilizing surface water
sources shall be completed by June 24, 1978. These analyses shall be
repeated at yearly intervals.
(2) Analyses for all community water systems utilizing only ground
water sources shall be completed by June 24, 1979. These analyses shall
be repeated at three-year intervals.
(3) For non-community water systems, whether supplied by surface or
ground sources, analyses for nitrate shall be completed by December 24,
1980. These analyses shall be repeated at intervals determined by the
State.
(4) The State has the authority to determine compliance or initiate
enforcement action based upon analytical results and other information
compiled by their sanctioned representatives and agencies.
(m) If the result of an analysis made under paragraph (l) of this
section indicates that the level of any contaminant listed in Sec.
141.11 exceeds the maximum contaminant level, the supplier of the water
shall report to the State within 7 days and initiate three additional
analyses at the same sampling point within one month.
(n) When the average of four analyses made pursuant to paragraph (m)
of this section, rounded to the same number of significant figures as
the maximum contaminant level for the substance in question, exceeds the
maximum contaminant level, the supplier of water shall notify the State
pursuant to Sec. 141.31 and give notice to the public pursuant to
subpart Q. Monitoring after public notification shall be at a frequency
designated by the State and shall continue until the maximum contaminant
level has not been exceeded in two successive samples or until a
monitoring schedule as a condition to a variance, exemption or
enforcement action shall become effective.
(o) The provisions of paragraphs (m) and (n) of this section
notwithstanding, compliance with the maximum contaminant level for
nitrate shall be determined on the basis of the mean of two analyses.
When a level exceeding the maximum contaminant level for nitrate is
found, a second analysis shall be initiated within 24 hours, and if the
mean of the two analyses exceeds the maximum contaminant level, the
supplier of water shall report his findings to the State pursuant to
Sec. 141.31 and shall notify the public pursuant to subpart Q.
(p) For the initial analyses required by paragraph (l) (1), (2) or
(3) of this section, data for surface waters acquired within one year
prior to the effective date and data for ground waters
[[Page 372]]
acquired within 3 years prior to the effective date of this part may be
substituted at the discretion of the State.
(q) [Reserved]
[56 FR 3579, Jan. 30, 1991, as amended at 56 FR 30274, July 1, 1991; 57
FR 31838, July 17, 1992; 59 FR 34322, July 1, 1994; 59 FR 62466, Dec. 5,
1994; 60 FR 33932, 34085, June 29, 1995; 64 FR 67461, Dec. 1, 1999; 65
FR 26022, May 4, 2000; 66 FR 7061, Jan. 22, 2001; 67 FR 65246, Oct. 23,
2002; 67 FR 65897, Oct. 29, 2002; 67 FR 68911, Nov. 13, 2002; 68 FR
14506, Mar. 25, 2003]
Sec. 141.24 Organic chemicals, sampling and analytical requirements.
(a)-(d) [Reserved]
(e) Analyses for the contaminants in this section shall be conducted
using the following EPA methods or their equivalent as approved by EPA.
(1) The following documents are incorporated by reference. This
incorporation by reference was approved by the Director of the Federal
Register in accordance with 5 U.S.C. 552(a) and 1 CFR part 51. Copies
may be inspected at EPA's Drinking Water Docket, 1301 Constitution
Avenue, NW., EPA West, Room B102, Washington DC 20460 (Telephone: 202-
566-2426); or at the National Archives and Records Administration
(NARA). For information on the availability of this material at NARA,
call 202-741-6030, or go to: http://www.archives.gov/federal--register/
code--of--federal--regulations/ibr--locations.html. Method 508A and
515.1 are in Methods for the Determination of Organic Compounds in
Drinking Water, EPA/600/4-88-039, December 1988, Revised, July 1991.
Methods 547, 550 and 550.1 are in Methods for the Determination of
Organic Compounds in Drinking Water--Supplement I, EPA/600-4-90-020,
July 1990. Methods 548.1, 549.1, 552.1 and 555 are in Methods for the
Determination of Organic Compounds in Drinking Water--Supplement II,
EPA/600/R-92-129, August 1992. Methods 502.2, 504.1, 505, 506, 507, 508,
508.1, 515.2, 524.2, 525.2, 531.1, 551.1 and 552.2 are in Methods for
the Determination of Organic Compounds in Drinking Water--Supplement
III, EPA/600/R-95-131, August 1995. Method 1613 is titled ``Tetra-
through Octa-Chlorinated Dioxins and Furans by Isotope-Dilution HRGC/
HRMS'', EPA/821-B-94-005, October 1994. These documents are available
from the National Technical Information Service, NTIS PB91-231480, PB91-
146027, PB92-207703, PB95-261616 and PB95-104774, U.S. Department of
Commerce, 5285 Port Royal Road, Springfield, Virginia 22161. The toll-
free number is 800-553-6847. Method 6651 shall be followed in accordance
with Standard Methods for the Examination of Water and Wastewater, 18th
edition (1992), 19th edition (1995), or 20th edition (1998), American
Public Health Association (APHA); any of these three editions may be
used. Method 6610 shall be followed in accordance with Standard Methods
for the Examination of Water and Wastewater, (18th Edition Supplement)
(1994), or with the 19th edition (1995) or 20th edition (1998) of
Standard Methods for the Examination of Water and Wastewater; any of
these three editions may be used. The APHA documents are available from
APHA, 1015 Fifteenth Street NW., Washington, D.C. 20005. Other required
analytical test procedures germane to the conduct of these analyses are
contained in Technical Notes on Drinking Water Methods, EPA/600/R-94-
173, October 1994, NTIS PB95-104766. EPA Methods 515.3 and 549.2 are
available from U.S. Environmental Protection Agency, National Exposure
Research Laboratory (NERL)-Cincinnati, 26 West Martin Luther King Drive,
Cincinnati, OH 45268. ASTM Method D 5317-93 is available in the Annual
Book of ASTM Standards, (1999), Vol. 11.02, ASTM International, 100 Barr
Harbor Drive, West Conshohocken, PA 19428, or in any edition published
after 1993. EPA Method 515.4, ``Determination of Chlorinated Acids in
Drinking Water by Liquid-Liquid Microextraction, Derivatization and Fast
Gas Chromatography with Electron Capture Detection,'' Revision 1.0,
April 2000, EPA /815/B-00/001 can be accessed and downloaded directly
on-line at www.epa.gov/safewater/methods/sourcalt.html. The Syngenta AG-
625, ``Atrazine in Drinking Water by Immunoassay'', February 2001 is
available from Syngenta Crop Protection, Inc., 410 Swing Road, Post
Office Box 18300, Greensboro, NC 27419, Phone number (336) 632-6000.
Method 531.2 ``Measurement of N-methylcarbamoyloximes and N-
methylcarbamates in Water by Direct Aqueous Injection HPLC with
[[Page 373]]
Postcolumn Derivatization,'' Revision 1.0, September 2001, EPA 815/B/01/
002 can be accessed and downloaded directly on-line at www.epa.gov/
safewater/methods/sourcalt.html.
----------------------------------------------------------------------------------------------------------------
Contaminant EPA method 1 Standard methods ASTM Other
----------------------------------------------------------------------------------------------------------------
1. Benzene........................ 502.2, 524.2........
2. Carbon tetrachloride........... 502.2, 524.2, 551.1.
3. Chlorobenzene.................. 502.2, 524.2........
4. 1,2-Dichlorobenzene............ 502.2, 524.2........
5. 1,4-Dichlorobenzene............ 502.2, 524.2........
6. 1,2-Dichloroethane............. 502.2, 524.2........
7. cis-Dichloroethylene........... 502.2, 524.2........
8. trans-Dichloroethylene......... 502.2, 524.2........
9. Dichloromethane................ 502.2, 524.2........
10. 1,2-Dichloropropane........... 502.2, 524.2........
11. Ethylbenzene.................. 502.2, 524.2........
12. Styrene....................... 502.2, 524.2........
13. Tetrachloroethylene........... 502.2, 524.2, 551.1.
14. 1,1,1-Trichloroethane......... 502.2, 524.2, 551.1.
15. Trichloroethylene............. 502.2, 524.2, 551.1.
16. Toluene....................... 502.2, 524.2........
17. 1,2,4-Trichlorobenzene........ 502.2, 524.2........
18. 1,1-Dichloroethylene.......... 502.2, 524.2........
19. 1,1,2-Trichloroethane......... 502.2, 524.2, 551.1.
20. Vinyl chloride................ 502.2, 524.2........
21. Xylenes (total)............... 502.2, 524.2........
22. 2,3,7,8-TCDD (dioxin)......... 1613................
23. 2,4-D 4 (as acid, salts and 515.2, 555, 515.1, .................... D5317-93.......
esters). 515.3, 515.4.
24. 2,4,5-TP 4 (Silvex)........... 515.2, 555, 515.1, .................... D5317-93.......
515.3, 515.4.
25. Alachlor 2.................... 507, 525.2, 508.1,
505, 551.1.
26. Atrazine 2.................... 507, 525.2, 508.1, .................... ............... Syngenta AG-
505, 551.1. 625.
27. Benzo(a)pyrene................ 525.2, 550, 550.1...
28. Carbofuran.................... 531.1, 531.2........ 6610................
29. Chlordane..................... 508, 525.2, 508.1,
505.
30. Dalapon....................... 552.1, 515.1, 552.2,
515.3, 515.4.
31. Di(2-ethylhexyl)adipate....... 506, 525.2..........
32. Di(2-ethylhexyl)phthalate..... 506, 525.2..........
33. Dibromochloropropane (DBCP)... 504.1, 551.1........
34. Dinoseb 4..................... 515.2, 555, 515.1,
515.3, 515.4.
35. Diquat........................ 549.2...............
36. Endothall..................... 548.1...............
37. Endrin........................ 508, 525.2, 508.1,
505, 551.1.
38. Ethylene dibromide (EDB)...... 504.1, 551.1........
39. Glyphosate.................... 547................. 6651................
40. Heptachlor.................... 508, 525.2, 508.1,
505, 551.1.
41. Heptachlor Epoxide............ 508, 525.2, 508.1,
505, 551.1.
42. Hexachlorobenzene............. 508, 525.2, 508.1,
505, 551.1.
43. Hexachlorocyclopentadiene..... 508, 525.2, 508.1,
505, 551.1.
44. Lindane....................... 508, 525.2, 508.1,
505, 551.1.
45. Methoxychlor.................. 508, 525.2, 508.1,
505, 551.1.
46. Oxamyl........................ 531.1, 531.2........ 6610................
47. PCBs 3 (as decachlorobiphenyl) 508A................
48. PCBs 3 (as Aroclors).......... 508.1, 508, 525.2,
505.
49. Pentachlorophenol............. 515.2, 525.2, 555, .................... D5317-93.......
515.1, 515.3, 515.4.
50. Picloram 4.................... 515.2, 555, 515.1, .................... D5317-93.......
515.3, 515.4.
51. Simazine 2.................... 507, 525.2, 508.1,
505, 551.1.
52. Toxaphene..................... 508, 508.1, 525.2,
505.
53. Total Trihalomethanes......... 502.2, 524.2, 551.1.
----------------------------------------------------------------------------------------------------------------
\1\ For previously approved EPA methods which remain available for compliance monitoring until June 1, 2001, see
paragraph (e)(2) of this section.
\2\ Substitution of the detector specified in Method 505, 507, 508 or 508.1 for the purpose of achieving lower
detection limits is allowed as follows. Either an electron capture or nitrogen phosphorous detector may be
used provided all regulatory requirements and quality control criteria are met.
\3\ PCBs are qualitatively identified as Aroclors and measured for compliance purposes as decachlorobiphenyl.
Users of Method 505 may have more difficulty in achieving the required detection limits than users of Methods
508.1, 525.2 or 508.
\4\ Accurate determination of the chlorinated esters requires hydrolysis of the sample as described in EPA
Methods 515.1, 515.2, 515.3, 515.4 and 555 and ASTM Method D5317-93.
(2) The following EPA methods will remain available for compliance
monitoring until June 1, 2001. The following
[[Page 374]]
documents are incorporated by reference. This incorporation by reference
was approved by the Director of the Federal Register in accordance with
5 U.S.C. 552(a) and 1 CFR Part 51. Copies may be inspected at EPA's
Drinking Water Docket, 401 M St., SW., Washington, DC 20460; or at the
National Archives and Records Administration (NARA). For information on
the availability of this material at NARA, call 202-741-6030, or go to:
http://www.archives.gov/federal--register/code--of--federal--
regulations/ibr--locations.html. EPA methods 502.2 Rev. 2.0, 505 Rev.
2.0, 507 Rev. 2.0, 508 Rev. 3.0, 531.1 Rev. 3.0 are in ``Methods for the
Determination of Organic Compounds in Drinking Water'', December 1988,
revised July 1991; methods 506 and 551 are in ``Methods for the
Determination of Organic Compounds in Drinking Water--Supplement I'',
July 1990; methods 515.2 Rev. 1.0 and 524.2 Rev. 4.0 are in ``Methods
for the Determination of Organic Compounds in Drinking Water--Supplement
II,'' August 1992; and methods 504.1 Rev. 1.0, 508.1 Rev. 1.0, 525.2
Rev.1.0 are available from US EPA NERL, Cincinnati, OH 45268
(f) Beginning with the initial compliance period, analysis of the
contaminants listed in Sec. 141.61(a) (1) through (21) for the purpose
of determining compliance with the maximum contaminant level shall be
conducted as follows:
(1) Groundwater systems shall take a minimum of one sample at every
entry point to the distribution system which is representative of each
well after treatment (hereafter called a sampling point). Each sample
must be taken at the same sampling point unless conditions make another
sampling point more representative of each source, treatment plant, or
within the distribution system.
(2) Surface water systems (or combined surface/ground) shall take a
minimum of one sample at points in the distribution system that are
representative of each source or at each entry point to the distribution
system after treatment (hereafter called a sampling point). Each sample
must be taken at the same sampling point unless conditions make another
sampling point more representative of each source, treatment plant, or
within the distribution system.
(3) If the system draws water from more than one source and the
sources are combined before distribution, the system must sample at an
entry point to the distribution system during periods of normal
operating conditions (i.e., when water representative of all sources is
being used).
(4) Each community and non-transient non-community water system
shall take four consecutive quarterly samples for each contaminant
listed in Sec. 141.61(a) (2) through (21) during each compliance
period, beginning in the initial compliance period.
(5) If the initial monitoring for contaminants listed in Sec.
141.61(a) (1) through (8) and the monitoring for the contaminants listed
in Sec. 141.61(a) (9) through (21) as allowed in paragraph (f)(18) has
been completed by December 31, 1992, and the system did not detect any
contaminant listed in Sec. 141.61(a) (1) through (21), then each ground
and surface water system shall take one sample annually beginning with
the initial compliance period.
(6) After a minimum of three years of annual sampling, the State may
allow groundwater systems with no previous detection of any contaiminant
listed in Sec. 141.61(a) to take one sample during each compliance
period.
(7) Each community and non-transient non-community ground water
system which does not detect a contaminant listed in Sec. 141.61(a) (1)
through (21) may apply to the State for a waiver from the requirements
of paragraphs (f)(5) and (f)(6) of this section after completing the
initial monitoring. (For purposes of this section, detection is defined
as =0.0005 mg/l.) A waiver shall be effective for no more
than six years (two compliance periods). States may also issue waivers
to small systems for the initial round of monitoring for 1,2,4-
trichlorobenzene.
(8) A State may grant a waiver after evaluating the following
factor(s):
(i) Knowledge of previous use (including transport, storage, or
disposal) of the contaminant within the watershed or zone of influence
of the system. If a determination by the State reveals no previous use
of the contaminant within
[[Page 375]]
the watershed or zone of influence, a waiver may be granted.
(ii) If previous use of the contaminant is unknown or it has been
used previously, then the following factors shall be used to determine
whether a waiver is granted.
(A) Previous analytical results.
(B) The proximity of the system to a potential point or non-point
source of contamination. Point sources include spills and leaks of
chemicals at or near a water treatment facility or at manufacturing,
distribution, or storage facilities, or from hazardous and municipal
waste landfills and other waste handling or treatment facilities.
(C) The environmental persistence and transport of the contaminants.
(D) The number of persons served by the public water system and the
proximity of a smaller system to a larger system.
(E) How well the water source is protected against contamination,
such as whether it is a surface or groundwater system. Groundwater
systems must consider factors such as depth of the well, the type of
soil, and wellhead protection. Surface water systems must consider
watershed protection.
(9) As a condition of the waiver a groundwater system must take one
sample at each sampling point during the time the waiver is effective
(i.e., one sample during two compliance periods or six years) and update
its vulnerability assessment considering the factors listed in paragraph
(f)(8) of this section. Based on this vulnerability assessment the State
must reconfirm that the system is non-vulnerable. If the State does not
make this reconfirmation within three years of the initial
determination, then the waiver is invalidated and the system is required
to sample annually as specified in paragraph (5) of this section.
(10) Each community and non-transient non-community surface water
system which does not detect a contaminant listed in Sec. 141.61(a) (1)
through (21) may apply to the State for a waiver from the requirements
of (f)(5) of this section after completing the initial monitoring.
Composite samples from a maximum of five sampling points are allowed,
provided that the detection limit of the method used for analysis is
less than one-fifth of the MCL. Systems meeting this criterion must be
determined by the State to be non-vulnerable based on a vulnerability
assessment during each compliance period. Each system receiving a waiver
shall sample at the frequency specified by the State (if any).
(11) If a contaminant listed in Sec. 141.61(a) (2) through (21) is
detected at a level exceeding 0.0005 mg/l in any sample, then:
(i) The system must monitor quarterly at each sampling point which
resulted in a detection.
(ii) The State may decrease the quarterly monitoring requirement spe
ci fied in paragraph (f)(11)(i) of this section provided it has
determined that the system is reliably and consistently below the
maximum contaminant level. In no case shall the State make this
determination unless a groundwater system takes a minimum of two
quarterly samples and a surface water system takes a minimum of four
quarterly samples.
(iii) If the State determines that the system is reliably and
consistently below the MCL, the State may allow the system to monitor
annually. Systems which monitor annually must monitor during the
quarter(s) which previously yielded the highest analytical result.
(iv) Systems which have three consecutive annual samples with no
detection of a contaminant may apply to the State for a waiver as
specified in paragraph (f)(7) of this section.
(v) Groundwater systems which have detected one or more of the
following two-carbon organic compounds: trichloroethylene,
tetrachloroethylene, 1,2-dichloroethane, 1,1,1-trichloroethane, cis-1,2-
dichloroethylene, trans-1,2-dichloroethylene, or 1,1-dichloroethylene
shall monitor quarterly for vinyl chloride. A vinyl chloride sample
shall be taken at each sampling point at which one or more of the two-
carbon organic compounds was detected. If the results of the first
analysis do not detect vinyl chloride, the State may reduce the
quarterly monitoring frequency of vinyl chloride monitoring to one
sample during each compliance period. Surface water systems
[[Page 376]]
are required to monitor for vinyl chloride as specified by the State.
