[Title 40 CFR ]
[Code of Federal Regulations (annual edition) - July 1, 2000 Edition]
[From the U.S. Government Printing Office]
[[Page i]]
40
Parts 136 to 149
Revised as of July 1, 2000
Protection of Environment
Containing a Codification of documents of general
applicability and future effect
As of July 1, 2000
With Ancillaries
Published by
Office of the Federal Register
National Archives and Records
Administration
As a Special Edition of the Federal Register
[[Page ii]]
U.S. GOVERNMENT PRINTING OFFICE
WASHINGTON : 2000
For sale by U.S. Government Printing Office
Superintendent of Documents, Mail Stop: SSOP, Washington, DC 20402-9328
[[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........ 841
Table of CFR Titles and Chapters........................ 859
Alphabetical List of Agencies Appearing in the CFR...... 877
List of CFR Sections Affected........................... 887
[[Page iv]]
----------------------------
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
permanent rules published in the Federal Register by the Executive
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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
Title 17 through Title 27..................................as of April 1
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collection request.
[[Page vi]]
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INCORPORATION BY REFERENCE
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What is a proper incorporation by reference? The Director of the
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approval is based are:
(a) The incorporation will substantially reduce the volume of
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(b) The matter incorporated is in fact available to the extent
necessary to afford fairness and uniformity in the administrative
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(c) The incorporating document is drafted and submitted for
publication in accordance with 1 CFR part 51.
Properly approved incorporations by reference in this volume are
listed in the Finding Aids at the end of this volume.
What if the material incorporated by reference cannot be found? If
you have any problem locating or obtaining a copy of material listed in
the Finding Aids of this volume as an approved incorporation by
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the revision dates of the 50 CFR titles.
[[Page vii]]
REPUBLICATION OF MATERIAL
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Raymond A. Mosley,
Director,
Office of the Federal Register.
July 1, 2000.
[[Page ix]]
THIS TITLE
Title 40--Protection of Environment is composed of twenty-four
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, parts 61-62, part 63 (63.1-63.1199), part 63
(63.1200-End), parts 64-71, parts 72-80, parts 81-85, part 86, parts 87-
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, 2000.
Chapter I--Environmental Protection Agency appears in all twenty-
four volumes. A Pesticide Tolerance Commodity/Chemical Index and Crop
Grouping Commodities Index appear in parts 150-189. A Toxic Substances
Chemical--CAS Number Index appears in parts 700-789 and part 790 to End.
Redesignation Tables appear in the volumes containing parts 50-51, parts
150-189, and parts 700-789. 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, Melanie L. Marcec was Chief Editor. The Code of
Federal Regulations publication program is under the direction of
Frances D. McDonald, assisted by Alomha S. Morris.
[[Page x]]
[[Page 1]]
TITLE 40--PROTECTION OF ENVIRONMENT
(This book contains parts 136 to 149)
--------------------------------------------------------------------
Part
chapter i--Environmental Protection Agency (Continued)...... 136
[[Page 3]]
CHAPTER I--ENVIRONMENTAL PROTECTION
AGENCY (CONTINUED)
--------------------------------------------------------------------
SUBCHAPTER D--WATER PROGRAMS (CONTINUED)
Part Page
136 Guidelines establishing test procedures for
the analysis of pollutants.............. 5
140 Marine sanitation device standard........... 330
141 National primary drinking water regulations. 334
142 National primary drinking water regulations
implementation.......................... 561
143 National secondary drinking water
regulations............................. 612
144 Underground injection control program....... 614
145 State UIC program requirements.............. 682
146 Underground injection control program:
Criteria and standards.................. 695
147 State underground injection control programs 726
148 Hazardous waste injection restrictions...... 824
149 Sole source aquifers........................ 833
[[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 references and the sources which are available are given in
paragraph (b) of this section. These test procedures are incorporated as
they exist on the day of approval and a notice of any 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
[[Page 6]]
the standard analytical test procedures incorporated by reference and
described in Tables IA, IB, IC, ID, 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 Secs. 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 used that 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
--------------------------------------------------------------------------------------------------------------------------------------------------------
Parameter and units Method \1\ EPA Standard methods, 18th Ed. ASTM USGS
--------------------------------------------------------------------------------------------------------------------------------------------------------
Bacteria:
1. Coliform (fecal), number Most Probable Number p. 132 \3\ 9221C E \4\ ........... ......................
per 100 mL. (MPN), 5 tube. p. 124 \3\ 9222D \4\ B-0050-85 \5\
3 dilution, or Membrane
filter (MF) \2\, single
step.