(12) Systems which violate the requirements of Sec. 141.61(a) (1)
through (21), as determined by paragraph (f)(15) of this section, must
monitor quarterly. After a minimum of four consecutive quarterly samples
which show the system is in compliance as specified in paragraph (f)(15)
of this section the system and the State determines that the system is
reliably and consistently below the maximum contaminant level, the
system may monitor at the frequency and times specified in paragraph
(f)(11)(iii) of this section.
(13) The State may require a confirmation sample for positive or
negative results. If a confirmation sample is required by the State, the
result must be averaged with the first sampling result and the average
is used for the compliance determination as specified by paragraph
(f)(15). States have discretion to delete results of obvious sampling
errors from this calculation.
(14) The State may reduce the total number of samples a system must
analyze by allowing the use of compositing. Composite samples from a
maximum of five sampling points are allowed, provided that the detection
limit of the method used for analysis is less than one-fifth of the MCL.
Compositing of samples must be done in the laboratory and analyzed
within 14 days of sample collection.
(i) If the concentration in the composite sample is greater than or
equal to 0.0005 mg/l for any contaminant listed in Sec. 141.61(a), then
a follow-up sample must be taken within 14 days at each sampling point
included in the composite, and be analyzed for that contaminant.
(ii) If duplicates of the original sample taken from each sampling
point used in the composite sample are available, the system may use
these instead of resampling. The duplicates must be analyzed and the
results reported to the State within 14 days after completing analysis
of the composite sample, provided the holding time of the sample is not
exceeded.
(iii) If the population served by the system is 3,300
persons, then compositing may only be permitted by the State at sampling
points within a single system. In systems serving <= 3,300 persons, the
State may permit compositing among different systems provided the 5-
sample limit is maintained.
(iv) Compositing samples prior to GC analysis.
(A) Add 5 ml or equal larger amounts of each sample (up to 5 samples
are allowed) to a 25 ml glass syringe. Special precautions must be made
to maintain zero headspace in the syringe.
(B) The samples must be cooled at 4 [deg]C during this step to
minimize volatilization losses.
(C) Mix well and draw out a 5-ml aliquot for analysis.
(D) Follow sample introduction, purging, and desorption steps
described in the method.
(E) If less than five samples are used for compositing, a
proportionately small syringe may be used.
(v) Compositing samples prior to GC/MS analysis.
(A) Inject 5-ml or equal larger amounts of each aqueous sample (up
to 5 samples are allowed) into a 25-ml purging device using the sample
introduction technique described in the method.
(B) The total volume of the sample in the purging device must be 25
ml.
(C) Purge and desorb as described in the method.
(15) Compliance with Sec. 141.61(a) (1) through (21) shall be
determined based on the analytical results obtained at each sampling
point. If one sampling point is in violation of an MCL, the system is in
violation of the MCL.
(i) For systems monitoring more than once per year, compliance with
the MCL is determined by a running annual average at each sampling
point.
(ii) Systems monitoring annually or less frequently whose sample
result exceeds the MCL must begin quarterly sampling. The system will
not be considered in violation of the MCL until it has completed one
year of quarterly sampling.
(iii) If any sample result will cause the running annual average to
exceed the MCL at any sampling point, the system is out of compliance
with the MCL immediately.
(iv) If a system fails to collect the required number of samples,
compliance
[[Page 377]]
will be based on the total number of samples collected.
(v) If a sample result is less than the detection limit, zero will
be used to calculate the annual average.
(16) [Reserved]
(17) Analysis under this section shall only be conducted by
laboratories that are certified by EPA or the State according to the
following conditions (laboratories may conduct sample analysis under
provisional certification until January 1, 1996):
(i) To receive certification to conduct analyses for the
contaminants in Sec. 141.61(a) (2) through (21) the laboratory must:
(A) Analyze Performance Evaluation (PE) samples provided by EPA, the
State, or by a third party (with the approval of the State or EPA) at
least once a year by each method for which the laboratory desires
certification.
(B) Achieve the quantitative acceptance limits under paragraphs
(f)(17)(i)(C) and (D) of this section for at least 80 percent of the
regulated organic contaminants included in the PE sample.
(C) Achieve quantitative results on the analyses performed under
paragraph (f)(17)(i)(A) of this section that are within 20% of the actual amount of the substances in the
Performance Evaluation sample when the actual amount is greater than or
equal to 0.010 mg/l.
(D) Achieve quantitative results on the analyses performed under
paragraph (f)(17)(i)(A) of this section that are within 40 percent of the actual amount of the substances in the
Performance Evaluation sample when the actual amount is less than 0.010
mg/l.
(E) Achieve a method detection limit of 0.0005 mg/l, according to
the procedures in appendix B of part 136.
(ii) To receive certification to conduct analyses for vinyl
chloride, the laboratory must:
(A) Analyze Performance Evaluation (PE) samples provided by EPA, the
State, or by a third party (with the approval of the State or EPA) at
least once a year by each method for which the laboratory desires
certification.
(B) Achieve quantitative results on the analyses performed under
paragraph (f)(17)(ii)(A) of this section that are within 40 percent of the actual amount of vinyl chloride in the
Performance Evaluation sample.
(C) Achieve a method detection limit of 0.0005 mg/l, according to
the procedures in appendix B of part 136.
(D) Obtain certification for the contaminants listed in Sec.
141.61(a)(2) through (21).
(18) States may allow the use of monitoring data collected after
January 1, 1988, required under section 1445 of the Act for purposes of
initial monitoring compliance. If the data are generally consistent with
the other requirements of this section, the State may use these data
(i.e., a single sample rather than four quarterly samples) to satisfy
the initial monitoring requirement of paragraph (f)(4) of this section.
Systems which use grandfathered samples and did not detect any
contaminant listed Sec. 141.61(a)(2) through (21) shall begin
monitoring annually in accordance with paragraph (f)(5) of this section
beginning with the initial compliance period.
(19) States may increase required monitoring where necessary to
detect variations within the system.
(20) Each certified laboratory must determine the method detection
limit (MDL), as defined in appendix B to part 136, at which it is
capable of detecting VOCs. The acceptable MDL is 0.0005 mg/l. This
concentration is the detection concentration for purposes of this
section.
(21) Each public water system shall monitor at the time designated
by the State within each compliance period.
(22) All new systems or systems that use a new source of water that
begin operation after January 22, 2004 must demonstrate compliance with
the MCL within a period of time specified by the State. The system must
also comply with the initial sampling frequencies specified by the State
to ensure a system can demonstrate compliance with the MCL. Routine and
increased monitoring frequencies shall be conducted in accordance with
the requirements in this section.
(g) [Reserved]
[[Page 378]]
(h) Analysis of the contaminants listed in Sec. 141.61(c) for the
purposes of determining compliance with the maximum contaminant level
shall be conducted as follows: \7\
---------------------------------------------------------------------------
\7\ Monitoring for the contaminants aldicarb, aldicarb sulfoxide,
and aldicarb sulfone shall be conducted in accordance with Sec. 141.40.
---------------------------------------------------------------------------
(1) Groundwater systems shall take a minimum of one sample at every
entry point to the distribution system which is representative of each
well after treatment (hereafter called a sampling point). Each sample
must be taken at the same sampling point unless conditions make another
sampling point more representative of each source or treatment plant.
(2) Surface water systems shall take a minimum of one sample at
points in the distribution system that are representative of each source
or at each entry point to the distribution system after treatment
(hereafter called a sampling point). Each sample must be taken at the
same sampling point unless conditions make another sampling point more
representative of each source or treatment plant.
Note: For purposes of this paragraph, surface water systems include
systems with a combination of surface and ground sources.
(3) If the system draws water from more than one source and the
sources are combined before distribution, the system must sample at an
entry point to the distribution system during periods of normal
operating conditions (i.e., when water representative of all sources is
being used).
(4) Monitoring frequency:
(i) Each community and non-transient non-community water system
shall take four consecutive quarterly samples for each contaminant
listed in Sec. 141.61(c) during each compliance period beginning with
the initial compliance period.
(ii) Systems serving more than 3,300 persons which do not detect a
contaminant in the initial compliance period may reduce the sampling
frequency to a minimum of two quarterly samples in one year during each
repeat compliance period.
(iii) Systems serving less than or equal to 3,300 persons which do
not detect a contaminant in the initial compliance period may reduce the
sampling frequency to a minimum of one sample during each repeat
compliance period.
(5) Each community and non-transient water system may apply to the
State for a waiver from the requirement of paragraph (h)(4) of this
section. A system must reapply for a waiver for each compliance period.
(6) A State may grant a waiver after evaluating the following
factor(s): Knowledge of previous use (including transport, storage, or
disposal) of the contaminant within the watershed or zone of influence
of the system. If a determination by the State reveals no previous use
of the contaminant within the watershed or zone of influence, a waiver
may be granted. If previous use of the contaminant is unknown or it has
been used previously, then the following factors shall be used to
determine whether a waiver is granted.
(i) Previous analytical results.
(ii) The proximity of the system to a potential point or non-point
source of contamination. Point sources include spills and leaks of
chemicals at or near a water treatment facility or at manufacturing,
distribution, or storage facilities, or from hazardous and municipal
waste landfills and other waste handling or treatment facilities. Non-
point sources include the use of pesticides to control insect and weed
pests on agricultural areas, forest lands, home and gardens, and other
land application uses.
(iii) The environmental persistence and transport of the pesticide
or PCBs.
(iv) How well the water source is protected against contamination
due to such factors as depth of the well and the type of soil and the
integrity of the well casing.
(v) Elevated nitrate levels at the water supply source.
(vi) Use of PCBs in equipment used in the production, storage, or
distribution of water (i.e., PCBs used in pumps, transformers, etc.).
(7) If an organic contaminant listed in Sec. 141.61(c) is detected
(as defined by paragraph (h)(18) of this section) in any sample, then:
(i) Each system must monitor quarterly at each sampling point which
resulted in a detection.
[[Page 379]]
(ii) The State may decrease the quarterly monitoring requirement
specified in paragraph (h)(7)(i) of this section provided it has
determined that the system is reliably and consistently below the
maximum contaminant level. In no case shall the State make this
determination unless a groundwater system takes a minimum of two
quarterly samples and a surface water system takes a minimum of four
quarterly samples.
(iii) After the State determines the system is reliably and
consistently below the maximum contaminant level the State may allow the
system to monitor annually. Systems which monitor annually must monitor
during the quarter that previously yielded the highest analytical
result.
(iv) Systems which have 3 consecutive annual samples with no
detection of a contaminant may apply to the State for a waiver as
specified in paragraph (h)(6) of this section.
(v) If monitoring results in detection of one or more of certain
related contaminants (aldicarb, aldicarb sulfone, aldicarb sulfoxide and
heptachlor, heptachlor epoxide), then subsequent monitoring shall
analyze for all related contaminants.
(8) Systems which violate the requirements of Sec. 141.61(c) as
determined by paragraph (h)(11) of this section must monitor quarterly.
After a minimum of four quarterly samples show the system is in
compliance and the State determines the system is reliably and
consistently below the MCL, as specified in paragraph (h)(11) of this
section, the system shall monitor at the frequency specified in
paragraph (h)(7)(iii) of this section.
(9) The State may require a confirmation sample for positive or
negative results. If a confirmation sample is required by the State, the
result must be averaged with the first sampling result and the average
used for the compliance determination as specified by paragraph (h)(11)
of this section. States have discretion to delete results of obvious
sampling errors from this calculation.
(10) The State may reduce the total number of samples a system must
analyze by allowing the use of compositing. Composite samples from a
maximum of five sampling points are allowed, provided that the detection
limit of the method used for analysis is less than one-fifth of the MCL.
Compositing of samples must be done in the laboratory and analyzed
within 14 days of sample collection.
(i) If the concentration in the composite sample detects one or more
contaminants listed in Sec. 141.61(c), then a follow-up sample must be
taken within 14 days at each sampling point included in the composite,
and be analyzed for that contaminant.
(ii) If duplicates of the original sample taken from each sampling
point used in the composite sample are available, the system may use
these instead of resampling. The duplicates must be analyzed and the
results reported to the State within 14 days after completion of the
composite analysis or before the holding time for the initial sample is
exceeded whichever is sooner.
(iii) If the population served by the system is 3,300
persons, then compositing may only be permitted by the State at sampling
points within a single system. In systems serving <= 3,300 persons, the
State may permit compositing among different systems provided the 5-
sample limit is maintained.
(11) Compliance with Sec. 141.61(c) shall be determined based on
the analytical results obtained at each sampling point. If one sampling
point is in violation of an MCL, the system is in violation of the MCL.
(i) For systems monitoring more than once per year, compliance with
the MCL is determined by a running annual average at each sampling
point.
(ii) Systems monitoring annually or less frequently whose sample
result exceeds the regulatory detection level as defined by paragraph
(h)(18) of this section must begin quarterly sampling. The system will
not be considered in violation of the MCL until it has completed one
year of quarterly sampling.
(iii) If any sample result will cause the running annual average to
exceed the MCL at any sampling point, the system is out of compliance
with the MCL immediately.
(iv) If a system fails to collect the required number of samples,
compliance
[[Page 380]]
will be based on the total number of samples collected.
(v) If a sample result is less than the detection limit, zero will
be used to calculate the annual average.
(12) [Reserved]
(13) Analysis for PCBs shall be conducted as follows using the
methods in paragraph (e) of this section:
(i) Each system which monitors for PCBs shall analyze each sample
using either Method 508.1, 525.2, 508 or 505. Users of Method 505 may
have more difficulty in achieving the required Aroclor detection limits
than users of Methods 508.1, 525.2 or 508.
(ii) If PCBs (as one of seven Aroclors) are detected (as designated
in this paragraph) in any sample analyzed using Method 505 or 508, the
system shall reanalyze the sample using Method 508A to quantitate PCBs
(as decachlorobiphenyl).
------------------------------------------------------------------------
Detection limit
Aroclor (mg/l)
------------------------------------------------------------------------
1016................................................. 0.00008
1221................................................. 0.02
1232................................................. 0.0005
1242................................................. 0.0003
1248................................................. 0.0001
1254................................................. 0.0001
1260................................................. 0.0002
------------------------------------------------------------------------
(iii) Compliance with the PCB MCL shall be determined based upon the
quantitative results of analyses using Method 508A.
(14) If monitoring data collected after January 1, 1990, are
generally consistent with the requirements of Sec. 141.24(h), then the
State may allow systems to use that data to satisfy the monitoring
requirement for the initial compliance period beginning January 1, 1993.
(15) The State may increase the required monitoring frequency, where
necessary, to detect variations within the system (e.g., fluctuations in
concentration due to seasonal use, changes in water source).
(16) The State has the authority to determine compliance or initiate
enforcement action based upon analytical results and other information
compiled by their sanctioned representatives and agencies.
(17) Each public water system shall monitor at the time designated
by the State within each compliance period.
(18) Detection as used in this paragraph shall be defined as greater
than or equal to the following concentrations for each contaminant.
------------------------------------------------------------------------
Detection
Contaminant limit (mg/
l)
------------------------------------------------------------------------
Alachlor................................................... .0002
Aldicarb................................................... .0005
Aldicarb sulfoxide......................................... .0005
Aldicarb sulfone........................................... .0008
Atrazine................................................... .0001
Benzo[a]pyrene............................................. .00002
Carbofuran................................................. .0009
Chlordane.................................................. .0002
Dalapon.................................................... .001
1,2-Dibromo-3-chloropropane (DBCP)......................... .00002
Di (2-ethylhexyl) adipate.................................. .0006
Di (2-ethylhexyl) phthalate................................ .0006
Dinoseb.................................................... .0002
Diquat..................................................... .0004
2,4-D...................................................... .0001
Endothall.................................................. .009
Endrin..................................................... .00001
Ethylene dibromide (EDB)................................... .00001
Glyphosate................................................. .006
Heptachlor................................................. .00004
Heptachlor epoxide......................................... .00002
Hexachlorobenzene.......................................... .0001
Hexachlorocyclopentadiene.................................. .0001
Lindane.................................................... .00002
Methoxychlor............................................... .0001
Oxamyl..................................................... .002
Picloram................................................... .0001
Polychlorinated biphenyls (PCBs) (as decachlorobiphenyl)... .0001
Pentachlorophenol.......................................... .00004
Simazine................................................... .00007
Toxaphene.................................................. .001
2,3,7,8-TCDD (Dioxin)...................................... .000000005
2,4,5-TP (Silvex).......................................... .0002
------------------------------------------------------------------------
(19) Anaylsis under this section shall only be conducted by
laboratories that have received certification by EPA or the State and
have met the following conditions:
(i) To receive certification to conduct analyses for the
contaminants in Sec. 141.61(c) the laboratory must:
(A) Analyze Performance Evaluation (PE) samples provided by EPA, the
State, or by a third party (with the approval of the State or EPA) at
least once a year by each method for which the laboratory desires
certification.
(B) For each contaminant that has been included in the PE sample
achieve quantitative results on the analyses that are within the
following acceptance limits:
------------------------------------------------------------------------
Contaminant Acceptance limits (percent)
------------------------------------------------------------------------
DBCP...................................... 40
EDB....................................... 40.
Alachlor.................................. 45.
Atrazine.................................. 45.
[[Page 381]]
Benzo[a]pyrene............................ 2 standard deviations.
Carbofuran................................ 45.
Chlordane................................. 45.
Dalapon................................... 2 standard deviations.
Di(2-ethylhexyl)adipate................... 2 standard deviations.
Di(2-ethylhexyl)phthalate................. 2 standard deviations.
Dinoseb................................... 2 standard deviations.
Diquat.................................... 2 standard deviations.
Endothall................................. 2 standard deviations.
Endrin.................................... 30.
Glyphosate................................ 2 standard deviations.
Heptachlor................................ 45.
Heptachlor epoxide........................ 45.
Hexachlorobenzene......................... 2 standard deviations.
Hexachloro- cyclopentadiene 2 standard deviations.
Lindane................................... 45.
Methoxychlor.............................. 45.
Oxamyl.................................... 2 standard deviations.
PCBs (as Decachlorobiphenyl) 0-200.
Picloram.................................. 2 standard deviations.
Simazine.................................. 2 standard deviations.
Toxaphene................................. 45.
Aldicarb.................................. 2 standard deviations.
Aldicarb sulfoxide........................ 2 standard deviations.
Aldicarb sulfone.......................... 2 standard deviations.
Pentachlorophenol......................... 50.
2,3,7,8-TCDD (Dioxin)..................... 2 standard deviations.
2,4-D..................................... 50.
2,4,5-TP (Silvex)......................... 50.
------------------------------------------------------------------------
(ii) [Reserved]
(20) All new systems or systems that use a new source of water that
begin operation after January 22, 2004 must demonstrate compliance with
the MCL within a period of time specified by the State. The system must
also comply with the initial sampling frequencies specified by the State
to ensure a system can demonstrate compliance with the MCL. Routine and
increased monitoring frequencies shall be conducted in accordance with
the requirements in this section.
(Approved by the Office of Management and Budget under control number
2040-0090)
[40 FR 59570, Dec. 24, 1975, as amended at 44 FR 68641, Nov. 29, 1979;
45 FR 57345, Aug. 27, 1980; 47 FR 10998, Mar. 12, 1982; 52 FR 25712,
July 8, 1987; 53 FR 5147, Feb. 19, 1988; 53 FR 25110, July 1, 1988; 56
FR 3583, Jan. 30, 1991; 56 FR 30277, July 1, 1991; 57 FR 22178, May 27,
1992; 57 FR 31841, July 17, 1992; 59 FR 34323, July 1, 1994; 59 FR
62468, Dec. 5, 1994; 60 FR 34085, June 29, 1995; 64 FR 67464, Dec. 1,
1999; 65 FR 26022, May 4, 2000; 66 FR 7063, Jan. 22, 2001; 67 FR 65250,
Oct. 23, 2002; 67 FR 65898, Oct. 29, 2002]
Sec. 141.25 Analytical methods for radioactivity.
(a) Analysis for the following contaminants shall be conducted to
determine compliance with Sec. 141.66 (radioactivity) in accordance
with the methods in the following table, or their equivalent determined
by EPA in accordance with Sec. 141.27.
[[Page 382]]
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
Reference (method or page number)
Contaminant Methodology ----------------------------------------------------------------------------------------------------------------------------------------------
EPA \1\ EPA \2\ EPA \3\ EPA \4\ SM \5\ ASTM \6\ USGS \7\ DOE \8\ Other
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
Naturally occurring:
Gross alpha\11\ and beta.. Evaporation...... 900.0....... p 1......... 00-01....... p 1......... 302, 7110 B.............. ............... R-1120-76...... ...........
Gross alpha\11\........... Co-precipitation. ............ ............ 00-02....... ............ 7110 C................... ...........
Radium 226................ Radon emanation.. 903.1....... p 16........ Ra-04....... p 19........ 305,7500-Ra C............ D 3454-97...... R-1141-76...... Ra-04...... N.Y.\9\
Radiochemi- cal.. 903.0....... p 13........ Ra-03....... ............ 304,7500-Ra B............ D 2460-97...... R-1140-76...... ...........
Radium 228................ Radiochemi- cal.. 904.0....... p 24........ Ra-05....... p 19........ 7500-Ra D................ ............... R-1142-76...... ........... N.Y.\9\,
N.J.\10\
Uranium \12\.............. Radiochemical.... 908.0....... ............ ............ ............ 7500-U B
Fluorometric..... 908.1....... ............ ............ ............ 7500-U C (17th Ed.)...... D 2907-97...... R-1180-76, R- U-04
1181-76.
ICP-MS........... 200.8 \13\.. ............ ............ ............ 3125..................... D 5673-03
Alpha ............ ............ 00-07....... p 33........ 7500-UC (18th, 19th or D 3972-97...... R-1182-76...... U-02.......
spectrometry. 20th Ed.).
Laser ............ ............ ............ ............ ......................... D 5174-97...... ...........
Phosphorimetry.
Man-made:
Radioact-................. Radiochemi-...... 901.0....... p 4......... ............ ............ 7500-CsB................. D 2459-72...... R-1111-76...... ...........
ive cesium................ cal..............
Gamma ray 901.1....... ............ ............ p 92........ 7120..................... D 3649-91...... R- 1110-76..... 4.5.2.3.... ...........
spectrometry.
Radioact-................. Radiochemi-...... 902.0....... p 6, p 9.... ............ ............ 7500-I B, 7500-I C, 7500- D 3649-91......
ive iodine................ cal.............. I D.
Gamma ray 901.1....... ............ ............ p 92........ 7120..................... D 4785-93...... ............... 4.5.2.3.... ...........
spectrometry.
Radioact-................. Radiochemi-...... 905.0....... p 29........ Sr-04....... p 65........ 303, 7500-Sr B........... ............... R-1160-76...... Sr-01, Sr- ...........
ive Strontium 89, 90...... cal.............. 02
Tritium................... Liquid 906.0....... p 34........ H-02........ p 87........ 306, 7500-3H B........... D 4107-91...... R-1171-76......
scintillation.
Gamma emitters............ Gamma ray........ 901.1....... ............ ............ p 92........ 7120..................... D 3649-91...... R-1110-76...... Ga-01-R.... ...........
Spectrometry..... 902.0, 901.0 ............ ............ ............ 7500-Cs B, 7500-I B...... D 4785-93......
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
The procedures shall be done in accordance with the documents listed below. The incorporation by reference of documents 1 through 10 was approved by the Director of the Federal Register in
accordance with 5 U.S.C. 552(a) and 1 CFR part 51. Copies of the documents may be obtained from the sources listed below. Information regarding obtaining these documents can be obtained from
the Safe Drinking Water Hotline at 800-426-4791. Documents may be inspected at EPA's Drinking Water Docket, EPA West, 1301 Constitution Avenue, NW., Room B135, Washington, DC (Telephone: 202-
566-2426); or at the National Archives and Records Administration (NARA). For information on the availability of this material at NARA, call 202-741-6030, or go to: http://www.archives.gov/
federal--register/code--of--federal--regulations/ibr--locations.html.
\1\ ``Prescribed Procedures for the Measurement of Radioactivity in Drinking Water'', EPA 600/4-80-032, August 1980. Available at the U.S. Department of Commerce, National Technical
Information Service (NTIS), 5285 Port Royal Road, Springfield, VA 22161 (Telephone (800) 553-6847), PB 80-224744, except Method 200.8, ``Determination of Trace Elements in Waters and Wastes
by Inductively Coupled Plasma-Mass Spectrometry,'' Revision 5.4, which is published in ``Methods for the Determination of Metals in Environmental Samples--Supplement I,'' EPA 600-R-94-111,
May 1994. Available at NTIS, PB95-125472.
\2\ ``Interim Radiochemical Methodology for Drinking Water'', EPA 600/4-75-008 (revised), March 1976. Available at NTIS, ibid. PB 253258.
\3\ ``Radiochemistry Procedures Manual'', EPA 520/5-84-006, December, 1987. Available at NTIS, ibid. PB 84-215581.
\4\ ``Radiochemical Analytical Procedures for Analysis of Environmental Samples'', March 1979. Available at NTIS, ibid. EMSL LV 053917.
[[Page 383]]
\5\ ``Standard Methods for the Examination of Water and Wastewater'', 13th, 17th, 18th, 19th Editions, or 20th edition, 1971, 1989, 1992, 1995, 1998. Available at American Public Health
Association, 1015 Fifteenth Street NW., Washington, DC 20005. Methods 302, 303, 304, 305 and 306 are only in the 13th edition. Methods 7110B, 7500-Ra B, 7500-Ra C, 7500-Ra D, 7500-U B, 7500-
Cs B, 7500-I B, 7500-I C, 7500-I D, 7500-Sr B, 7500-3H B are in the 17th, 18th, 19th and 20th editions. Method 7110 C is in the 18th, 19th and 20th editions. Method 7500-U C Fluorometric
Uranium is only in the 17th Edition, and 7500-U C Alpha spectrometry is only in the 18th, 19th and 20th editions. Method 7120 is only in the 19th and 20th editions. Methods 302, 303, 304,
305 and 306 are only in the 13th edition. Method 3125 is only in the 20th edition.
\6\ Annual Book of ASTM Standards, Vol. 11.01 and 11.02, 1999; ASTM International any year containing the cited version of the method may be used. Copies of these two volumes and the 2003
version of D 5673-03 may be obtained from ASTM International. 100 Barr Harbor Drive, P.O. Box C700, West Conshohocken, PA, 19428-2959.
\7\ ``Methods for Determination of Radioactive Substances in Water and Fluvial Sediments'', Chapter A5 in Book 5 of Techniques of Water-Resources Investigations of the United States Geological
Survey, 1977. Available at U.S. Geological Survey (USGS) Information Services, Box 25286, Federal Center, Denver, CO 80225-0425.
\8\ ``EML Procedures Manual'', 28th (1997) or 27th (1990) Editions, Volumes 1 and 2; either edition may be used. In the 27th Edition Method Ra-04 is listed as Ra-05 and Method Ga-01-R is
listed as Sect. 4.5.2.3. Available at the Environmental Measurements Laboratory, U.S. Department of Energy (DOE), 376 Hudson Street, New York, NY 10014-3621.
\9\ ``Determination of Ra-226 and Ra-228 (Ra-02)'', January 1980, Revised June 1982. Available at Radiological Sciences Institute for Laboratories and Research, New York State Department of
Health, Empire State Plaza, Albany, NY 12201.
\10\ ``Determination of Radium 228 in Drinking Water'', August 1980. Available at State of New Jersey, Department of Environmental Protection, Division of Environmental Quality, Bureau of
Radiation and Inorganic Analytical Services, 9 Ewing Street, Trenton, NJ 08625.
\11\ Natural uranium and thorium-230 are approved as gross alpha calibration standards for gross alpha with co-precipitation and evaporation methods; americium-241 is approved with co-
precipitation methods.
\12\ If uranium (U) is determined by mass, a 0.67 pCi/[micro]g of uranium conversion factor must be used. This conversion factor is based on the 1:1 activity ratio of U-234 and U-238 that is
characteristic of naturally occurring uranium.
\13\ ``Determination of Trace Elements in Waters and Wastes by Inductively Coupled Plasma-Mass Spectrometry,'' Revision 5.4, which is published in ``Methods for the Determination of Metals in
Environmental Samples--Supplement I,'' EPA 600-R-94-111, May 1994. Available at NTIS, PB 95-125472.
[[Page 384]]
(b) When the identification and measurement of radionuclides other
than those listed in paragraph (a) of this section is required, the
following references are to be used, except in cases where alternative
methods have been approved in accordance with Sec. 141.27.
(1) Procedures for Radiochemical Analysis of Nuclear Reactor Aqueous
Solutions, H. L. Krieger and S. Gold, EPA-R4-73-014. USEPA, Cincinnati,
Ohio, May 1973.
(2) HASL Procedure Manual, Edited by John H. Harley. HASL 300, ERDA
Health and Safety Laboratory, New York, NY., 1973.
(c) For the purpose of monitoring radioactivity concentrations in
drinking water, the required sensitivity of the radioanalysis is defined
in terms of a detection limit. The detection limit shall be that
concentration which can be counted with a precision of plus or minus 100
percent at the 95 percent confidence level (1.96[sigma] where [sigma] is
the standard deviation of the net counting rate of the sample).
(1) To determine compliance with Sec. 141.66(b), (c), and (e) the
detection limit shall not exceed the concentrations in Table B to this
paragraph.
Table B--Detection Limits for Gross Alpha Particle Activity, Radium 226,
Radium 228, and Uranium
------------------------------------------------------------------------
Contaminant Detection limit
------------------------------------------------------------------------
Gross alpha particle activity.............. 3 pCi/L.
Radium 226................................. 1 pCi/L.
Radium 228................................. 1 pCi/L.
Uranium.................................... 1 [micro]g/L
------------------------------------------------------------------------
(2) To determine compliance with Sec. 141.66(d) the detection
limits shall not exceed the concentrations listed in Table C to this
paragraph.
Table C--Detection Limits for Man-made Beta Particle and Photon Emitters
------------------------------------------------------------------------
Radionuclide Detection limit
------------------------------------------------------------------------
Tritium................................... 1,000 pCi/1.
Strontium-89.............................. 10 pCi/1.
Strontium-90.............................. 2 pCi/1.
Iodine-131................................ 1 pCi/1.
Cesium-134................................ 10 pCi/1.
Gross beta................................ 4 pCi/1.
Other radionuclides....................... \1/10\ of the applicable
limit.
------------------------------------------------------------------------
(d) To judge compliance with the maximum contaminant levels listed
in Sec. 141.66, averages of data shall be used and shall be rounded to
the same number of significant figures as the maximum contaminant level
for the substance in question.
(e) The State has the authority to determine compliance or initiate
enforcement action based upon analytical results or other information
compiled by their sanctioned representatives and agencies.
[41 FR 28404, July 9, 1976, as amended at 45 FR 57345, Aug. 27, 1980; 62
FR 10173, Mar. 5, 1997; 65 FR 76745, Dec. 7, 2000; 67 FR 65250, Oct. 23,
2002; 69 FR 38855, June 29, 2004; 69 FR 52180, Aug. 25, 2004]
Sec. 141.26 Monitoring frequency and compliance requirements for
radionuclides in community water systems.
(a) Monitoring and compliance requirements for gross alpha particle
activity, radium-226, radium-228, and uranium. (1) Community water
systems (CWSs) must conduct initial monitoring to determine compliance
with Sec. 141.66(b), (c), and (e) by December 31, 2007. For the
purposes of monitoring for gross alpha particle activity, radium-226,
radium-228, uranium, and beta particle and photon radioactivity in
drinking water, ``detection limit'' is defined as in Sec. 141.25(c).
(i) Applicability and sampling location for existing community water
systems or sources. All existing CWSs using ground water, surface water
or systems using both ground and surface water (for the purpose of this
section hereafter referred to as systems) must sample at every entry
point to the distribution system that is representative of all sources
being used (hereafter called a sampling point) under normal operating
conditions. The system must take each sample at the same sampling point
unless conditions make another sampling point more representative of
each source or the State has designated a distribution system location,
in accordance with paragraph (a)(2)(ii)(C) of this section.
(ii) Applicability and sampling location for new community water
systems or sources. All new CWSs or CWSs that use a new source of water
must begin to conduct initial monitoring for the new source within the
first quarter after
[[Page 385]]
initiating use of the source. CWSs must conduct more frequent monitoring
when ordered by the State in the event of possible contamination or when
changes in the distribution system or treatment processes occur which
may increase the concentration of radioactivity in finished water.
(2) Initial monitoring: Systems must conduct initial monitoring for
gross alpha particle activity, radium-226, radium-228, and uranium as
follows:
(i) Systems without acceptable historical data, as defined below,
must collect four consecutive quarterly samples at all sampling points
before December 31, 2007.
(ii) Grandfathering of data: States may allow historical monitoring
data collected at a sampling point to satisfy the initial monitoring
requirements for that sampling point, for the following situations.
(A) To satisfy initial monitoring requirements, a community water
system having only one entry point to the distribution system may use
the monitoring data from the last compliance monitoring period that
began between June 2000 and December 8, 2003.
(B) To satisfy initial monitoring requirements, a community water
system with multiple entry points and having appropriate historical
monitoring data for each entry point to the distribution system may use
the monitoring data from the last compliance monitoring period that
began between June 2000 and December 8, 2003.
(C) To satisfy initial monitoring requirements, a community water
system with appropriate historical data for a representative point in
the distribution system may use the monitoring data from the last
compliance monitoring period that began between June 2000 and December
8, 2003, provided that the State finds that the historical data
satisfactorily demonstrate that each entry point to the distribution
system is expected to be in compliance based upon the historical data
and reasonable assumptions about the variability of contaminant levels
between entry points. The State must make a written finding indicating
how the data conforms to the these requirements.
(iii) For gross alpha particle activity, uranium, radium-226, and
radium-228 monitoring, the State may waive the final two quarters of
initial monitoring for a sampling point if the results of the samples
from the previous two quarters are below the detection limit.
(iv) If the average of the initial monitoring results for a sampling
point is above the MCL, the system must collect and analyze quarterly
samples at that sampling point until the system has results from four
consecutive quarters that are at or below the MCL, unless the system
enters into another schedule as part of a formal compliance agreement
with the State.
(3) Reduced monitoring: States may allow community water systems to
reduce the future frequency of monitoring from once every three years to
once every six or nine years at each sampling point, based on the
following criteria.
(i) If the average of the initial monitoring results for each
contaminant (i.e., gross alpha particle activity, uranium, radium-226,
or radium-228) is below the detection limit specified in Table B, in
Sec. 141.25(c)(1), the system must collect and analyze for that
contaminant using at least one sample at that sampling point every nine
years.
(ii) For gross alpha particle activity and uranium, if the average
of the initial monitoring results for each contaminant is at or above
the detection limit but at or below \1/2\ the MCL, the system must
collect and analyze for that contaminant using at least one sample at
that sampling point every six years. For combined radium-226 and radium-
228, the analytical results must be combined. If the average of the
combined initial monitoring results for radium-226 and radium-228 is at
or above the detection limit but at or below \1/2\ the MCL, the system
must collect and analyze for that contaminant using at least one sample
at that sampling point every six years.
(iii) For gross alpha particle activity and uranium, if the average
of the initial monitoring results for each contaminant is above \1/2\
the MCL but at or below the MCL, the system must collect and analyze at
least one sample at that sampling point every three years. For combined
radium-226 and radium-
[[Page 386]]
228, the analytical results must be combined. If the average of the
combined initial monitoring results for radium-226 and radium-228 is
above \1/2\ the MCL but at or below the MCL, the system must collect and
analyze at least one sample at that sampling point every three years.
(iv) Systems must use the samples collected during the reduced
monitoring period to determine the monitoring frequency for subsequent
monitoring periods (e.g., if a system's sampling point is on a nine year
monitoring period, and the sample result is above \1/2\ MCL, then the
next monitoring period for that sampling point is three years).
(v) If a system has a monitoring result that exceeds the MCL while
on reduced monitoring, the system must collect and analyze quarterly
samples at that sampling point until the system has results from four
consecutive quarters that are below the MCL, unless the system enters
into another schedule as part of a formal compliance agreement with the
State.
(4) Compositing: To fulfill quarterly monitoring requirements for
gross alpha particle activity, radium-226, radium-228, or uranium, a
system may composite up to four consecutive quarterly samples from a
single entry point if analysis is done within a year of the first
sample. States will treat analytical results from the composited as the
average analytical result to determine compliance with the MCLs and the
future monitoring frequency. If the analytical result from the
composited sample is greater than \1/2\ MCL, the State may direct the
system to take additional quarterly samples before allowing the system
to sample under a reduced monitoring schedule.
(5) A gross alpha particle activity measurement may be substituted
for the required radium-226 measurement provided that the measured gross
alpha particle activity does not exceed 5 pCi/l. A gross alpha particle
activity measurement may be substituted for the required uranium
measurement provided that the measured gross alpha particle activity
does not exceed 15 pCi/l. The gross alpha measurement shall have a
confidence interval of 95% (1.65[sigma], where [sigma] is the standard
deviation of the net counting rate of the sample) for radium-226 and
uranium. When a system uses a gross alpha particle activity measurement
in lieu of a radium-226 and/or uranium measurement, the gross alpha
particle activity analytical result will be used to determine the future
monitoring frequency for radium-226 and/or uranium. If the gross alpha
particle activity result is less than detection, \1/2\ the detection
limit will be used to determine compliance and the future monitoring
frequency.