2. Coliform (fecal) in MPN, 5 tube, 3 dilution, p. 132 \3\ 9221C E \4\ ........... ......................
presence of chlorine, number or. p. 124 \3\ 9222D \4\
per 100 mL. MF, single step \6\.......
3. Coliform (total), number MPN, 5 tube, 3 dilution, p. 114 \3\ 9221B \4\ ........... ......................
per 100 mL. or. p. 108 \3\ 9222B \4\ B-0025-85 \5\
MF \2\ single step or two
step.
4. Coliform (total), in MPN, 5 tube, 3 dilution, p. 114 \3\ 9221B \4\ ........... ......................
presence of chlorine, number or. p. 111 \3\ 9222(B+B.5c) \4\
per 100 mL. MF \2\ with enrichment....
5. Fecal streptococci, number MPN, 5 tube, 3 dilution... p. 139 \3\ 9230B \4\ ........... ......................
per 100 mL. MF \2\, or................ p. 136 \3\ 9230C \4\ B-0055-85 \5\
Plate count............... p. 143 \3\
Aquatic Toxicity:
6. Toxicity, acute, fresh Daphnia, Ceriodaphnia, Sec. 9 \7\ ........................... ........... ......................
water organisms, LC50, Fathead Minnow, Rainbow
percent effluent. Trout, Brook Trout, or
Bannerfish Shiner
mortality.
7. Toxicity, acute, estuarine Mysid, Sheepshead Minnow, Sec. 9 \7\ ........................... ........... ......................
and marine organisms, LC50, or Menidia spp. mortality.
percent effluent.
8. Toxicity, chronic, fresh Fathead minnow larval 1000.0 \8\ ........................... ........... ......................
water organisms, NOEC or survival and growth. 1001.0 \8\
IC25, percent effluent. Fathead minnow embryo-
larval survival and 1002.0 \8\
teratogenicity. 1003.0 \8\
Ceriodaphnia survival and
reproduction.
Selenastrum growth........
9. Toxicity, chronic, Sheepshead minnow larval 1004.0 \9\ ........................... ........... ......................
estuarine and marine survival and growth. 1005.0 \9\
organisms, NOEC or IC25, Sheepshead minnow embryo-
percent effluent. larval survival and 1006.0 \9\
teratogenicity. 1007.0 \9\
Menidia beryllina larval 1008.0 \9\
and growth. 1009.0 \9\
Mysidopsis bahia survival,
growth, and fecundity.
Arbacia punctulata
fertilization.
Champia parvula
reproduction.
--------------------------------------------------------------------------------------------------------------------------------------------------------
Notes to Table IA:
\1\ The method must be specified when results are reported.
\2\ A 0.45 um 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. 1992. Standard Methods for the Examination of Water and Wastewater. American Public Health Association. 18th Edition. Amer. Publ. Hlth.
Assoc., Washington, DC.
\5\ 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 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\ USEPA. 1993. Methods for Measuring the Acute Toxicity of Effluents to Freshwater and Marine Organisms. Fourth Edition. Environmental Monitoring
Systems Laboratory, U.S. Environmental Protection Agency, Cincinnati, Ohio. August 1993, EPA/600/4-90/027F.
[[Page 8]]
\8\ USEPA. 1994. Short-term Methods for Estimating the Chronic Toxicity of Effluents and Receiving Waters to Freshwater Organisms. Third Edition.
Environmental Monitoring Systems Laboratory, U.S. Environmental Protection Agency USEPA. 1994, Cincinnati, Ohio (July 1994, EPA/600/4-91/002).
\9\ Short-term Methods for Estimating the Chronic Toxicity of Effluents and Receiving Waters to Marine and Estuarine Organisms. Second Edition.
Environmental Monitoring Systems Laboratory, U.S. Environmental Protection Agency, Cincinnati, Ohio (July 1994, EPA/600/4-91/003). These methods do
not apply to marine waters of the Pacific Ocean.