(b) Monitoring and compliance requirements for beta particle and
photon radioactivity. To determine compliance with the maximum
contaminant levels in Sec. 141.66(d) for beta particle and photon
radioactivity, a system must monitor at a frequency as follows:
(1) Community water systems (both surface and ground water)
designated by the State as vulnerable must sample for beta particle and
photon radioactivity. Systems must collect quarterly samples for beta
emitters and annual samples for tritium and strontium-90 at each entry
point to the distribution system (hereafter called a sampling point),
beginning within one quarter after being notified by the State. Systems
already designated by the State must continue to sample until the State
reviews and either reaffirms or removes the designation.
(i) If the gross beta particle activity minus the naturally
occurring potassium-40 beta particle activity at a sampling point has a
running annual average (computed quarterly) less than or equal to 50
pCi/L (screening level), the State may reduce the frequency of
monitoring at that sampling point to once every 3 years. Systems must
collect all samples required in paragraph (b)(1) of this section during
the reduced monitoring period.
(ii) For systems in the vicinity of a nuclear facility, the State
may allow the CWS to utilize environmental surveillance data collected
by the nuclear facility in lieu of monitoring at the system's entry
point(s), where the State determines if such data is applicable to a
particular water system. In the event that there is a release from a
nuclear facility, systems which are using surveillance data must begin
monitoring at the community water
[[Page 387]]
system's entry point(s) in accordance with paragraph (b)(1) of this
section.
(2) Community water systems (both surface and ground water)
designated by the State as utilizing waters contaminated by effluents
from nuclear facilities must sample for beta particle and photon
radioactivity. Systems must collect quarterly samples for beta emitters
and iodine-131 and annual samples for tritium and strontium-90 at each
entry point to the distribution system (hereafter called a sampling
point), beginning within one quarter after being notified by the State.
Systems already designated by the State as systems using waters
contaminated by effluents from nuclear facilities must continue to
sample until the State reviews and either reaffirms or removes the
designation.
(i) Quarterly monitoring for gross beta particle activity shall be
based on the analysis of monthly samples or the analysis of a composite
of three monthly samples. The former is recommended.
(ii) For iodine-131, a composite of five consecutive daily samples
shall be analyzed once each quarter. As ordered by the State, more
frequent monitoring shall be conducted when iodine-131 is identified in
the finished water.
(iii) Annual monitoring for strontium-90 and tritium shall be
conducted by means of the analysis of a composite of four consecutive
quarterly samples or analysis of four quarterly samples. The latter
procedure is recommended.
(iv) If the gross beta particle activity minus the naturally
occurring potassium-40 beta particle activity at a sampling point has a
running annual average (computed quarterly) less than or equal to 15
pCi/L (screening level), the State may reduce the frequency of
monitoring at that sampling point to every 3 years. Systems must collect
the same type of samples required in paragraph (b)(2) of this section
during the reduced monitoring period.
(v) For systems in the vicinity of a nuclear facility, the State may
allow the CWS to utilize environmental surveillance data collected by
the nuclear facility in lieu of monitoring at the system's entry
point(s), where the State determines if such data is applicable to a
particular water system. In the event that there is a release from a
nuclear facility, systems which are using surveillance data must begin
monitoring at the community water system's entry point(s) in accordance
with paragraph (b)(2) of this section.
(3) Community water systems designated by the State to monitor for
beta particle and photon radioactivity can not apply to the State for a
waiver from the monitoring frequencies specified in paragraph (b)(1) or
(b)(2) of this section.
(4) Community water systems may analyze for naturally occurring
potassium-40 beta particle activity from the same or equivalent sample
used for the gross beta particle activity analysis. Systems are allowed
to subtract the potassium-40 beta particle activity value from the total
gross beta particle activity value to determine if the screening level
is exceeded. The potassium-40 beta particle activity must be calculated
by multiplying elemental potassium concentrations (in mg/L) by a factor
of 0.82.
(5) If the gross beta particle activity minus the naturally
occurring potassium-40 beta particle activity exceeds the appropriate
screening level, an analysis of the sample must be performed to identify
the major radioactive constituents present in the sample and the
appropriate doses must be calculated and summed to determine compliance
with Sec. 141.66(d)(1), using the formula in Sec. 141.66(d)(2). Doses
must also be calculated and combined for measured levels of tritium and
strontium to determine compliance.
(6) Systems must monitor monthly at the sampling point(s) which
exceed the maximum contaminant level in Sec. 141.66(d) beginning the
month after the exceedance occurs. Systems must continue monthly
monitoring until the system has established, by a rolling average of 3
monthly samples, that the MCL is being met. Systems who establish that
the MCL is being met must return to quarterly monitoring until they meet
the requirements set forth in paragraph (b)(1)(i) or (b)(2)(iv) of this
section.
(c) General monitoring and compliance requirements for
radionuclides. (1) The
[[Page 388]]
State may require more frequent monitoring than specified in paragraphs
(a) and (b) of this section, or may require confirmation samples at its
discretion. The results of the initial and confirmation samples will be
averaged for use in compliance determinations.
(2) Each public water systems shall monitor at the time designated
by the State during each compliance period.
(3) Compliance: Compliance with Sec. 141.66 (b) through (e) will be
determined based on the analytical result(s) obtained at each sampling
point. If one sampling point is in violation of an MCL, the system is in
violation of the MCL.
(i) For systems monitoring more than once per year, compliance with
the MCL is determined by a running annual average at each sampling
point. If the average of any sampling point is greater than the MCL,
then the system is out of compliance with the MCL.
(ii) For systems monitoring more than once per year, if any sample
result will cause the running average to exceed the MCL at any sample
point, the system is out of compliance with the MCL immediately.
(iii) Systems must include all samples taken and analyzed under the
provisions of this section in determining compliance, even if that
number is greater than the minimum required.
(iv) If a system does not collect all required samples when
compliance is based on a running annual average of quarterly samples,
compliance will be based on the running average of the samples
collected.
(v) If a sample result is less than the detection limit, zero will
be used to calculate the annual average, unless a gross alpha particle
activity is being used in lieu of radium-226 and/or uranium. If the
gross alpha particle activity result is less than detection, \1/2\ the
detection limit will be used to calculate the annual average.
(4) States have the discretion to delete results of obvious sampling
or analytic errors.
(5) If the MCL for radioactivity set forth in Sec. 141.66 (b)
through (e) is exceeded, the operator of a community water system must
give notice to the State pursuant to Sec. 141.31 and to the public as
required by subpart Q of this part.
[65 FR 76745, Dec. 7, 2000, as amended at 69 FR 38855, June 29, 2004]
Sec. 141.27 Alternate analytical techniques.
(a) With the written permission of the State, concurred in by the
Administrator of the U.S. EPA, an alternate analytical technique may be
employed. An alternate technique shall be accepted only if it is
substantially equivalent to the prescribed test in both precision and
accuracy as it relates to the determination of compliance with any MCL.
The use of the alternate analytical technique shall not decrease the
frequency of monitoring required by this part.
[45 FR 57345, Aug. 27, 1980]
Sec. 141.28 Certified laboratories.
(a) For the purpose of determining compliance with Sec. Sec. 141.21
through 141.27, 141.30, 141.40, 141.74 and 141.89, samples may be
considered only if they have been analyzed by a laboratory certified by
the State except that measurements for alkalinity, calcium,
conductivity, disinfectant residual, orthophosphate, pH, silica,
temperature and turbidity may be performed by any person acceptable to
the State.
(b) Nothing in this part shall be construed to preclude the State or
any duly designated representative of the State from taking samples or
from using the results from such samples to determine compliance by a
supplier of water with the applicable requirements of this part.
[45 FR 57345, Aug. 27, 1980; 47 FR 10999, Mar. 12, 1982, as amended at
59 FR 34323, July 1, 1994; 64 FR 67465, Dec. 1, 1999]
Sec. 141.29 Monitoring of consecutive public water systems.
When a public water system supplies water to one or more other
public water systems, the State may modify the monitoring requirements
imposed by this part to the extent that the interconnection of the
systems justifies treating them as a single system for monitoring
purposes. Any modified monitoring shall be conducted pursuant to a
schedule specified by the State
[[Page 389]]
and concurred in by the Administrator of the U.S. Environmental
Protection Agency.
Sec. 141.30 Total trihalomethanes sampling, analytical and other
requirements.
(a) Community water system which serve a population of 10,000 or
more individuals and which add a disinfectant (oxidant) to the water in
any part of the drinking water treatment process shall analyze for total
trihalomethanes in accordance with this section. For systems serving
75,000 or more individuals, sampling and analyses shall begin not later
than 1 year after the date of promulgation of this regulation. For
systems serving 10,000 to 74,999 individuals, sampling and analyses
shall begin not later than 3 years after the date of promulgation of
this regulation. For the purpose of this section, the minimum number of
samples required to be taken by the system shall be based on the number
of treatment plants used by the system, except that multiple wells
drawing raw water from a single aquifer may, with the State approval, be
considered one treatment plant for determining the minimum number of
samples. All samples taken within an established frequency shall be
collected within a 24-hour period.
(b)(1) For all community water systems utilizing surface water
sources in whole or in part, and for all community water systems
utilizing only ground water sources that have not been determined by the
State to qualify for the monitoring requirements of paragraph (c) of
this section, analyses for total trihalomethanes shall be performed at
quarterly intervals on at least four water samples for each treatment
plant used by the system. At least 25 percent of the samples shall be
taken at locations within the distribution system reflecting the maximum
residence time of the water in the system. The remaining 75 percent
shall be taken at representative locations in the distribution system,
taking into account number of persons served, different sources of water
and different treatment methods employed. The results of all analyses
per quarter shall be arithmetically averaged and reported to the State
within 30 days of the system's receipt of such results. Results shall
also be reported to EPA until such monitoring requirements have been
adopted by the State. All samples collected shall be used in the
computation of the average, unless the analytical results are
invalidated for technical reasons. Sampling and analyses shall be
conducted in accordance with the methods listed in paragraph (e) of this
section.
(2) Upon the written request of a community water system, the
monitoring frequency required by paragraph (b)(1) of this section may be
reduced by the State to a minimum of one sample analyzed for TTHMs per
quarter taken at a point in the distribution system reflecting the
maximum residence time of the water in the system, upon a written
determination by the State that the data from at least 1 year of
monitoring in accordance with paragraph (b)(1) of this section and local
conditions demonstrate that total trihalomethane concentrations will be
consistently below the maximum contaminant level.
(3) If at any time during which the reduced monitoring frequency
prescribed under this paragraph applies, the results from any analysis
exceed 0.10 mg/l of TTHMs and such results are confirmed by at least one
check sample taken promptly after such results are received, or if the
system makes any significant change to its source of water or treatment
program, the system shall immediately begin monitoring in accordance
with the requirements of paragraph (b)(1) of this section, which
monitoring shall continue for at least 1 year before the frequency may
be reduced again. At the option of the State, a system's monitoring
frequency may and should be increased above the minimum in those cases
where it is necessary to detect variations of TTHM levels within the
distribution system.
(c)(1) Upon written request to the State, a community water system
utilizing only ground water sources may seek to have the monitoring
frequency required by paragraph (b)(1) of this section reduced to a
minimum of one sample for maximum TTHM potential per year for each
treatment plant used by
[[Page 390]]
the system taken at a point in the distribution system reflecting
maximum residence time of the water in the system. The system shall
submit the results of at least one sample for maximum TTHM potential
using the procedure specified in paragraph (g) of this section. A sample
must be analyzed from each treatment plant used by the system and be
taken at a point in the distribution system reflecting the maximum
residence time of the water in the system. The system's monitoring
frequency may only be reduced upon a written determination by the State
that, based upon the data submitted by the system, the system has a
maximum TTHM potential of less than 0.10 mg/l and that, based upon an
assessment of the local conditions of the system, the system is not
likely to approach or exceed the maximum contaminant level for total
TTHMs. The results of all analyses shall be reported to the State within
30 days of the system's receipt of such results. Results shall also be
reported to EPA until such monitoring requirements have been adopted by
the State. All samples collected shall be used for determining whether
the system must comply with the monitoring requirements of paragraph (b)
of this section, unless the analytical results are invalidated for
technical reasons. Sampling and analyses shall be conducted in
accordance with the methods listed in paragraph (e) of this section.
(2) If at any time during which the reduced monitoring frequency
prescribed under paragraph (c)(1) of this section applies, the results
from any analysis taken by the system for maximum TTHM potential are
equal to or greater than 0.10 mg/l, and such results are confirmed by at
least one check sample taken promptly after such results are received,
the system shall immediately begin monitoring in accordance with the
requirements of paragraph (b) of this section and such monitoring shall
continue for at least one year before the frequency may be reduced
again. In the event of any significant change to the system's raw water
or treatment program, the system shall immediately analyze an additional
sample for maximum TTHM potential taken at a point in the distribution
system reflecting maximum residence time of the water in the system for
the purpose of determining whether the system must comply with the
monitoring requirements of paragraph (b) of this section. At the option
of the State, monitoring frequencies may and should be increased above
the minimum in those cases where this is necessary to detect variation
of TTHM levels within the distribution system.
(d) Compliance with Sec. 141.12 shall be determined based on a
running annual average of quarterly samples collected by the system as
prescribed in paragraph (b)(1) or (2) of this section. If the average of
samples covering any 12 month period exceeds the Maximum Contaminant
Level, the supplier of water shall report to the State pursuant to Sec.
141.31 and notify the public pursuant to subpart Q. Monitoring after
public notification shall be at a frequency designated by the State and
shall continue until a monitoring schedule as a condition to a variance,
exemption or enforcement action shall become effective.
(e) Sampling and analyses made pursuant to this section shall be
conducted by one of the total trihalomethanes methods as directed in
Sec. 141.24(e), and the Technical Notes on Drinking Water Methods, EPA-
600/R-94-173, October 1994, which is available from NTIS, PB-104766, or
in Sec. 141.131(b). Samples for TTHM shall be dechlorinated upon
collection to prevent further production of trihalomethanes, according
to the procedures described in the methods, except acidification is not
required if only THMs or TTHMs are to be determined. Samples for maximum
TTHM potential should not be dechlorinated or acidified, and should be
held for seven days at 25 [deg]C (or above) prior to analysis.
(f) Before a community water system makes any significant
modifications to its existing treatment process for the purposes of
achieving compliance with Sec. 141.12, such system must submit and
obtain State approval of a detailed plan setting forth its proposed
modification and those safeguards that it will implement to ensure that
the bacteriological quality of the drinking water served by such system
will not
[[Page 391]]
be adversely affected by such modification. Each system shall comply
with the provisions set forth in the State-approved plan. At a minimum,
a State approved plan shall require the system modifying its
disinfection practice to:
(1) Evaluate the water system for sanitary defects and evaluate the
source water for biological quality;
(2) Evaluate its existing treatment practices and consider
improvements that will minimize disinfectant demand and optimize
finished water quality throughout the distribution system;
(3) Provide baseline water quality survey data of the distribution
system. Such data should include the results from monitoring for
coliform and fecal coliform bacteria, fecal streptococci, standard plate
counts at 35 [deg]C and 20 [deg]C, phosphate, ammonia nitrogen and total
organic carbon. Virus studies should be required where source waters are
heavily contaminated with sewage effluent;
(4) Conduct additional monitoring to assure continued maintenance of
optimal biological quality in finished water, for example, when
chloramines are introduced as disinfectants or when pre-chlorination is
being discontinued. Additional monitoring should also be required by the
State for chlorate, chlorite and chlorine dioxide when chlorine dioxide
is used. Standard plate count analyses should also be required by the
State as appropriate before and after any modifications;
(5) Consider inclusion in the plan of provisions to maintain an
active disinfectant residual throughout the distribution system at all
times during and after the modification.
(g) The water sample for determination of maximum total
trihalomethane potential is taken from a point in the distribution
system that reflects maximum residence time. Procedures for sample
collection and handling are given in the methods. No reducing agent is
added to ``quench'' the chemical reaction producing THMs at the time of
sample collection. The intent is to permit the level of THM precursors
to be depleted and the concentration of THMs to be maximized for the
supply being tested. Four experimental parameters affecting maximum THM
production are pH, temperature, reaction time and the presence of a
disinfectant residual. These parameters are dealt with as follows:
Measure the disinfectant residual at the selected sampling point.
Proceed only if a measurable disinfectant residual is present. Collect
triplicate 40 ml water samples at the pH prevailing at the time of
sampling, and prepare a method blank according to the methods. Seal and
store these samples together for seven days at 25 [deg]C or above. After
this time period, open one of the sample containers and check for
disinfectant residual. Absence of a disinfectant residual invalidates
the sample for further analysis. Once a disinfectant residual has been
demonstrated, open another of the sealed samples and determine total THM
concentration using an approved analytical method.
(h) The requirements in paragraphs (a) through (g) of this section
apply to subpart H community water systems which serve a population of
10,000 or more until December 31, 2001. The requirements in paragraphs
(a) through (g) of this section apply to community water systems which
use only ground water not under the direct influence of surface water
that add a disinfectant (oxidant) in any part of the treatment process
and serve a population of 10,000 or more until December 31, 2003. After
December 31, 2003, this section is no longer applicable.
[44 FR 68641, Nov. 29, 1979, as amended at 45 FR 15545, 15547, Mar. 11,
1980; 58 FR 41345, Aug. 3, 1993; 59 FR 62469, Dec. 5, 1994; 60 FR 34085,
June 29, 1995; 63 FR 69464, Dec. 16, 1998; 65 FR 26022, May 4, 2000; 66
FR 3776, Jan. 16, 2001]
Subpart D_Reporting and Recordkeeping
Sec. 141.31 Reporting requirements.
(a) Except where a shorter period is specified in this part, the
supplier of water shall report to the State the results of any test
measurement or analysis required by this part within (1) The first ten
days following the month in which the result is received, or (2) the
first ten days following the end of the required monitoring period as
stipulated by the State, whichever of these is shortest.
[[Page 392]]
(b) Except where a different reporting period is specified in this
part, the supplier of water must report to the State within 48 hours the
failure to comply with any national primary drinking water regulation
(including failure to comply with monitoring requirements) set forth in
this part.
(c) The supplier of water is not required to report analytical
results to the State in cases where a State laboratory performs the
analysis and reports the results to the State office which would
normally receive such notification from the supplier.
(d) The public water system, within 10 days of completing the public
notification requirements under Subpart Q of this part for the initial
public notice and any repeat notices, must submit to the primacy agency
a certification that it has fully complied with the public notification
regulations. The public water system must include with this
certification a representative copy of each type of notice distributed,
published, posted, and made available to the persons served by the
system and to the media.
(e) The water supply system shall submit to the State within the
time stated in the request copies of any records required to be
maintained under Sec. 141.33 hereof or copies of any documents then in
existence which the State or the Administrator is entitled to inspect
pursuant to the authority of section 1445 of the Safe Drinking Water Act
or the equivalent provisions of State law.
[40 FR 59570, Dec. 24, 1975, as amended at 45 FR 57345, Aug. 27, 1980;
65 FR 26022, May 4, 2000]
Sec. 141.32 Public notification.
The requirements in this section apply until the requirements of
Subpart Q of this part are applicable. Public water systems where EPA
directly implements the public water system supervision program must
comply with the requirements in Subpart Q of this part on October 31,
2000. All other public water systems must comply with the requirements
in Subpart Q of this part on May 6, 2002 or on the date the State-
adopted rule becomes effective, whichever comes first.
(a) Maximum contaminant levels (MCLs), maximum residual disinfectant
levels (MRDLs). The owner or operator of a public water system which
fails to comply with an applicable MCL or treatment technique
established by this part or which fails to comply with the requirements
of any schedule prescribed pursuant to a variance or exemption, shall
notify persons served by the system as follows:
(1) Except as provided in paragraph (a)(3) of this section, the
owner or operator of a public water system must give notice:
(i) By publication in a daily newspaper of general circulation in
the area served by the system as soon as possible, but in no case later
than 14 days after the violation or failure. If the area served by a
public water system is not served by a daily newspaper of general
circulation, notice shall instead be given by publication in a weekly
newspaper of general circulation serving the area; and
(ii) By mail delivery (by direct mail or with the water bill), or by
hand delivery, not later than 45 days after the violation or failure.
The State may waive mail or hand delivery if it determines that the
owner or operator of the public water system in violation has corrected
the violation or failure within the 45-day period. The State must make
the waiver in writing and within the 45-day period; and
(iii) For violations of the MCLs of contaminants or MRDLs of
disinfectants that may pose an acute risk to human health, by furnishing
a copy of the notice to the radio and television stations serving the
area served by the public water system as soon as possible but in no
case later than 72 hours after the violation. The following violations
are acute violations:
(A) Any violations specified by the State as posing an acute risk to
human health.
(B) Violation of the MCL for nitrate or nitrite as defined in Sec.
141.62 and determined according to Sec. 141.23(i)(3).
(C) Violation of the MCL for total coliforms, when fecal coliforms
or E. coli are present in the water distribution system, as specified in
Sec. 141.63(b).
(D) Occurrence of a waterborne disease outbreak, as defined in Sec.
141.2, in
[[Page 393]]
an unfiltered system subject to the requirements of subpart H of this
part, after December 30, 1991 (see Sec. 141.71(b)(4)).
(E) Violation of the MRDL for chlorine dioxide as defined in Sec.
141.65 and determined according to Sec. 141.133(c)(2).
(2) Except as provided in paragraph (a)(3) of this section,
following the initial notice given under paragraph (a)(1) of this
section, the owner or operator of the public water system must give
notice at least once every three months by mail delivery (by direct mail
or with the water bill) or by hand delivery, for as long as the
violation or failure exists.
(3)(i) In lieu of the requirements of paragraphs (a) (1) and (2) of
this section, the owner or operator of a community water system in an
area that is not served by a daily or weekly newspaper of general
circulation must give notice by hand delivery or by continuous posting
in conspicuous places within the area served by the system. Notice by
hand delivery or posting must begin as soon as possible, but no later
than 72 hours after the violation or failure for acute violations (as
defined in paragraph (a)(1)(iii) of this section), or 14 days after the
violation or failure (for any other violation). Posting must continue
for as long as the violation or failure exists. Notice by hand delivery
must be repeated at least every three months for as long as the
violation or failure exists.
(ii) In lieu of the requirements of paragraphs (a) (1) and (2) of
this section, the owner or operator of a non-community water system may
give notice by hand delivery or by continuous posting in conspicuous
places within the area served by the system. Notice by hand delivery or
posting must begin as soon as possible, but no later than 72 hours after
the violation or failure for acute violations (as defined in paragraph
(a)(1)(iii) of this section), or 14 days after the violation or failure
(for any other violation). Posting must continue for as long as the
violation or failure exists. Notice by hand delivery must be repeated at
least every three months for as long as the violation or failure exists.
(b) Other violations, variances, exemptions. The owner or operator
of a public water system which fails to perform monitoring required by
section 1445(a) of the Act (including monitoring required by the
National Primary Drinking Water Regulations (NPDWRs) of this part),
fails to comply with a testing procedure established by this part, is
subject to a variance granted under section 1415(a)(1)(A) or 1415(a)(2)
of the Act, or is subject to an exemption under section 1416 of the Act,
shall notify persons served by the system as follows:
(1) Except as provided in paragraph (b)(3) or (b)(4) of this
section, the owner or operator of a public water system must give notice
within three months of the violation or granting of a variance or
exemption by publication in a daily newspaper of general circulation in
the area served by the system. If the area served by a public water
system is not served by a daily newspaper of general circulation, notice
shall instead be given by publication in a weekly newspaper of general
circulation serving the area.
(2) Except as provided in paragraph (b)(3) or (b)(4) of this
section, following the initial notice given under paragraph (b)(1) of
this section, the owner or operator of the public water system must give
notice at least once every three months by mail delivery (by direct mail
or with the water bill) or by hand delivery, for as long as the
violation exists. Repeat notice of the existence of a variance or
exemption must be given every three months for as long as the variance
or exemption remains in effect.
(3)(i) In lieu of the requirements of paragraphs (b)(1) and (b)(2)
of this section, the owner or operator of a community water system in an
area that is not served by a daily or weekly newspaper of general
circulation must give notice, within three months of the violation or
granting of the variance or exemption, by hand delivery or by continuous
posting in conspicuous places with the area served by the system.
Posting must continue for as long as the violation exists or a variance
or exemption remains in effect. Notice by hand delivery must be repeated
at least every three months for as long as the violation exists or a
variance or exemption remains in effect.
[[Page 394]]
(ii) In lieu of the requirements of paragraphs (b)(1) and (b)(2) of
this section, the owner or operator of a non-community water system may
give notice, within three months of the violation or the granting of the
variance or exemption, by hand delivery or by continuous posting in
conspicuous places within the area served by the system. Posting must
continue for as long as the violation exists, or a variance or exemption
remains in effect. Notice by hand delivery must be repeated at least
every three months for as long as the violation exists or a variance or
exemption remains in effect.
(4) In lieu of the requirements of paragraphs (b)(1), (b)(2), and
(b)(3) of this section, the owner or operator of a public water system,
at the discretion of the State, may provide less frequent notice for
minor monitoring violations as defined by the State, if EPA has approved
the State's application for a program revision under Sec. 142.16.
Notice of such violations must be given no less frequently than
annually.
(c) Notice to new billing units. The owner or operator of a
community water system must give a copy of the most recent public notice
for any outstanding violation of any maximum contaminant level, or any
maximum residual disinfectant level, or any treatment technique
requirement, or any variance or exemption schedule to all new billing
units or new hookups prior to or at the time service begins.
(d) General content of public notice. Each notice required by this
section must provide a clear and readily understandable explanation of
the violation, any potential adverse health effects, the population at
risk, the steps that the public water system is taking to correct such
violation, the necessity for seeking alternative water supplies, if any,
and any preventive measures the consumer should take until the violation
is corrected. Each notice shall be conspicuous and shall not contain
unduly technical language, unduly small print, or similar problems that
frustrate the purpose of the notice. Each notice shall include the
telephone number of the owner, operator, or designee of the public water
system as a source of additional information concerning the notice.
Where appropriate, the notice shall be multi-lingual.
(e) Mandatory health effects language. When providing the
information on potential adverse health effects required by paragraph
(d) of this section in notices of violations of maximum contaminant
levels or treatment technique requirements, or notices of the granting
or the continued existence of exemptions or variances, or notices of
failure to comply with a variance or exemption schedule, the owner or
operator of a public water system shall include the language specified
below for each contaminant. (If language for a particular contaminant is
not specified below at the time notice is required, this paragraph does
not apply.)
(1) Trichloroethylene. The United States Environmental Protection
Agency (EPA) sets drinking water standards and has determined that
trichloroethylene is a health concern at certain levels of exposure.
This chemical is a common metal cleaning and dry cleaning fluid. It
generally gets into drinking water by improper waste disposal. This
chemical has been shown to cause cancer in laboratory animals such as
rats and mice when the animals are exposed at high levels over their
lifetimes. Chemicals that cause cancer in laboratory animals also may
increase the risk of cancer in humans who are exposed at lower levels
over long periods of time. EPA has set forth the enforceable drinking
water standard for trichloroethylene at 0.005 parts per million (ppm) to
reduce the risk of cancer or other adverse health effects which have
been observed in laboratory animals. Drinking water which meets this
standard is associated with little to none of this risk and should be
considered safe.
(2) Carbon tetrachloride. The United States Environmental Protection
Agency (EPA) sets drinking water standards and has determined that
carbon tetrachloride is a health concern at certain levels of exposure.
This chemical was once a popular household cleaning fluid. It generally
gets into drinking water by improper waste disposal. This chemical has
been shown to cause cancer in laboratory animals such as rats and mice
when the animals are exposed at high levels over
[[Page 395]]
their lifetimes. Chemicals that cause cancer in laboratory animals also
may increase the risk of cancer in humans who are exposed at lower
levels over long periods of of time. EPA has set the enforceable
drinking water standard for carbon tetrachloride at 0.005 parts per
million (ppm) to reduce the risk of cancer or other adverse health
effects which have been observed in laboratory animals. Drinking water
which meets this standard is associated with little to none of this risk
and should be considered safe.
(3) 1,2-Dichloroethane. The United States Environmental Protection
Agency (EPA) sets drinking water standards and has determined that 1,2-
dichloroethane is a health concern at certain levels of exposure. This
chemical is used as a cleaning fluid for fats, oils, waxes, and resins.
It generally gets into drinking water from improper waste disposal. This
chemical has been shown to cause cancer in laboratory animals such as
rats and mice when the animals are exposed at high levels over their
lifetimes. Chemicals that cause cancer in laboratory animals also may
increase the risk of cancer in humans who are exposed at lower levels
over long periods of time. EPA has set the enforceable drinking water
standard for 1,2-dichloroethane at 0.005 parts per million (ppm) to
reduce the risk of cancer or other adverse health effects which have
been observed in laboratory animals. Drinking water which meets this
standard is associated with little to none of this risk and should be
considered safe.
(4) Vinyl chloride. The United States Environmental Protection
Agency (EPA) sets drinking water standards and has determined that vinyl
chloride is a health concern at certain levels of exposure. This
chemical is used in industry and is found in drinking water as a result
of the breakdown of related solvents. The solvents are used as cleaners
and degreasers of metals and generally get into drinking water by
improper waste disposal. This chemical has been associated with
significantly increased risks of cancer among certain industrial workers
who were exposed to relatively large amounts of this chemical during
their working careers. This chemical has also been shown to cause cancer
in laboratory animals when the animals are exposed at high levels over
their lifetimes. Chemicals that cause increased risk of cancer among
exposed industrial workers and in laboratory animals also may increase
the risk of cancer in humans who are exposed at lower levels over long
periods of time. EPA has set the enforceable drinking water standard for
vinyl chloride at 0.002 part per million (ppm) to reduce the risk of
cancer or other adverse health effects which have been observed in
humans and laboratory animals. Drinking water which meets this standard
is associated with little to none of this risk and should be considered
safe.
(5) Benzene. The United States Environmental Protection Agency (EPA)
sets drinking water standards and has determined that benzene is a
health concern at certain levels of exposure. This chemical is used as a
solvent and degreaser of metals. It is also a major component of
gasoline. Drinking water contamination generally results from leaking
undergound gasoline and petroleum tanks or improper waste disposal. This
chemical has been associated with significantly increased risks of
leukemia among certain industrial workers who were exposed to relatively
large amounts of this chemical during their working careers. This
chemical has also been shown to cause cancer in laboratory animals when
the animals are exposed at high levels over their lifetimes. Chemicals
that cause increased risk of cancer among exposed industrial workers and
in laboratory animals also may increase the risk of cancer in humans who
are exposed at lower levels over long periods of time. EPA has set the
enforceable drinking water standard for benzene at 0.005 parts per
million (ppm) to reduce the risk of cancer or other adverse health
effects which have been observed in humans and laboratory animals.
Drinking water which meets this standard is associated with little to
none of this risk and should be considered safe.
(6) 1,1-Dichloroethylene. The United States Environmental Protection
Agency (EPA) sets drinking water standards and has determined that 1,1-
dichloroethylene is a health concern at
[[Page 396]]
certain levels of exposure. This chemical is used in industry and is
found in drinking water as a result of the breakdown of related
solvents. The solvents are used as cleaners and degreasers of metals and
generally get into drinking water by improper waste disposal. This
chemical has been shown to cause liver and kidney damage in laboratory
animals such as rats and mice when the animals are exposed at high
levels over their lifetimes. Chemicals which cause adverse effects in
laboratory animals also may cause adverse health effects in humans who
are exposed at lower levels over long periods of time. EPA has set the
enforceable drinking water standard for 1,1-dichloroethylene at 0.007
parts per million (ppm) to reduce the risk of these adverse health
effects which have been observed in laboratory animals. Drinking water
which meets this standard is associated with little to none of this risk
and should be considered safe.
(7) Para-dichlorobenzene. The United States Environmental Protection
Agency (EPA) sets drinking water standards and has determined that para-
dichlorobenzene is a health concern at certain levels of exposure. This
chemical is a component of deodorizers, moth balls, and pesticides. It
generally gets into drinking water by improper waste disposal. This
chemical has been shown to cause liver and kidney damage in laboratory
animals such as rats and mice when the animals are exposed to high
levels over their lifetimes. Chemicals which cause adverse effects in
laboratory animals also may cause adverse health effects in humans who
are exposed at lower levels over long periods of time. EPA has set the
enforceable drinking water standard for para-dichlorobenzene at 0.075
parts per million (ppm) to reduce the risk of these adverse health
effects which have been observed in laboratory animals. Drinking water
which meets this standard is associated with little to none of this risk
and should be considered safe.
(8) 1,1,1-Trichloroethane. The United States Environmental
Protection Agency (EPA) sets drinking water standards and has determined
that the 1,1,1-trichloroethane is a health concern at certain levels of
exposure. This chemical is used as a cleaner and degreaser of metals. It
generally gets into drinking water by improper waste disposal. This
chemical has been shown to damage the liver, nervous system, and
circulatory system of laboratory animals such as rats and mice when the
animals are exposed at high levels over their lifetimes. Some industrial
workers who were exposed to relatively large amounts of this chemical
during their working careers also suffered damage to the liver, nervous
system, and circulatory system. Chemicals which cause adverse effects
among exposed industrial workers and in laboratory animals also may
cause adverse health effects in humans who are exposed at lower levels
over long periods of time. EPA has set the enforceable drinking water
standard for 1,1,1-trichloroethane at 0.2 parts per million (ppm) to
protect against the risk of these adverse health effects which have been
observed in humans and laboratory animals. Drinking water which meets
this standard is associated with little to none of this risk and should
be considered safe.
(9) Fluoride.
[Note: EPA is not specifying language that must be included in a
public notice for a violation of the fluoride maximum contaminant level
in this section because Sec. 143.5 of this part includes the necessary
information. See paragraph (f) of this section.]
(10) Microbiological contaminants (for use when there is a violation
of the treatment technique requirements for filtration and disinfection
in subpart H or subpart P of this part). The United States Environmental
Protection Agency (EPA) sets drinking water standards and has determined
that the presence of microbiological contaminants are a health concern
at certain levels of exposure. If water is inadequately treated,
microbiological contaminants in that water may cause disease. Disease
symptoms may include diarrhea, cramps, nausea, and possibly jaundice,
and any associated headaches and fatigue. These symptoms, however, are
not just associated with disease-causing organisms in drinking water,
but also may be caused by a number of factors other than your drinking
water. EPA has set enforceable requirements for treating drinking water
to reduce the risk of these adverse health
[[Page 397]]
effects. Treatment such as filtering and disinfecting the water removes
or destroys microbiological contaminants. Drinking water which is
treated to meet EPA requirements is associated with little to none of
this risk and should be considered safe.
(11) Total coliforms (To be used when there is a violation of Sec.
141.63(a), and not a violation of Sec. 141.63(b)). The United States
Environmental Protection Agency (EPA) sets drinking water standards and
has determined that the presence of total coliforms is a possible health
concern. Total coliforms are common in the environment and are generally
not harmful themselves. The presence of these bacteria in drinking
water, however, generally is a result of a problem with water treatment
or the pipes which distribute the water, and indicates that the water
may be contaminated with organisms that can cause disease. Disease
symptoms may include diarrhea, cramps, nausea, and possibly jaundice,
and any associated headaches and fatigue. These symptoms, however, are
not just associated with disease-causing organisms in drinking water,
but also may be caused by a number of factors other than your drinking
water. EPA has set an enforceable drinking water standard for total
coliforms to reduce the risk of these adverse health effects. Under this
standard, no more than 5.0 percent of the samples collected during a
month can contain these bacteria, except that systems collecting fewer
than 40 samples/month that have one total coliform-positive sample per
month are not violating the standard. Drinking water which meets this
standard is usually not associated with a health risk from disease-
causing bacteria and should be considered safe.
(12) Fecal Coliforms/E. coli (To be used when there is a violation
of Sec. 141.63(b) or both Sec. 141.63 (a) and (b)). The United States
Environmental Protection Agency (EPA) sets drinking water standards and
has determined that the presence of fecal coliforms or E. coli is a
serious health concern. Fecal coliforms and E. coli are generally not
harmful themselves, but their presence in drinking water is serious
because they usually are associated with sewage or animal wastes. The
presence of these bacteria in drinking water is generally a result of a
problem with water treatment or the pipes which distribute the water,
and indicates that the water may be contaminated with organisms that can
cause disease. Disease symptoms may include diarrhea, cramps, nausea,
and possibly jaundice, and associated headaches and fatigue. These
symptoms, however, are not just associated with disease-causing
organisms in drinking water, but also may be caused by a number of
factors other than your drinking water. EPA has set an enforceable
drinking water standard for fecal coliforms and E. coli to reduce the
risk of these adverse health effects. Under this standard all drinking
water samples must be free of these bacteria. Drinking water which meets
this standard is associated with little or none of this risk and should
be considered safe. State and local health authorities recommend that
consumers take the following precautions: [To be inserted by the public
water system, according to instructions from State or local
authorities].