Table IB.--List of Approved Inorganic Test Procedures
--------------------------------------------------------------------------------------------------------------------------------------------------------
Reference (method number or page)
Parameter, units and method -------------------------------------------------------------------------------------------------------------------------
EPA 1,35 STD methods 18th ed. ASTM USGS \2\ Other
--------------------------------------------------------------------------------------------------------------------------------------------------------
1. Acidity, as CaCO3, mg/L:
Electrometric endpoint or 305.1 2310 B(4a)................ D1067-92
phenolphthalein endpoint.
2. Alkalinity, as CaCO3, mg/L:
Electrometric or 310.1 2320 B.................... D1067-92..................... I-1030-85................ 973.43.\3\
Colorimetric titration to 310.2 I-2030-85................
pH 4.5, manual or
automated.
3. Aluminum--Total,\4\ mg/L;
Digestion \4\ followed by:
AA direct aspiration \36\. 202.1 3111 D.................... ............................. I-3051-85
AA furnace................ 202.2 3113 B
Inductively Coupled Plasma/ \5\ 200.7 3120 B
Atomic Emission
Spectrometry (ICP/AES)
\36\.
Direct Current Plasma ........... .......................... D4190-82(88)................. ......................... Note 34.
(DCP) \36\.
Colorimetric (Eriochrome ........... 3500-Al D
cyanine R).
4. Ammonia (as N), mg/L:
Manual, distillation (at 350.2 4500-NH3B................. ............................. ......................... 973.49.\3\
pH 9.5),\6\ followed by.
Nesslerization............ 350.2 4500-NH3C................. D1426-93(A).................. I-3520-85................ 973.49.\3\
Titration................. 350.2 4500-NH3E
Electrode................. 350.3 4500-NH3F or G............ D1426-93(B)
Automated phenate, or..... 350.1 4500-NH3H................. ............................. I-4523-85
Automated electrode....... ........... .......................... ............................. ......................... Note 7.
5. Antimony-Total,\4\ mg/L;
Digestion \4\ followed by:
AA direct aspiration \36\. 204.1 3111 B
AA furnace................ 204.2 3113 B
ICP/AES \36\.............. \5\ 200.7 3120 B
6. Arsenic-Total,\4\ mg/L:
Digestion \4\ followed by. 206.5
AA gaseous hydride.... 206.3 3114 B 4.d................ D2972-93(B).................. I-3062-85
AA furnace............ 206.2 3113 B.................... D2972-93(C)
ICP/AES,\36\ or....... \5\ 200.7 3120 B
Colorimetric (SDDC)... 206.4 3500-As C................. D2972-93(A).................. I-3060-85
7. Barium--Total,\4\ mg/L;
Digestion \4\ followed by:
AA direct aspiration \36\. 208.1 3111 D.................... ............................. I-3084-85
AA furnace................ 208.2 3113 B.................... D4382-91
ICP/AES \36\.............. \5\ 200.7 3120 B
DCP \36\.................. ........... .......................... ............................. ......................... Note 34.
8. Beryllium--Total,\4\ mg/L;
Digestion \4\ followed by:
AA direct aspiration...... 210.1 3111 D.................... D3645-93(88)(A).............. I-3095-85
AA furnace................ 210.2 3113 B.................... D3645-93(88)(B)
ICP/AES................... \5\ 200.7 3120 B
DCP, or................... ........... .......................... D4190-82(88)................. ......................... Note 34.
[[Page 9]]
Colorimetric (aluminon)... ........... 3500-Be D
9. Biochemical oxygen demand
(BOD5), mg/L:
Dissolved Oxygen Depletion 405.1 5210 B.................... ............................. I-1578-78 \8\............ 973.44,\3\ p. 17.\9\
10. Boron \37\--Total, mg/L:
Colorimetric (curcumin)... 212.3 4500-B B.................. ............................. I-3112-85
ICP/AES, or............... \5\ 200.7 3120 B
DCP....................... ........... .......................... D4190-82(88)................. ......................... Note 34
11. Bromide, mg/L:
Titrimetric............... 320.1 .......................... D1246-82(88)(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............... D3557-90(A or B)............. I-3135-85 or I-3136-85... 974.27,\3\ p. 37.\9\
AA furnace................ 213.2 3113 B.................... D3557-90(D)
ICP/AES \36\.............. \5\ 200.7 3120 B.................... ............................. I-1472-85
DCP \36\.................. ........... .......................... D4190-82(88)................. ......................... Note 34.