(13) Lead. The United States Environmental Protection Agency (EPA)
sets drinking water standards and has determined that lead is a health
concern at certain exposure levels. Materials that contain lead have
frequently been used in the construction of water supply distribution
systems, and plumbing systems in private homes and other buildings. The
most commonly found materials include service lines, pipes, brass and
bronze fixtures, and solders and fluxes. Lead in these materials can
contaminate drinking water as a result of the corrosion that takes place
when water comes into contact with those materials. Lead can cause a
variety of adverse health effects in humans. At relatively low levels of
exposure, these effects may include interference with red blood cell
chemistry, delays in normal physical and mental development in babies
and young children, slight deficits in the attention span, hearing, and
learning abilities of children, and slight increases in the blood
pressure of some adults. EPA's national primary drinking water
regulation requires all
[[Page 398]]
public water systems to optimize corrosion control to minimize lead
contamination resulting from the corrosion of plumbing materials. Public
water systems serving 50,000 people or fewer that have lead
concentrations below 15 parts per billion (ppb) in more than 90% of tap
water samples (the EPA ``action level'') have optimized their corrosion
control treatment. Any water system that exceeds the action level must
also monitor their source water to determine whether treatment to remove
lead in source water is needed. Any water system that continues to
exceed the action level after installation of corrosion control and/or
source water treatment must eventually replace all lead service lines
contributing in excess of 15 (ppb) of lead to drinking water. Any water
system that exceeds the action level must also undertake a public
education program to inform consumers of ways they can reduce their
exposure to potentially high levels of lead in drinking water.
(14) Copper. The United States Environmental Protection Agency (EPA)
sets drinking water standards and has determined that copper is a health
concern at certain exposure levels. Copper, a reddish-brown metal, is
often used to plumb residential and commercial structures that are
connected to water distribution systems. Copper contaminating drinking
water as a corrosion byproduct occurs as the result of the corrosion of
copper pipes that remain in contact with water for a prolonged period of
time. Copper is an essential nutrient, but at high doses it has been
shown to cause stomach and intestinal distress, liver and kidney damage,
and anemia. Persons with Wilson's disease may be at a higher risk of
health effects due to copper than the general public. EPA's national
primary drinking water regulation requires all public water systems to
install optimal corrosion control to minimize copper contamination
resulting from the corrosion of plumbing materials. Public water systems
serving 50,000 people or fewer that have copper concentrations below 1.3
parts per million (ppm) in more than 90% of tap water samples (the EPA
``action level'') are not required to install or improve their
treatment. Any water system that exceeds the action level must also
monitor their source water to determine whether treatment to remove
copper in source water is needed.
(15) Asbestos. The United States Environmental Protection Agency
(EPA) sets drinking water standards and has determined that asbestos
fibers greater than 10 micrometers in length are a health concern at
certain levels of exposure. Asbestos is a naturally occurring mineral.
Most asbestos fibers in drinking water are less than 10 micrometers in
length and occur in drinking water from natural sources and from
corroded asbestos-cement pipes in the distribution system. The major
uses of asbestos were in the production of cements, floor tiles, paper
products, paint, and caulking; in transportation-related applications;
and in the production of textiles and plastics. Asbestos was once a
popular insulating and fire retardent material. Inhalation studies have
shown that various forms of asbestos have produced lung tumors in
laboratory animals. The available information on the risk of developing
gastrointestinal tract cancer associated with the ingestion of asbestos
from drinking water is limited. Ingestion of intermediate-range
chrysotile asbestos fibers greater than 10 micrometers in length is
associated with causing benign tumors in male rats. Chemicals that cause
cancer in laboratory animals also may increase the risk of cancer in
humans who are exposed over long periods of time. EPA has set the
drinking water standard for asbestos at 7 million long fibers per liter
to reduce the potential risk of cancer or other adverse health effects
which have been observed in laboratory animals. Drinking water which
meets the EPA standard is associated with little to none of this risk
and should be considered safe with respect to asbestos.
(16) Barium. The United States Environmental Protection Agency (EPA)
sets drinking water standards and has determined that barium is a health
concern at certain levels of exposure. This inorganic chemical occurs
naturally in some aquifers that serve as sources of ground water. It is
also used in oil and gas drilling muds, automotive paints, bricks, tiles
and jet fuels. It generally gets into drinking
[[Page 399]]
water after dissolving from naturally occurring minerals in the ground.
This chemical may damage the heart and cardiovascular system, and is
associated with high blood pressure in laboratory animals such as rats
exposed to high levels during their lifetimes. In humans, EPA believes
that effects from barium on blood pressure should not occur below 2
parts per million (ppm) in drinking water. EPA has set the drinking
water standard for barium at 2 parts per million (ppm) to protect
against the risk of these adverse health effects. Drinking water that
meets the EPA standard is associated with little to none of this risk
and is considered safe with respect to barium.
(17) Cadmium. The United States Environmental Protection Agency
(EPA) sets drinking water standards and has determined that cadmium is a
health concern at certain levels of exposure. Food and the smoking of
tobacco are common sources of general exposure. This inorganic metal is
a contaminant in the metals used to galvanize pipe. It generally gets
into water by corrosion of galvanized pipes or by improper waste
disposal. This chemical has been shown to damage the kidney in animals
such as rats and mice when the animals are exposed at high levels over
their lifetimes. Some industrial workers who were exposed to relatively
large amounts of this chemical during working careers also suffered
damage to the kidney. EPA has set the drinking water standard for
cadmium at 0.005 parts per million (ppm) to protect against the risk of
these adverse health effects. Drinking water that meets the EPA standard
is associated with little to none of this risk and is considered safe
with respect to cadmium.
(18) Chromium. The United States Environmental Protection Agency
(EPA) sets drinking water standards and has determined that chromium is
a health concern at certain levels of exposure. This inorganic metal
occurs naturally in the ground and is often used in the electroplating
of metals. It generally gets into water from runoff from old mining
operations and improper waste disposal from plating operations. This
chemical has been shown to damage the kidney, nervous system, and the
circulatory system of laboratory animals such as rats and mice when the
animals are exposed at high levels. Some humans who were exposed to high
levels of this chemical suffered liver and kidney damage, dermatitis and
respiratory problems. EPA has set the drinking water standard for
chromium at 0.1 parts per million (ppm) to protect against the risk of
these adverse health effects. Drinking water that meets the EPA standard
is associated with little to none of this risk and is considered safe
with respect to chromium.
(19) Mercury. The United States Environmental Protection Agency
(EPA) sets drinking water standards and has determined that mercury is a
health concern at certain levels of exposure. This inorganic metal is
used in electrical equipment and some water pumps. It usually gets into
water as a result of improper waste disposal. This chemical has been
shown to damage the kidney of laboratory animals such as rats when the
animals are exposed at high levels over their lifetimes. EPA has set the
drinking water standard for mercury at 0.002 parts per million (ppm) to
protect against the risk of these adverse health effects. Drinking water
that meets the EPA standard is associated with little to none of this
risk and is considered safe with respect to mercury.
(20) Nitrate. The United States Environmental Protection Agency
(EPA) sets drinking water standards and has determined that nitrate
poses an acute health concern at certain levels of exposure. Nitrate is
used in fertilizer and is found in sewage and wastes from human and/or
farm animals and generally gets into drinking water from those
activities. Excessive levels of nitrate in drinking water have caused
serious illness and sometimes death in infants under six months of age.
The serious illness in infants is caused because nitrate is converted to
nitrite in the body. Nitrite interferes with the oxygen carrying
capacity of the child's blood. This is an acute disease in that symptoms
can develop rapidly in infants. In most cases, health deteriorates over
a period of days. Symptoms
[[Page 400]]
include shortness of breath and blueness of the skin. Clearly, expert
medical advice should be sought immediately if these symptoms occur. The
purpose of this notice is to encourage parents and other responsible
parties to provide infants with an alternate source of drinking water.
Local and State health authorities are the best source for information
concerning alternate sources of drinking water for infants. EPA has set
the drinking water standard at 10 parts per million (ppm) for nitrate to
protect against the risk of these adverse effects. EPA has also set a
drinking water standard for nitrite at 1 ppm. To allow for the fact that
the toxicity of nitrate and nitrite are additive, EPA has also
established a standard for the sum of nitrate and nitrite at 10 ppm.
Drinking water that meets the EPA standard is associated with little to
none of this risk and is considered safe with respect to nitrate.
(21) Nitrite. The United States Environmental Protection Agency
(EPA) sets drinking water standards and has determined that nitrite
poses an acute health concern at certain levels of exposure. This
inorganic chemical is used in fertilizers and is found in sewage and
wastes from humans and/or farm animals and generally gets into drinking
water as a result of those activities. While excessive levels of nitrite
in drinking water have not been observed, other sources of nitrite have
caused serious illness and sometimes death in infants under six months
of age. The serious illness in infants is caused because nitrite
interferes with the oxygen carrying capacity of the child's blood. This
is an acute disease in that symptoms can develop rapidly. However, in
most cases, health deteriorates over a period of days. Symptoms include
shortness of breath and blueness of the skin. Clearly, expert medical
advice should be sought immediately if these symptoms occur. The purpose
of this notice is to encourage parents and other responsible parties to
provide infants with an alternate source of drinking water. Local and
State health authorities are the best source for information concerning
alternate sources of drinking water for infants. EPA has set the
drinking water standard at 1 part per million (ppm) for nitrite to
protect against the risk of these adverse effects. EPA has also set a
drinking water standard for nitrate (converted to nitrite in humans) at
10 ppm and for the sum of nitrate and nitrite at 10 ppm. Drinking water
that meets the EPA standard is associated with little to none of this
risk and is considered safe with respect to nitrite.
(22) Selenium. The United States Environmental Protection Agency
(EPA) sets drinking water standards and has determined that selenium is
a health concern at certain high levels of exposure. Selenium is also an
essential nutrient at low levels of exposure. This inorganic chemical is
found naturally in food and soils and is used in electronics, photocopy
operations, the manufacture of glass, chemicals, drugs, and as a
fungicide and a feed additive. In humans, exposure to high levels of
selenium over a long period of time has resulted in a number of adverse
health effects, including a loss of feeling and control in the arms and
legs. EPA has set the drinking water standard for selenium at 0.05 parts
per million (ppm) to protect against the risk of these adverse health
effects. Drinking water that meets the EPA standard is associated with
little to none of this risk and is considered safe with respect to
selenium.
(23) Acrylamide. The United States Environmental Protection Agency
(EPA) sets drinking water standards and has determined that acrylamide
is a health concern at certain levels of exposure. Polymers made from
acrylamide are sometimes used to treat water supplies to remove
particulate contaminants. Acrylamide has been shown to cause cancer in
laboratory animals such as rats and mice when the animals are exposed at
high levels over their lifetimes. Chemicals that cause cancer in
laboratory animals also may increase the risk of cancer in humans who
are exposed over long periods of time. Sufficiently large doses of
acrylamide are known to cause neurological injury. EPA has set the
drinking water standard for acrylamide using a treatment technique to
reduce the risk of cancer or other adverse health effects which have
been observed in laboratory animals. This treatment technique limits the
amount
[[Page 401]]
of acrylamide in the polymer and the amount of the polymer which may be
added to drinking water to remove particulates. Drinking water systems
which comply with this treatment technique have little to no risk and
are considered safe with respect to acrylamide.
(24) Alachlor. The United States Environmental Protection Agency
(EPA) sets drinking water standards and has determined that alachlor is
a health concern at certain levels of exposure. This organic chemical is
a widely used pesticide. When soil and climatic conditions are
favorable, alachlor may get into drinking water by runoff into surface
water or by leaching into ground water. This chemical has been shown to
cause cancer in laboratory animals such as rats and mice when the
animals are exposed at high levels over their lifetimes. Chemicals that
cause cancer in laboratory animals also may increase the risk of cancer
in humans who are exposed over long periods of time. EPA has set the
drinking water standard for alachlor at 0.002 parts per million (ppm) to
reduce the risk of cancer or other adverse health effects which have
been observed in laboratory animals. Drinking water that meets this
standard is associated with little to none of this risk and is
considered safe with respect to alachlor.
(25) Aldicarb. The United States Environmental Protection Agency
(EPA) sets drinking water standards and has determined that aldicarb is
a health concern at certain levels of exposure. Aldicarb is a widely
used pesticide. Under certain soil and climatic conditions (e.g., sandy
soil and high rainfall), aldicarb may leach into ground water after
normal agricultural applications to crops such as potatoes or peanuts or
may enter drinking water supplies as a result of surface runoff. This
chemical has been shown to damage the nervous system in laboratory
animals such as rats and dogs exposed to high levels. EPA has set the
drinking water standard for aldicarb at 0.003 parts per million (ppm) to
protect against the risk of adverse health effects. Drinking water that
meets the EPA standard is associated with little to none of this risk
and is considered safe with respect to aldicarb.
(26) Aldicarb sulfoxide. The United States Environmental Protection
Agency (EPA) sets drinking water standards and has determined that
aldicarb sulfoxide is a health concern at certain levels of exposure.
Aldicarb is a widely used pesticide. Aldicarb sulfoxide in ground water
is primarily a breakdown product of aldicarb. Under certain soil and
climatic conditions (e.g., sandy soil and high rainfall), aldicarb
sulfoxide may leach into ground water after normal agricultural
applications to crops such as potatoes or peanuts or may enter drinking
water supplies as a result of surface runoff. This chemical has been
shown to damage the nervous system in laboratory animals such as rats
and dogs exposed to high levels. EPA has set the drinking water standard
for aldicarb sulfoxide at 0.004 parts per million (ppm) to protect
against the risk of adverse health effects. Drinking water that meets
the EPA standard is associated with little to none of this risk and is
considered safe with respect to aldicarb sulfoxide.
(27) Aldicarb sulfone. The United States Environmental Protection
Agency (EPA) sets drinking water standards and has determined that
aldicarb sulfone is a health concern at certain levels of exposure.
Aldicarb is a widely used pesticide. Aldicarb sulfone is formed from the
breakdown of aldicarb and is considered for registration as a pesticide
under the name aldoxycarb. Under certain soil and climatic conditions
(e.g., sandy soil and high rainfall), aldicarb sulfone may leach into
ground water after normal agricultural applications to crops such as
potatoes or peanuts or may enter drinking water supplies as a result of
surface runoff. This chemical has been shown to damage the nervous
system in laboratory animals such as rats and dogs exposed to high
levels. EPA has set the drinking water standard for aldicarb sulfone at
0.002 parts per million (ppm) to protect against the risk of adverse
health effects. Drinking water that meets the EPA standard is associated
with little to none of this risk and is considered safe with respect to
aldicarb sulfone.
(28) Atrazine. The United States Environmental Protection Agency
(EPA)
[[Page 402]]
sets drinking water standards and has determined that atrazine is a
health concern at certain levels of exposure. This organic chemical is a
herbicide. When soil and climatic conditions are favorable, atrazine may
get into drinking water by runoff into surface water or by leaching into
ground water. This chemical has been shown to affect offspring of rats
and the heart of dogs. EPA has set the drinking water standard for
atrazine at 0.003 parts per million (ppm) to protect against the risk of
these adverse health effects. Drinking water that meets the EPA standard
is associated with little to none of this risk and is considered safe
with respect to atrazine.
(29) Carbofuran. The United States Environmental Protection Agency
(EPA) sets drinking water standards and has determined that carbofuran
is a health concern at certain levels of exposure. This organic chemical
is a pesticide. When soil and climatic conditions are favorable,
carbofuran may get into drinking water by runoff into surface water or
by leaching into ground water. This chemical has been shown to damage
the nervous and reproductive systems of laboratory animals such as rats
and mice exposed at high levels over their lifetimes. Some humans who
were exposed to relatively large amounts of this chemical during their
working careers also suffered damage to the nervous system. Effects on
the nervous system are generally rapidly reversible. EPA has set the
drinking water standard for carbofuran at 0.04 parts per million (ppm)
to protect against the risk of these adverse health effects. Drinking
water that meets the EPA standard is associated with little to none of
this risk and is considered safe with respect to carbofuran.
(30) Chlordane. The United States Environmental Protection Agency
(EPA sets drinking water standards and has determined that chlordane is
a health concern at certain levels of exposure. This organic chemical is
a pesticide used to control termites. Chlordane is not very mobile in
soils. It usually gets into drinking water after application near water
supply intakes or wells. This chemical has been shown to cause cancer in
laboratory animals such as rats and mice when the animals are exposed at
high levels over their lifetimes. Chemicals that cause cancer in
laboratory animals also may increase the risk of cancer in humans who
are exposed over long periods of time. EPA has set the drinking water
standard for chlordane at 0.002 parts per million (ppm) to reduce the
risk of cancer or other adverse health effects which have been observed
in laboratory animals. Drinking water that meets the EPA standard is
associated with little to none of this risk and is considered safe with
respect to chlordane.
(31) Dibromochloropropane (DBCP). The United States Environmental
Protection Agency (EPA) sets drinking water standards and has determined
that DBCP is a health concern at certain levels of exposure. This
organic chemical was once a popular pesticide. When soil and climatic
conditions are favorable, dibromochloropropane may get into drinking
water by runoff into surface water or by leaching into ground water.
This chemical has been shown to cause cancer in laboratory animals such
as rats and mice when the animals are exposed at high levels over their
lifetimes. Chemicals that cause cancer in laboratory animals also may
increase the risk of cancer in humans who are exposed over long periods
of time. EPA has set the drinking water standard for DBCP at 0.0002
parts per million (ppm) to reduce the risk of cancer or other adverse
health effects which have been observed in laboratory animals. Drinking
water that meets the EPA standard is associated with little to none of
this risk and is considered safe with respect to DBCP.
(32) o-Dichlorobenzene. The United States Environmental Protection
Agency (EPA) sets drinking water standards and has determined that o-
dichlorobenzene is a health concern at certain levels of exposure. This
organic chemical is used as a solvent in the production of pesticides
and dyes. It generally gets into water by improper waste disposal. This
chemical has been shown to damage the liver, kidney and the blood cells
of laboratory animals such as rats and mice exposed to high levels
during their lifetimes. Some industrial workers who were exposed to
[[Page 403]]
relatively large amounts of this chemical during working careers also
suffered damage to the liver, nervous system, and circulatory system.
EPA has set the drinking water standard for o-dichlorobenzene at 0.6
parts per million (ppm) to protect against the risk of these adverse
health effects. Drinking water that meets the EPA standard is associated
with little to none of this risk and is considered safe with respect to
o-dichlorobenzene.
(33) cis-1,2-Dichloroethylene. The United States Environmental
Protection Agency (EPA) establishes drinking water standards and has
determined that cis-1,2-dichloroethylene is a health concern at certain
levels of exposure. This organic chemical is used as a solvent and
intermediate in chemical production. It generally gets into water by
improper waste disposal. This chemical has been shown to damage the
liver, nervous system, and circulatory system of laboratory animals such
as rats and mice when exposed at high levels over their lifetimes. Some
humans who were exposed to relatively large amounts of this chemical
also suffered damage to the nervous system. EPA has set the drinking
water standard for cis-1,2-dichloroethylene at 0.07 parts per million
(ppm) to protect against the risk of these adverse health effects.