Voltametry,\11\ or........ ........... .......................... D3557-90(C)
Colorimetric (Dithizone).. ........... 3500-Cd D
13. Calcium--Total,\4\ mg/L;
Digestion \4\ followed by:
AA direct aspiration...... 215.1 3111 B.................... D511-93(B)................... I-3152-85
ICP/AES................... \5\ 200.7 3120 B
DCP, or................... ........... .......................... ............................. ......................... Note 34.
Titrimetric (EDTA)........ 215.2 3500-Ca D................. D511-93(A)
14. Carbonaceous biochemical
oxygen demand (CBOD5), mg/L
\12\:
Dissolved Oxygen Depletion ........... 5210 B
with nitrification
inhibitor.
15. Chemical oxygen demand 410.1 5220 C.................... D1252-88(A).................. I-3560-85................ 973.46,\3\ p. 17.\9\
(COD), mg/L; Titrimetric, or. 410.2 I-3562-85................
410.3
Spectrophotometric, manual 410.4 5220 D.................... D1252-88(B).................. I-3561-85................ Notes 13 or 14.
or automated.
16. Chloride, mg/L:
Titrimetric (silver ........... 4500-Cl- B................ D512-89(B)................... I-1183-85
nitrate) or.
(Mercuric nitrate)........ 325.3 4500-Cl- C................ D512-89(A)................... I-1184-85................ 973.51.\3\
Colorimetric, manual or... ........... .......................... ............................. I-1187-85
Automated (Ferricyanide).. 325.1 or 4500-Cl-E................. ............................. I-2187-85
325.2
17. Chlorine--Total residual,
mg/L; Titrimetric:
Amperometric direct....... 330.1 4500-Cl D................. D1253-86(92)
Iodometric direct......... 330.3 4500-Cl B
Back titration ether end- 330.2 4500-Cl C
point \15\ or.
DPD-FAS................... 330.4 4500-Cl F
Spectrophotometric, DPD... 330.5 4500-Cl G
Or Electrode.............. ........... .......................... ............................. ......................... Note 16.
18. Chromium VI dissolved, mg/
L; 0.45 micron filtration
followed by:
AA chelation-extraction or 218.4 3111 C.................... ............................. I-1232-85
Colorimetric ........... 3500-Cr D................. D1687-92(A).................. I-1230-85
(Diphenylcarbazide).
19. Chromium--Total,\4\ mg/L;
Digestion \4\ followed by:
AA direct aspiration \36\. 218.1 3111 B.................... D1687-92(B).................. I-3236-85................ 974.27.\3\
AA chelation-extraction... 218.3 3111 C
AA furnace................ 218.2 3113 B.................... D1687-92(C)
[[Page 10]]
ICP/AES \36\.............. \5\ 200.7 3120 B
DCP,\36\ or............... ........... .......................... D4190-82(88)................. ......................... Note 34.
Colorimetric ........... 3500-Cr D
(Diphenylcarbazide)
20. Cobalt--Total,\4\ mg/L;
Digestion \4\ followed by:
AA direct aspiration...... 219.1 3111 B or C............... D3558-90(A or B)............. I-3239-85................ p. 37.\9\
AA furnace................ 219.2 3113 B.................... D3558-90(C)
ICP/AES................... \5\ 200.7 3120 B
DCP....................... ........... .......................... D4190-82(88)................. ......................... Note 34.
21. Color platinum cobalt
units or dominant wavelength,
hue, luminance purity:
Colorimetric (ADMI), or... 110.1 2120 E.................... ............................. ......................... Note 18.
(Platinum cobalt), or..... 110.2 2120 B.................... ............................. I-1250-85................ .....................
Spectrophotometric........ 110.3 2120 C
22. Copper--Total,4 mg/L;
Digestion 4 followed by:
AA direct aspiration 36... 220.1 3111 B or C............... D1688-90(A or B)............. I-3270-85 or I3271-85.... 974.27 3 p. 37.9
AA furnace................ 220.2 3113 B.................... D1688-90(C)
ICP/AES 36................ 5 200.7 3120 B
DCP 36 or................. ........... .......................... D4190-82(88)................. ......................... Note 34.
Colorimetric (Neocuproine) ........... 3500-Cu D
or.
(Bicinchoninate).......... ........... Or E...................... ............................. ......................... Note 19.
23. Cyanide--Total, mg/L:
Manual distillation with ........... 4500-CN C................. D2036-91(A)
MgCl2 followed by.