Drinking water that meets the EPA standard is associated with little to
none of this risk and is considered safe with respect to cis-1,2-
dichloroethylene.
(34) trans-1,2-Dichloroethylene. The United States Environmental
Protection Agency (EPA) establishes drinking water standards and has
determined that trans-1,2-dichloroethylene is a health concern at
certain levels of exposure. This organic chemical is used as a solvent
and intermediate in chemical production. It generally gets into water by
improper waste disposal. This chemical has been shown to damage the
liver, nervous system, and the circulatory system of laboratory animals
such as rats and mice when exposed at high levels over their lifetimes.
Some humans who were exposed to relatively large amounts of this
chemical also suffered damage to the nervous system. EPA has set
drinking water standard for trans-1,2-dichloroethylene at 0.1 parts per
million (ppm) to protect against the risk of these adverse health
effects. Drinking water that meets the EPA standard is associated with
little to none of this risk and is considered safe with respect to
trans-1,2-dichloroethylene.
(35) 1,2-Dichloropropane. The United States Environmental Protection
Agency (EPA) sets drinking water standards and has determined that 1,2-
dichloropropane is a health concern at certain levels of exposure. This
organic chemical is used as a solvent and pesticide. When soil and
climatic conditions are favorable, 1,2-dichloropropane may get into
drinking water by runoff into surface water or by leaching into ground
water. It may also get into drinking water through improper waste
disposal. This chemical has been shown to cause cancer in laboratory
animals such as rats and mice when the animals are exposed at high
levels over their lifetimes. Chemicals that cause cancer in laboratory
animals also may increase the risk of cancer in humans who are exposed
over long periods of time. EPA has set the drinking water standard for
1,2-dichloropropane at 0.005 parts per million (ppm) to reduce the risk
of cancer or other adverse health effects which have been observed in
laboratory animals. Drinking water that meets the EPA standard is
associated with little to none of this risk and is considered safe with
respect to 1,2-dichloropropane.
(36) 2,4-D. The United States Environmental Protection Agency (EPA)
sets drinking water standards and has determined that 2,4-D is a health
concern at certain levels of exposure. This organic chemical is used as
a herbicide and to control algae in reservoirs. When soil and climatic
conditions are favorable, 2,4-D may get into drinking water by runoff
into surface water or by leaching into ground water. This chemical has
been shown to damage the liver and kidney of laboratory animals such as
rats exposed at high levels during their lifetimes. Some humans who were
exposed to relatively large amounts of this chemical also suffered
damage to the nervous system. EPA has set the drinking water standard
for 2,4-D at 0.07 parts per million (ppm) to protect against the risk of
[[Page 404]]
these adverse health effects. Drinking water that meets the EPA standard
is associated with little to none of this risk and is considered safe
with respect to 2,4-D.
(37) Epichlorohydrin. The United States Environmental Protection
Agency (EPA) sets drinking water standards and has determined that
epichlorohydrin is a health concern at certain levels of exposure.
Polymers made from epichlorohydrin are sometimes used in the treatment
of water supplies as a flocculent to remove particulates.
Epichlorohydrin generally gets into drinking water by improper use of
these polymers. This chemical has been shown to cause cancer in
laboratory animals such as rats and mice when the animals are exposed at
high levels over their lifetimes. Chemicals that cause cancer in
laboratory animals also may increase the risk of cancer in humans who
are exposed over long periods of time. EPA has set the drinking water
standard for epichlorohydrin using a treatment technique to reduce the
risk of cancer or other adverse health effects which have been observed
in laboratory animals. This treatment technique limits the amount of
epichlorohydrin in the polymer and the amount of the polymer which may
be added to drinking water as a flocculent to remove particulates.
Drinking water systems which comply with this treatment technique have
little to no risk and are considered safe with respect to
epichlorohydrin.
(38) Ethylbenzene. The United States Environmental Protection Agency
(EPA) sets drinking water standards and has determined ethylbenzene is a
health concern at certain levels of exposure. This organic chemical is a
major component of gasoline. It generally gets into water by improper
waste disposal or leaking gasoline tanks. This chemical has been shown
to damage the kidney, liver, and nervous system of laboratory animals
such as rats exposed to high levels during their lifetimes. EPA has set
the drinking water standard for ethylbenzene at 0.7 part per million
(ppm) to protect against the risk of these adverse health effects.
Drinking water that meets the EPA standard is associated with little to
none of this risk and is considered safe with respect to ethylbenzene.
(39) Ethylene dibromide (EDB). The United States Environmental
Protection Agency (EPA) sets drinking water standards and has determined
that EDB is a health concern at certain levels of exposure. This organic
chemical was once a popular pesticide. When soil and climatic conditions
are favorable, EDB may get into drinking water by runoff into surface
water or by leaching into ground water. This chemical has been shown to
cause cancer in laboratory animals such as rats and mice when the
animals are exposed at high levels over their lifetimes. Chemicals that
cause cancer in laboratory animals also may increase the risk of cancer
in humans who are exposed over long periods of time. EPA has set the
drinking water standard for EDB at 0.00005 part per million (ppm) to
reduce the risk of cancer or other adverse health effects which have
been observed in laboratory animals. Drinking water that meets this
standard is associated with little to none of this risk and is
considered safe with respect to EDB.
(40) Heptachlor. The United States Environmental Protection Agency
(EPA) sets drinking water standards and has determined that heptachlor
is a health concern at certain levels of exposure. This organic chemical
was once a popular pesticide. When soil and climatic conditions are
favorable, heptachlor may get into drinking water by runoff into surface
water or by leaching into ground water. This chemical has been shown to
cause cancer in laboratory animals such as rats and mice when the
animals are exposed at high levels over their lifetimes. Chemicals that
cause cancer in laboratory animals also may increase the risk of cancer
in humans who are exposed over long periods of time. EPA has set the
drinking water standards for heptachlor at 0.0004 part per million (ppm)
to reduce the risk of cancer or other adverse health effects which have
been observed in laboratory animals. Drinking water that meets this
standard is associated with little to none of this risk and is
considered safe with respect to heptachlor.
[[Page 405]]
(41) Heptachlor epoxide. The United States Environmental Protection
Agency (EPA) sets drinking water standards and has determined that
heptachlor epoxide is a health concern at certain levels of exposure.
This organic chemical was once a popular pesticide. When soil and
climatic conditions are favorable, heptachlor expoxide may get into
drinking water by runoff into surface water or by leaching into ground
water. This chemical has been shown to cause cancer in laboratory
animals such as rats and mice when the animals are exposed at high
levels over their lifetimes. Chemicals that cause cancer in laboratory
animals also may increase the risk of cancer in humans who are exposed
over long periods of time. EPA has set the drinking water standards for
heptachlor epoxide at 0.0002 part per million (ppm) to reduce the risk
of cancer or other adverse health effects which have been observed in
laboratory animals. Drinking water that meets this standard is
associated with little to none of this risk and is considered safe with
respect to heptachlor epoxide.
(42) Lindane. The United States Environmental Protection Agency
(EPA) sets drinking water standards and has determined that lindane is a
health concern at certain levels of exposure. This organic chemical is
used as a pesticide. When soil and climatic conditions are favorable,
lindane may get into drinking water by runoff into surface water or by
leaching into ground water. This chemical has been shown to damage the
liver, kidney, nervous system, and immune system of laboratory animals
such as rats, mice and dogs exposed at high levels during their
lifetimes. Some humans who were exposed to relatively large amounts of
this chemical also suffered damage to the nervous system and circulatory
system. EPA has established the drinking water standard for lindane at
0.0002 part per million (ppm) to protect against the risk of these
adverse health effects. Drinking water that meets the EPA standard is
associated with little to none of this risk and is considered safe with
respect to lindane.
(43) Methoxychlor. The United States Environmental Protection Agency
(EPA) sets drinking water standards and has determined that methoxychlor
is a health concern at certain levels of exposure. This organic chemical
is used as a pesticide. When soil and climatic conditions are favorable,
methoxychlor may get into drinking water by runoff into surface water or
by leaching into ground water. This chemical has been shown to damage
the liver, kidney, nervous system, and reproductive system of laboratory
animals such as rats exposed at high levels during their lifetimes. It
has also been shown to produce growth retardation in rats. EPA has set
the drinking water standard for methoxychlor at 0.04 part per million
(ppm) to protect against the risk of these adverse health effects.
Drinking water that meets the EPA standard is associated with little to
none of this risk and is considered safe with respect to methoxychlor.
(44) Monochlorobenzene. The United States Environmental Protection
Agency (EPA) sets drinking water standards and has determined that
monochlorobenzene is a health concern at certain levels of exposure.
This organic chemical is used as a solvent. It generally gets into water
by improper waste disposal. This chemical has been shown to damage the
liver, kidney and nervous system of laboratory animals such as rats and
mice exposed to high levels during their lifetimes. EPA has set the
drinking water standard for monochlorobenzene at 0.1 part per million
(ppm) to protect against the risk of these adverse health effects.
Drinking water that meets the EPA standard is associated with little to
none of this risk and is considered safe with respect to
monochlorobenzene.
(45) Polychlorinated biphenyls (PCBs). The United States
Environmental Protection Agency (EPA) sets drinking water standards and
has determined that polychlorinated biphenyls (PCBs) are a health
concern at certain levels of exposure. These organic chemicals were once
widely used in electrical transformers and other industrial equipment.
They generally get into drinking water by improper waste disposal or
leaking electrical industrial equipment. This chemical has been shown to
cause cancer in laboratory animals such as rats and mice when the
animals are exposed at high levels
[[Page 406]]
over their lifetimes. Chemicals that cause cancer in laboratory animals
also may increase the risk of cancer in humans who are exposed over long
periods of time. EPA has set the drinking water standard for PCBs at
0.0005 part per million (ppm) to reduce the risk of cancer or other
adverse health effects which have been observed in laboratory animals.
Drinking water that meets this standard is associated with little to
none of this risk and is considered safe with respect to PCBs.
(46) Pentachlorophenol. The United States Environmental Protection
Agency (EPA) sets drinking water standards and has determined that
pentachlorophenol is a health concern at certain levels of exposure.
This organic chemical is used as a wood preservative, herbicide,
disinfectant, and defoliant. It generally gets into drinking water by
runoff into surface water or leaching into ground water. This chemical
has been shown to produce adverse reproductive effects and to damage the
liver and kidneys of laboratory animals such as rats exposed to high
levels during their lifetimes. Some humans who were exposed to
relatively large amounts of this chemical also suffered damage to the
liver and kidneys. This chemical has been shown to cause cancer in
laboratory animals such as rats and mice when the animals are exposed to
high levels over their lifetimes. Chemicals that cause cancer in
laboratory animals also may increase the risk of cancer in humans who
are exposed over long periods of time. EPA has set the drinking water
standard for pentachlorophenol at 0.001 parts per million (ppm) to
protect against the risk of cancer or other adverse health effects.
Drinking water that meets the EPA standard is associated with little to
none of this risk and is considered safe with respect to
pentachlorophenol.
(47) Styrene. The United States Environmental Protection Agency
(EPA) sets drinking water standards and has determined that styrene is a
health concern at certain levels of exposure. This organic chemical is
commonly used to make plastics and is sometimes a component of resins
used for drinking water treatment. Styrene may get into drinking water
from improper waste disposal. This chemical has been shown to damage the
liver and nervous system in laboratory animals when exposed at high
levels during their lifetimes. EPA has set the drinking water standard
for styrene at 0.1 part per million (ppm) to protect against the risk of
these adverse health effects. Drinking water that meets the EPA standard
is associated with little to none of this risk and is considered safe
with respect to styrene.
(48) Tetrachloroethylene. The United States Environmental Protection
Agency (EPA) sets drinking water standards and has determined that
tetrachloroethylene is a health concern at certain levels of exposure.
This organic chemical has been a popular solvent, particularly for dry
cleaning. It generally gets into drinking water by improper waste
disposal. This chemical has been shown to cause cancer in laboratory
animals such as rats and mice when the animals are exposed at high
levels over their lifetimes. Chemicals that cause cancer in laboratory
animals also may increase the risk of cancer in humans who are exposed
over long periods of time. EPA has set the drinking water standard for
tetrachloroethylene at 0.005 part per million (ppm) to reduce the risk
of cancer or other adverse health effects which have been observed in
laboratory animals. Drinking water that meets this standard is
associated with little to none of this risk and is considered safe with
respect to tetrachloroethylene.
(49) Toluene. The United States Environmental Protection Agency
(EPA) sets drinking water standards and has determined that toluene is a
health concern at certain levels of exposure. This organic chemical is
used as a solvent and in the manufacture of gasoline for airplanes. It
generally gets into water by improper waste disposal or leaking
underground storage tanks. This chemical has been shown to damage the
kidney, nervous system, and circulatory system of laboratory animals
such as rats and mice exposed to high levels during their lifetimes.
Some industrial workers who were exposed to relatively large amounts of
this chemical during working careers
[[Page 407]]
also suffered damage to the liver, kidney and nervous system. EPA has
set the drinking water standard for toluene at 1 part per million (ppm)
to protect against the risk of adverse health effects. Drinking water
that meets the EPA standard is associated with little to none of this
risk and is considered safe with respect to toluene.
(50) Toxaphene. The United States Environmental Protection Agency
(EPA) sets drinking water standards and has determined that toxaphene is
a health concern at certain levels of exposure. This organic chemical
was once a pesticide widely used on cotton, corn, soybeans, pineapples
and other crops. When soil and climatic conditions are favorable,
toxaphene may get into drinking water by runoff into surface water or by
leaching into ground water. This chemical has been shown to cause cancer
in laboratory animals such as rats and mice when the animals are exposed
at high levels over their lifetimes. Chemicals that cause cancer in
laboratory animals also may increase the risk of cancer in humans who
are exposed over long periods of time. EPA has set the drinking water
standard for toxaphene at 0.003 part per million (ppm) to reduce the
risk of cancer or other adverse health effects which have been observed
in laboratory animals. Drinking water that meets this standard is
associated with little to none of this risk and is considered safe with
respect to toxaphene.
(51) 2,4,5-TP. The United States Environmental Protection Agency
(EPA) sets drinking water standards and has determined that 2,4,5-TP is
a health concern at certain levels of exposure. This organic chemical is
used as a herbicide. When soil and climatic conditions are favorable,
2,4,5-TP may get into drinking water by runoff into surface water or by
leaching into ground water. This chemical has been shown to damage the
liver and kidney of laboratory animals such as rats and dogs exposed to
high levels during their lifetimes. Some industrial workers who were
exposed to relatively large amounts of this chemical during working
careers also suffered damage to the nervous system. EPA has set the
drinking water standard for 2,4,5-TP at 0.05 part per million (ppm) to
protect against the risk of these adverse health effects. Drinking water
that meets the EPA standard is associated with little to none of this
risk and is considered safe with respect to 2,4,5-TP.
(52) Xylenes. The United States Environmental Protection Agency
(EPA) sets drinking water standards and has determined that xylene is a
health concern at certain levels of exposure. This organic chemical is
used in the manufacture of gasoline for airplanes and as a solvent for
pesticides, and as a cleaner and degreaser of metals. It usually gets
into water by improper waste disposal. This chemical has been shown to
damage the liver, kidney and nervous system of laboratory animals such
as rats and dogs exposed to high levels during their lifetimes. Some
humans who were exposed to relatively large amounts of this chemical
also suffered damage to the nervous system. EPA has set the drinking
water standard for xylene at 10 parts per million (ppm) to protect
against the risk of these adverse health effects. Drinking water that
meets the EPA standard is associated with little to none of this risk
and is considered safe with respect to xylene.
(53) Antimony. The United States Environmental Protection Agency
(EPA) sets drinking water standards and has determined that antimony is
a health concern at certain levels of exposure. This inorganic chemical
occurs naturally in soils, ground water and surface waters and is often
used in the flame retardant industry. It is also used in ceramics,
glass, batteries, fireworks and explosives. It may get into drinking
water through natural weathering of rock, industrial production,
municipal waste disposal or manufacturing processes. This chemical has
been shown to decrease longevity, and altered blood levels of
cholesterol and glucose in laboratory animals such as rats exposed to
high levels during their lifetimes. EPA has set the drinking water
standard for antimony at 0.006 parts per million (ppm) to protect
against the risk of these adverse health effects. Drinking water which
meets the EPA standard is associated with little to none of this risk
and should be considered safe with respect to antimony.
[[Page 408]]
(54) Beryllium. The United States Environmental Protection Agency
(EPA) sets drinking water standards and has determined that beryllium is
a health concern at certain levels of exposure. This inorganic metal
occurs naturally in soils, ground water and surface waters and is often
used in electrical equipment and electrical components. It generally
gets into water from runoff from mining operations, discharge from
processing plants and improper waste disposal. Beryllium compounds have
been associated with damage to the bones and lungs and induction of
cancer in laboratory animals such as rats and mice when the animals are
exposed at high levels over their lifetimes. There is limited evidence
to suggest that beryllium may pose a cancer risk via drinking water
exposure. Therefore, EPA based the health assessment on noncancer
effects with an extra uncertainty factor to account for possible
carcinogenicity. Chemicals that cause cancer in laboratory animals also
may increase the risk of cancer in humans who are exposed over long
periods of time. EPA has set the drinking water standard for beryllium
at 0.004 part per million (ppm) to protect against the risk of these
adverse health effects. Drinking water which meets the EPA standard is
associated with little to none of this risk and should be considered
safe with respect to beryllium.
(55) Cyanide. The United States Environmental Protection Agency
(EPA) sets drinking water standards and has determined that cyanide is a
health concern at certain levels of exposure. This inorganic chemical is
used in electroplating, steel processing, plastics, synthetic fabrics
and fertilizer products. It usually gets into water as a result of
improper waste disposal. This chemical has been shown to damage the
spleen, brain and liver of humans fatally poisoned with cyanide. EPA has
set the drinking water standard for cyanide at 0.2 parts per million
(ppm) to protect against the risk of these adverse health effects.
Drinking water which meets the EPA standard is associated with little to
none of this risk and should be considered safe with respect to cyanide.
(56) [Reserved]
(57) Thallium. The United States Environmental Protection Agency
(EPA) sets drinking water standards and has determined that thallium is
a health concern at certain high levels of exposure. This inorganic
metal is found naturally in soils and is used in electronics,
pharmaceuticals, and the manufacture of glass and alloys. This chemical
has been shown to damage the kidney, liver, brain and intestines of
laboratory animals when the animals are exposed at high levels over
their lifetimes. EPA has set the drinking water standard for thallium at
0.002 parts per million (ppm) to protect against the risk of these
adverse health effects. Drinking water which meets the EPA standard is
associated with little to none of this risk and should be considered
safe with respect to thallium.
(58) Benzo[a]pyrene. The United States Environmental Protection
Agency (EPA) sets drinking water standards and has determined that
benzo[a]pyrene is a health concern at certain levels of exposure.