Titrimetric, or........... ........... 4500-CN D................. ............................. ......................... p. 22.9
Spectrophotometric, manual 31 335.2 4500-CN E................. D2036-91(A).................. I-3300-85
or.
Automated 20.............. 31 335.3
24. Available Cyanide, mg/L
Cyanide amenable to 335.1 4500-CN G................. D2036-91(B)..................
chlorination (CATC),
Manual distillation with
MgCl2 followed by
titrimetry or
spectrophotometry.
Flow injection and ligand ............................. ......................... 44 OIA-1677
exchange, followed by
amperometry.
25. Fluoride--Total, mg/L:
Manual distillation 6 ........... 4500-F B
followed by.
Electrode, manual or...... 340.2 4500-F C.................. D1179-93(B)
Automated................. ........... .......................... ............................. I-4327-85
Colorimetric (SPADNS)..... 340.1 4500-F D.................. D1179-93(A)
Or Automated complexone... 340.3 4500-F E
26. Gold--Total,4 mg/L;
Digestion 4 followed by:
AA direct aspiration...... 231.1 3111 B
AA furnace, or............ 231.2
DCP....................... ........... .......................... ............................. ......................... Note 34.
27. Hardness--Total, as CaCO3,
mg/L
Automated colorimetric,... 130.1
[[Page 11]]
Titrimetric (EDTA), or Ca 130.2 2340 B or C............... 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, 150.1 4500-H= B................. D1293-84(90)(A or B)......... I-1586-85................ 973.41.3
or.
Automated electrode....... ........... .......................... ............................. ......................... Note 21.
29. Iridium--Total,4 mg/L;
Digestion 4 followed by:
AA direct aspiration or... 235.1 3111 B
AA furnace................ 235.2
30. Iron--Total,4 mg/L;
Digestion 4 followed by:
AA direct aspiration 36... 236.1 3111 B or C............... D1068-90(A or B)............. I-3381-85................ 974.27.3
AA furnace................ 236.2 3113 B.................... D1068-90(C)
ICP/AES 36................ 5 200.7 3120 B
DCP 36 or................. ........... .......................... D4190-82(88)................. ......................... Note 34.
Colorimetric ........... 3500-Fe D................. D1068-90(D).................. ......................... Note 22.
(Phenanthroline).
31. Kjeldahl Nitrogen--Total,
(as N), mg/L:
Digestion and distillation 351.3 4500-NH3B or C............ D3590-89(A).................. ......................... .....................
followed by:.
Titration................. 351.3 4500-NH3E................. D3590-89(A).................. ......................... 973.483.
Nesslerization............ 351.3 4500-NH3C................. D3590-89(A).................. ......................... .....................
Electrode................. 351.3 4500-NH3F or G............ ............................. ......................... .....................
Automated phenate 351.1 .......................... ............................. I-4551-788............... .....................
colorimetric.
Semi-automated block 351.2 .......................... D3590-89(B).................. ......................... .....................
digester colorimetric.
Manual or block digester 351.4 .......................... D3590-89(A).................. ......................... .....................
potentiometric.
Block Digester, followed
by:.
Auto distillation and ........... .......................... ............................. ......................... Note 39.
Titration, or.
Nesslerization............ ........... .......................... ............................. ......................... Note 40.
Flow injection gas ........... .......................... ............................. ......................... Note 41.
diffusion.
32. Lead--Total,4 mg/L;
Digestion \4\ followed by:
AA direct aspiration 36... 239.1 3111 B or C............... D3559-90(A or B)............. I-3399-85................ 974.27.3
AA furnace................ 239.2 3113 B.................... D3559-90(D)
ICP/AES 36................ 5 200.7 3120 B
DCP 36.................... ........... .......................... D4190-82(88)................. ......................... Note 34.
Voltametry 11 or.......... ........... .......................... D3559-90(C)
Colorimetric (Dithizone).. ........... 3500-Pb D
33. Magnesium--Total,\4\ mg/L;
Digestion \4\ followed by:
AA direct aspiration...... 242.1 3111 B.................... D511-93(B)................... I-3447-85................ 974.27.\3\
ICP/AES................... \5\ 200.7 3120 B
DCP, or................... ........... .......................... ............................. ......................... Note 34.
Gravimetric............... ........... 3500-Mg D
34. Manganese--Total,\4\ mg/L;
Digestion \4\ followed by:
AA direct aspiration \36\. 243.1 3111 B.................... D858-90(A or B).............. I-3454-85................ 974.27.\3\
AA furnace................ 243.2 3113 B.................... D858-90(C)
ICP/AES \36\.............. \5\ 200.7 3120 B
DCP \36\ or............... ........... .......................... D4190-82(88)................. ......................... Note 34.
Colorimetric (Persulfate), ........... 3500-Mn D................. ............................. ......................... 920.203.\3\
or.
(Periodate)............... ........... .......................... ............................. ......................... Note 23.
35. Mercury--Total,\4\ mg/L:
Cold vapor, manual, or.... 245.1 3112 B.................... D3223-91..................... I-3462-85................ \3\ 977.22
Automated................. 245.2 .......................... ............................. ......................... .....................
[[Page 12]]
Oxidation, purge and trap, \43\ 1631 .......................... ............................. ......................... .....................
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.................... ............................. I-3490-85
AA furnace................ 246.2 3113 B
ICP/AES................... \5\ 200.7 3120 B
DCP....................... ........... .......................... ............................. ......................... Note 34.
37. Nickel--Total,\4\ mg/L;
Digestion \4\ followed by:
AA direct aspiration \36\. 249.1 3111 B or C............... D1886-90(A or B)............. I-3499-85
AA furnace................ 249.2 3113 B.................... D1886-90(C)
ICP/AES \36\.............. \5\ 200.7 3120 B
DCP \36\, or.............. ........... .......................... D4190-82(88)................. ......................... Note 34.
Colorimetric (heptoxime).. ........... 3500-Ni D
38. Nitrate (as N), mg/L:
Colorimetric (Brucine 352.1 .......................... ............................. ......................... 973.50,\3\ 419 D,\17\
sulfate), or Nitrate- p. 28.\9\
nitrite N minus Nitrite N
(See parameters 39 and
40).
39. Nitrate-nitrite (as N), mg/
L:
Cadmium reduction, Manual 353.3 4500-NO3- E............... D3867-90(B)
or.
Automated, or............. 353.2 4500-NO3- F............... D3867-90(A).................. I-4545-85
Automated hydrazine....... 353.1 4500-NO3- H
40. Nitrite (as N), mg/L;
Spectrophotometric:
Manual or................. 354.1 4500-NO2- B............... ............................. ......................... Note 25.
Automated (Diazotization). ........... .......................... ............................. I-4540-85
41. Oil and grease--Total 413.1 5520 B\38\................
recoverable, mg/L:
Gravimetric (extraction)
Oil and grease and non- 1664, Rev.
polar material, mg/L: A
Hexane extractable
material (HEM): n-Hexane
extraction and
gravimetry\42\.
Silica gel treated HEM 1664, Rev.
(SGT-HEM): Silica gel A
treatment and
gravimetry\42\.
42. Organic carbon--Total
(TOC), mg/L:
Combustion or oxidation... 415.1 5310 B, C, or D........... D2579-93 (A or B)............ ......................... 973.47,3 p. 14.24
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.................. ............................. I-4601-85................ 973.56.3
Manual single reagent..... 365.2 4500-P E.................. 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
AA furnace................ 252.2
46. Oxygen, dissolved, mg/L:
Winkler (Azide 360.2 4500-O C.................. D888-92(A)................... I-1575-78 8.............. 973.45B.3
modification), or.
[[Page 13]]
Electrode................. 360.1 4500-O G.................. D888-92(B)................... I-1576-78 8
47. Palladium--Total,4 mg/L;
Digestion 4 followed by:
AA direct aspiration, or.. 253.1 3111 B.................... ............................. ......................... 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 365.2 4500-P B,5................ ............................. ......................... 973.55.\3\
followed by.
Manual or................. 365.2 or 4500-P E.................. D515-88(A)
365.3
Automated ascorbic acid 365.1 4500-P F.................. ............................. I-4600-85................ 973.56.\3\
reduction.
Semi-automated block 365.4 .......................... D515-88(B)
digestor.
51. Platinum--Total,\4\ mg/L;
Digestion \4\ followed by:
AA direct aspiration........ 255.1 3111 B
AA furnace................ 255.2
DCP....................... ........... .......................... ............................. ......................... Note 34.