Cigarette smoke and charbroiled meats are common source of general
exposure. The major source of benzo[a]pyrene in drinking water is the
leaching from coal tar lining and sealants in water storage tanks. This
chemical has been shown to cause cancer in animals such as rats and mice
when the animals are exposed at high levels. EPA has set the drinking
water standard for benzo[a]pyrene at 0.0002 parts per million (ppm) to
protect against the risk of cancer. Drinking water which meets the EPA
standard is associated with little to none of this risk and should be
considered safe with respect to benzo[a]pyrene.
(59) Dalapon. The United States Environmental Protection Agency
(EPA) sets drinking water standards and has determined that dalapon is a
health concern at certain levels of exposure. This organic chemical is a
widely used herbicide. It may get into drinking water after application
to control grasses in crops, drainage ditches and along railroads. This
chemical has been shown to cause damage to the kidney and liver in
laboratory animals when the animals are exposed to high levels over
their lifetimes. EPA has set the
[[Page 409]]
drinking water standard for dalapon at 0.2 parts per million (ppm) to
protect against the risk of these adverse health effects. Drinking water
which meets the EPA standard is associated with little to none of this
risk and should be considered safe with respect to dalapon.
(60) Dichloromethane. The United States Environmental Protection
Agency (EPA) sets drinking water standards and has determined that
dichloromethane (methylene chloride) is a health concern at certain
levels of exposure. This organic chemical is a widely used solvent. It
is used in the manufacture of paint remover, as a metal degreaser and as
an aerosol propellant. It generally gets into drinking water after
improper discharge of waste disposal. This chemical has been shown to
cause cancer in laboratory animals such as rats and mice when the
animals are exposed at high levels over their lifetimes. Chemicals that
cause cancer in laboratory animals also may increase the risk of cancer
in humans who are exposed over long periods of time. EPA has set the
drinking water standard for dichloromethane at 0.005 parts per million
(ppm) to reduce the risk of cancer or other adverse health effects which
have been observed in laboratory animals. Drinking water which meets
this standard is associated with little to none of this risk and should
be considered safe with respect to dichloromethane.
(61) Di (2-ethylhexyl)adipate. The United States Environmental
Protection Agency (EPA) sets drinking water standards and has determined
that di(2-ethylhexyl)adipate is a health concern at certain levels of
exposure. Di(2-ethylhexyl)adipate is a widely used plasticizer in a
variety of products, including synthetic rubber, food packaging
materials and cosmetics. It may get into drinking water after improper
waste disposal. This chemical has been shown to damage liver and testes
in laboratory animals such as rats and mice exposed to high levels. EPA
has set the drinking water standard for di(2-ethylhexyl)adipate at 0.4
parts per million (ppm) to protect against the risk of adverse health
effects. Drinking water which meets the EPA standards is associated with
little to none of this risk and should be considered safe with respect
to di(2-ethylhexyl)adipate.
(62) Di(2-ethylhexyl)phthalate. The United States Environmental
Protection Agency (EPA) sets drinking water standards and has determined
that di(2-ethylhexyl)phthalate is a health concern at certain levels of
exposure. Di(2-ethylhexyl)phthalate is a widely used plasticizer, which
is primarily used in the production of polyvinyl chloride (PVC) resins.
It may get into drinking water after improper waste disposal. This
chemical has been shown to cause cancer in laboratory animals such as
rats and mice exposed to high levels over their lifetimes. EPA has set
the drinking water standard for di(2-ethylhexyl)phthalate at 0.006 parts
per million (ppm) to reduce the risk of cancer or other adverse health
effects which have been observed in laboratory animals. Drinking water
which meets the EPA standard is associated with little to none of this
risk and should be considered safe with respect to di(2-
ethylhexyl)phthalate.
(63) Dinoseb. The United States Environmental Protection Agency
(EPA) sets drinking water standards and has determined that dinoseb is a
health concern at certain levels of exposure. Dinoseb is a widely used
pesticide and generally gets into drinking water after application on
orchards, vineyards and other crops. This chemical has been shown to
damage the thyroid and reproductive organs in laboratory animals such as
rats exposed to high levels. EPA has set the drinking water standard for
dinoseb at 0.007 parts per million (ppm) to protect against the risk of
adverse health effects. Drinking water which meets the EPA standard is
associated with little to none of this risk and should be considered
safe with respect to dinoseb.
(64) Diquat. The United States Environmental Protection Agency (EPA)
sets drinking water standards and has determined that diquat is a health
concern at certain levels of exposure. This organic chemical is a
herbicide used to control terrestrial and aquatic weeds. It may get into
drinking water by runoff into surface water. This chemical has been
shown to damage the liver, kidney and gastrointestinal tract and
[[Page 410]]
causes cataract formation in laboratory animals such as dogs and rats
exposed at high levels over their lifetimes. EPA has set the drinking
water standard for diquat at 0.02 parts per million (ppm) to protect
against the risk of these adverse health effects. Drinking water which
meets the EPA standard is associated with little to none of this risk
and should be considered safe with respect to diquat.
(65) Endothall. The United States Environmental Protection Agency
(EPA) has determined that endothall is a health concern at certain
levels of exposure. This organic chemical is a herbicide used to control
terrestrial and aquatic weeds. It may get into water by runoff into
surface water. This chemical has been shown to damage the liver, kidney,
gastrointestinal tract and reproductive system of laboratory animals
such as rats and mice exposed at high levels over their lifetimes. EPA
has set the drinking water standard for endothall at 0.1 parts per
million (ppm) to protect against the risk of these adverse health
effects. Drinking water which meets the EPA standard is associated with
little to none of this risk and should be considered safe with respect
to endothall.
(66) Endrin. The United States Environmental Protection Agency (EPA)
sets drinking water standards and has determined that endrin is a health
concern at certain levels of exposure. This organic chemical is a
pesticide no longer registered for use in the United States. However,
this chemical is persistent in treated soils and accumulates in
sediments and aquatic and terrestrial biota. This chemical has been
shown to cause damage to the liver, kidney and heart in laboratory
animals such as rats and mice when the animals are exposed at high
levels over their lifetimes. EPA has set the drinking water standard for
endrin at 0.002 parts per million (ppm) to protect against the risk of
these adverse health effects which have been observed in laboratory
animals. Drinking water that meets the EPA standard is associated with
little to none of this risk and should be considered safe with respect
to endrin.
(67) Glyphosate. The United States Environmental Protection Agency
(EPA) sets drinking water standards and has determined that glyphosate
is a health concern at certain levels of exposure. This organic chemical
is a herbicide used to control grasses and weeds. It may get into
drinking water by runoff into surface water. This chemical has been
shown to cause damage to the liver and kidneys in laboratory animals
such as rats and mice when the animals are exposed at high levels over
their lifetimes. EPA has set the drinking water standard for glyphosate
at 0.7 parts per million (ppm) to protect against the risk of these
adverse health effects. Drinking water which meets the EPA standard is
associated with little to none of this risk and should be considered
safe with respect to glyphosate.
(68) Hexachlorobenzene. The United States Environmental Protection
Agency (EPA) sets drinking water standards and has determined that
hexachlorobenzene is a health concern at certain levels of exposure.
This organic chemical is produced as an impurity in the manufacture of
certain solvents and pesticides. This chemical has been shown to cause
cancer in laboratory animals such as rats and mice when the animals are
exposed to high levels during their lifetimes. Chemicals that cause
cancer in laboratory animals also may increase the risk of cancer in
humans who are exposed over long periods of time. EPA has set the
drinking water standard for hexachlorobenzene at 0.001 parts per million
(ppm) to protect against the risk of cancer and other adverse health
effects. Drinking water which meets the EPA standard is associated with
little to none of this risk and should be considered safe with respect
to hexachlorobenzene.
(69) Hexachlorocyclopentadiene. The United States Environmental
Protection Agency (EPA) establishes drinking water standards and has
determined that hexachlorocyclopentadiene is a health concern at certain
levels of exposure. This organic chemical is used as an intermediate in
the manufacture of pesticides and flame retardants. It may get into
water by discharge from production facilities. This chemical has been
shown to damage the kidney and the stomach of laboratory animals
[[Page 411]]
when exposed at high levels over their lifetimes. EPA has set the
drinking water standard for hexachlorocyclopentadiene at 0.05 parts per
million (ppm) to protect against the risk of these adverse health
effects. Drinking water which meets the EPA standard is associated with
little to none of this risk and should be considered safe with respect
to hexachlorocyclopentadiene.
(70) Oxamyl. The United States Environmental Protection Agency (EPA)
establishes drinking water standards and has determined that oxamyl is a
health concern at certain levels of exposure. This organic chemical is
used as a pesticide for the control of insects and other pests. It may
get into drinking water by runoff into surface water or leaching into
ground water. This chemical has been shown to damage the kidneys of
laboratory animals such as rats when exposed at high levels over their
lifetimes. EPA has set the drinking water standard for oxamyl at 0.2
parts per million (ppm) to protect against the risk of these adverse
health effects. Drinking water which meets the EPA standard is
associated with little to none of this risk and should be considered
safe with respect to oxamyl.
(71) Picloram. The United States Environmental Protection Agency
(EPA) sets drinking water standards and has determined that picloram is
a health concern at certain levels of exposure. This organic chemical is
used as a pesticide for broadleaf weed control. It may get into drinking
water by runoff into surface water or leaching into ground water as a
result of pesticide application and improper waste disposal. This
chemical has been shown to cause damage to the kidneys and liver in
laboratory animals such as rats when the animals are exposed at high
levels over their lifetimes. EPA has set the drinking water standard for
picloram at 0.5 parts per million (ppm) to protect against the risk of
these adverse health effects. Drinking water which meets the EPA
standard is associated with little to none of this risk and should be
considered safe with respect to picloram.
(72) Simazine. The United States Environmental Protection Agency
(EPA) sets drinking water standards and has determined that simazine is
a health concern at certain levels of exposure. This organic chemical is
a herbicide used to control annual grasses and broadleaf weeds. It may
leach into ground water or runs off into surface water after
application. This chemical may cause cancer in laboratory animals such
as rats and mice exposed at high levels during their lifetimes.
Chemicals that cause cancer in laboratory animals also may increase the
risk of cancer in humans who are exposed over long periods of time. EPA
has set the drinking water standard for simazine at 0.004 parts per
million (ppm) to reduce the risk of cancer or other adverse health
effects. Drinking water which meets the EPA standard is associated with
little to none of this risk and should be considered safe with respect
to simazine.
(73) 1,2,4-Trichlorobenzene. The United States Environmental
Protection Agency (EPA) sets drinking water standards and has determined
that 1,2,4-trichlorobenzene is a health concern at certain levels of
exposure. This organic chemical is used as a dye carrier and as a
precursor in herbicide manufacture. It generally gets into drinking
water by discharges from industrial activities. This chemical has been
shown to cause damage to several organs, including the adrenal glands.
EPA has set the drinking water standard for 1,2,4-trichlorobenzene at
0.07 parts per million (ppm) to protect against the risk of these
adverse health effects. Drinking water which meets the EPA standard is
associated with little to none of this risk and should be considered
safe with respect to 1,2,4-trichlorobenzene.
(74) 1,1,2-Trichloroethane. The United States Environmental
Protection Agency (EPA) sets drinking water standards and has determined
1,1,2-trichloroethane is a health concern at certain levels of exposure.
This organic chemical is an intermediate in the production of 1,1-
dichloroethylene. It generally gets into water by industrial discharge
of wastes. This chemical has been shown to damage the kidney and liver
of laboratory animals such as rats exposed to high levels during their
lifetimes. EPA has set the drinking water standard for 1,1,2-
trichloroethane at
[[Page 412]]
0.005 parts per million (ppm) to protect against the risk of these
adverse health effects. Drinking water which meets the EPA standard is
associated with little to none of this risk and should be considered
safe with respect to 1,1,2-trichloroethane.
(75) 2,3,7,8-TCDD (Dioxin). The United States Environmental
Protection Agency (EPA) sets drinking water standards and has determined
that dioxin is a health concern at certain levels of exposure. This
organic chemical is an impurity in the production of some pesticides. It
may get into drinking water by industrial discharge of wastes. This
chemical has been shown to cause cancer in laboratory animals such as
rats and mice when the animals are exposed at high levels over their
lifetimes. Chemicals that cause cancer in laboratory animals also may
increase the risk of cancer in humans who are exposed over long periods
of time. EPA has set the drinking water standard for dioxin at
0.00000003 parts per million (ppm) to reduce the risk of cancer or other
adverse health effects which have been observed in laboratory animals.
Drinking water which meets this standard is associated with little to
none of this risk and should be considered safe with respect to dioxin.
(76) Chlorine. The United States Environmental Protection Agency
(EPA) sets drinking water standards and has determined that chlorine is
a health concern at certain levels of exposure. Chlorine is added to
drinking water as a disinfectant to kill bacteria and other disease-
causing microorganisms and is also added to provide continuous
disinfection throughout the distribution system. Disinfection is
required for surface water systems. However, at high doses for extended
periods of time, chlorine has been shown to affect blood and the liver
in laboratory animals. EPA has set a drinking water standard for
chlorine to protect against the risk of these adverse effects. Drinking
water which meets this EPA standard is associated with little to none of
this risk and should be considered safe with respect to chlorine.
(77) Chloramines. The United States Environmental Protection Agency
(EPA) sets drinking water standards and has determined that chloramines
are a health concern at certain levels of exposure. Chloramines are
added to drinking water as a disinfectant to kill bacteria and other
disease-causing microorganisms and are also added to provide continuous
disinfection throughout the distribution system. Disinfection is
required for surface water systems. However, at high doses for extended
periods of time, chloramines have been shown to affect blood and the
liver in laboratory animals. EPA has set a drinking water standard for
chloramines to protect against the risk of these adverse effects.
Drinking water which meets this EPA standard is associated with little
to none of this risk and should be considered safe with respect to
chloramines.
(78) Chlorine dioxide. The United States Environmental Protection
Agency (EPA) sets drinking water standards and has determined that
chlorine dioxide is a health concern at certain levels of exposure.
Chlorine dioxide is used in water treatment to kill bacteria and other
disease-causing microorganisms and can be used to control tastes and
odors. Disinfection is required for surface water systems. However, at
high doses, chlorine dioxide-treated drinking water has been shown to
affect blood in laboratory animals. Also, high levels of chlorine
dioxide given to laboratory animals in drinking water have been shown to
cause neurological effects on the developing nervous system. These
neurodevelopmental effects may occur as a result of a short-term
excessive chlorine dioxide exposure. To protect against such potentially
harmful exposures, EPA requires chlorine dioxide monitoring at the
treatment plant, where disinfection occurs, and at representative points
in the distribution system serving water users. EPA has set a drinking
water standard for chlorine dioxide to protect against the risk of these
adverse effects.
Note: In addition to the language in this introductory text of
paragraph (e)(78), systems must include either the language in paragraph
(e)(78)(i) or (e)(78)(ii) of this section. Systems with a violation at
the treatment plant, but not in the distribution system, are required to
use the language in paragraph (e)(78)(i) of this section and treat
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the violation as a nonacute violation. Systems with a violation in the
distribution system are required to use the language in paragraph
(e)(78)(ii) of this section and treat the violation as an acute
violation.
(i) The chlorine dioxide violations reported today are the result of
exceedances at the treatment facility only, and do not include
violations within the distribution system serving users of this water
supply. Continued compliance with chlorine dioxide levels within the
distribution system minimizes the potential risk of these violations to
present consumers.
(ii) The chlorine dioxide violations reported today include
exceedances of the EPA standard within the distribution system serving
water users. Violations of the chlorine dioxide standard within the
distribution system may harm human health based on short-term exposures.
Certain groups, including pregnant women, infants, and young children,
may be especially susceptible to adverse effects of excessive exposure
to chlorine dioxide-treated water. The purpose of this notice is to
advise that such persons should consider reducing their risk of adverse
effects from these chlorine dioxide violations by seeking alternate
sources of water for human consumption until such exceedances are
rectified. Local and State health authorities are the best sources for
information concerning alternate drinking water.
(79) Disinfection byproducts and treatment technique for DBPs. The
United States Environmental Protection Agency (EPA) sets drinking water
standards and requires the disinfection of drinking water. However, when
used in the treatment of drinking water, disinfectants react with
naturally-occurring organic and inorganic matter present in water to
form chemicals called disinfection byproducts (DBPs). EPA has determined
that a number of DBPs are a health concern at certain levels of
exposure. Certain DBPs, including some trihalomethanes (THMs) and some
haloacetic acids (HAAs), have been shown to cause cancer in laboratory
animals. Other DBPs have been shown to affect the liver and the nervous
system, and cause reproductive or developmental effects in laboratory
animals. Exposure to certain DBPs may produce similar effects in people.
EPA has set standards to limit exposure to THMs, HAAs, and other DBPs.
(80) Bromate. The United States Environmental Protection Agency
(EPA) sets drinking water standards and has determined that bromate is a
health concern at certain levels of exposure. Bromate is formed as a
byproduct of ozone disinfection of drinking water. Ozone reacts with
naturally occurring bromide in the water to form bromate. Bromate has
been shown to produce cancer in rats. EPA has set a drinking water
standard to limit exposure to bromate.
(81) Chlorite. The United States Environmental Protection Agency
(EPA) sets drinking water standards and has determined that chlorite is
a health concern at certain levels of exposure. Chlorite is formed from
the breakdown of chlorine dioxide, a drinking water disinfectant.
Chlorite in drinking water has been shown to affect blood and the
developing nervous system. EPA has set a drinking water standard for
chlorite to protect against these effects. Drinking water which meets
this standard is associated with little to none of these risks and
should be considered safe with respect to chlorite.
(f) Public notices for fluoride. Notice of violations of the maximum
contaminant level for fluoride, notices of variances and exemptions from
the maximum contaminant level for fluoride, and notices of failure to
comply with variance and exemption schedules for the maximum contaminant
level for fluoride shall consist of the public notice prescribed in
Sec. 143.5(b), plus a description of any steps which the system is
taking to come into compliance.
(g) Public notification by the State. The State may give notice to
the public required by this section on behalf of the owner or operator
of the public water system if the State complies with the requirements
of this section. However, the owner or operator of the public
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water system remains legally responsible for ensuring that the
requirements of this section are met.
[52 FR 41546, Oct. 28, 1987, as amended at 54 FR 15188, Apr. 17, 1989;
54 FR 27527, 27566, June 29, 1989; 55 FR 25064, June 19, 1990; 56 FR
3587, Jan. 30, 1991; 56 FR 26548, June 7, 1991; 56 FR 30279, July 1,
1991; 57 FR 31843, July 17, 1992; 59 FR 34323, July 1, 1994; 60 FR
33932, June 29, 1995; 63 FR 69464, 69515, Dec. 16, 1998; 65 FR 26022,
May 4, 2000]