52. Potassium--Total,\4\ mg/L;
Digestion \4\ followed by:
AA direct aspiration...... 258.1 3111 B.................... ............................. I-3630-85................ 973.53.\3\
ICP/AES................... \5\ 200.7 3120 B
Flame photometric, or..... ........... 3500-K D
Colorimetric.............. ........... .......................... ............................. ......................... 317 B.\17\
53. Residue--Total, mg/L:
Gravimetric, 103-105 deg.. 160.3 2540 B.................... ............................. I-3750-85
54. Residue--filterable, mg/L:
Gravimetric, 180 deg...... 160.1 2540 C.................... ............................. I-1750-85
55. Residue--nonfilterable
(TSS), mg/L:
Gravimetric, 103-105 deg. 160.2 2540 D.................... ............................. I-3765-85
post washing of residue.
56. Residue--settleable, mg/L:
Volumetric, (Imhoff cone), 160.5 2540 F
or 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
AA furnace................ 265.2
59. Ruthenium--Total,\4\ mg/L;
Digestion \4\ followed by:
AA direct aspiration, or.. 267.1 3111 B
AA furnace................ 267.2
60. Selenium--Total,\4\ mg/L;
Digestion \4\ followed by:
AA furnace................ 270.2 3113 B.................... D3859-93(B)
ICP/AES,\36\ or........... \5\ 200.7 3120 B
AA gaseous hydride........ ........... 3114 B.................... D3859-93(A).................. I-3667-85
61. Silica \37\--Dissolved, mg/
L; 0.45 micron filtration
followed by:
Colorimetric, Manual or... 370.1 4500-Si D................. D859-88...................... I-1700-85
[[Page 14]]
Automated ........... .......................... ............................. I-2700-85
(Molybdosilicate), or.
ICP....................... \5\ 200.7 3120 B
62. Silver--Total,\4\ mg/L;
Digestion 4, 29 followed by:
AA direct aspiration...... 272.1 3111 B or C............... ............................. I-3720-85................ 974.27,\3\ p. 37.\9\
AA furnace................ 272.2 3113 B
ICP/AES................... \5\ 200.7 3120 B
DCP....................... ........... .......................... ............................. ......................... Note 34.
63. Sodium--Total,\4\ mg/L;
Digestion \4\ followed by:
AA direct aspiration...... 273.1 3111 B.................... ............................. I-3735-85................ 973.54.\3\
ICP/AES................... \5\ 200.7 3120 B
DCP, or................... ........... .......................... ............................. ......................... Note 34.
Flame photometric......... ........... 3500 Na D
64. Specific conductance,
micromhos/cm at 25 deg.C:
Wheatstone bridge......... 120.1 2510 B.................... D1125-91(A).................. I-1780-85................ 973.40.\3\
65. Sulfate (as SO4), mg/L:
Automated colorimetric 375.1
(barium chloranilate).
Gravimetric............... 375.3 4500-SO4-2 C or D......... ............................. ......................... 925.54.\3\
Turbidimetric, or......... 375.4 .......................... D516-90...................... ......................... 426C.\30\
66. Sulfide (as S), mg/L:
Titrimetric (iodine), or.. 376.1 4500-S-2E................. ............................. I-3840-85
Colorimetric (methylene 376.2 4500-S-2D
blue).
67. Sulfite (as SO3), mg/L:
Titrimetric (iodine- 377.1 4500-SO3-2 B
iodate).
68. Surfactants, mg/L:
Colorimetric (methylene 425.1 5540 C.................... D2330-88
blue).
69. Temperature, deg.C:
Thermometric.............. 170.1 2550 B.................... ............................. ......................... Note 32.
70. Thallium--Total,\4\ mg/L;
Digestion \4\ followed by:
AA direct aspiration...... 279.1 3111 B
AA furnace................ 279.2
ICP/AES, or............... \5\ 200.7 3120 B
71. Tin--Total,\4\ mg/L;
Digestion \4\ followed by:
AA direct aspiration...... 282.1 3111 B.................... ............................. I-3850-78 \8\
AA furnace, or............ 282.2 3113 B
ICP/AES................... \5\ 200.7
72. Titanium--Total,\4\ mg/L;
Digestion \4\ followed by:
AA direct aspiration...... 283.1 3111 D
AA furnace................ 283.2
DCP....................... ........... .......................... ............................. ......................... Note 34.
73. Turbidity, NTU:
Nephelometric............. 180.1 2130 B.................... D1889-88(A).................. I-3860-85
74. Vanadium--Total,\4\ mg/L;
Digestion \4\ followed by:
AA direct aspiration...... 286.1 3111 D
AA furnace................ 286.2 .......................... D3373-93
[[Page 15]]
ICP/AES................... \5\ 200.7 3120 B
DCP, or................... ........... .......................... D4190-82(88)................. ......................... Note 34.
Colorimetric (Gallic acid) ........... 3500-V D
75. Zinc--Total,\4\ mg/L;
Digestion \4\ followed by:
AA direct aspiration \36\. 289.1 3111 B or C............... D1691-90 (A or B)............ I-3900-85................ 974.27,\3\ p. 37.\9\
AA furnace................ 289.2
ICP/AES \36\.............. \5\ 200.7 3120 B
DCP,\36\ or............... ........... .......................... D4190-82(88)................. ......................... Note 34.
Colorimetric (Dithizone) ........... 3500-Zn E
or.
(Zincon).................. ........... 3500-Zn F................. ............................. ......................... Note 33.
--------------------------------------------------------------------------------------------------------------------------------------------------------
Table IB 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).
\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 IB 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, 1430 Broadway, New York, NY 10018.
\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 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 the nitrification inhibitor.
\13\ OIC Chemical Oxygen Demand Method, Oceanography International Corporation, 1978, 512 West Loop, P.O. Box 2980, College Station, TX 77840.
\14\ Chemical Oxygen Demand, Method 8000, Hach Handbook of Water Analysis, 1979, Hach Chemical Company, P.O. 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, P.O. Box 389, Loveland, CO 80537.
[[Page 16]]
\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 mainfold 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, P.O. 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, P.O. 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 spectophotometric 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.
\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, Fison Instruments, Inc., 32 Commerce Center, Cherry Hill Drive, Danvers, MA 01923.
\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, P.O. 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 the trichlorofluoromethane extraction solvent is approved.
\39\ Nitrogen, Total Kjeldahl, Method PAI-DK01 (Block Digestion, Steam Distillation, Titrimetric Detection), revised 12/22/94, Perstop Analytical
Corporation.
\40\ Nitrogen, Total Kjeldahl, Method PAI-DK02 (Block Digestion, Steam Distillation, Colorimetric Detection), revised 12/22/94, Perstop Analytical
Corporation.
\41\ Nitrogen, Total Kjeldahl, Method PAI-DK03 (Block Digestion, Automated FIA Gas Diffusion), revised 12/22/94, Perstop Analytical Corporation.
\42\ Method 1664, Revision A ``n-Hexane Extractable Material (HEM; Oil and Grease) and Silica Gel Treated n-Hexane Extractablke 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\ 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,
P.O. Box 9010, College Station, TX 77842-9010.
Table IC.--List of Approved Test Procedures for Non-Pesticide Organic Compounds
--------------------------------------------------------------------------------------------------------------------------------------------------------
EPA method number 2 7
Parameter \1\ --------------------------------------------------------------------------------------------------------------------------
GC GC/MS HPLC Standard method 18th Ed. ASTM Other
--------------------------------------------------------------------------------------------------------------------------------------------------------
1. Acenaphthene............. 610 625, 1625 610 6410 B, 6440 B D4657-92
2. Acenaphthylene........... 610 625, 1625 610 6410 B, 6440 B D4657-92
3. Acrolein................. 603 \4\ 604, 1624 ......... ................................. ....................
4. Acrylonitrile............ 603 \4\ 624, 1624 610 ................................. ....................
5. Anthracene............... 610 625, 1625 610 6410 B, 6440 B D4657-92
6. Benzene.................. 602 624, 1624 ......... 6210 B, 6220 B ....................
7. Benzidine................ .................. \5\ 625, 1625 605 ................................. .................... Note 3, p.1.
8. Benzo(a)anthracene....... 610 625, 1625 610 6410 B, 6440 B D4657-92
9. Benzo(a)pyrene........... 610 625, 1625 610 6410 B, 6440 B D4657-92
[[Page 17]]
10. Benzo(b)fluoranthene.... 610 625, 1625 610 6410 B, 6440 B D4657-92
11. Benzo(g, h, i)perylene.. 610 625, 1625 610 6410 B, 6440 B D4657-92
12. Benzo(k)fluoranthene.... 610 625, 1625 610 6410 B, 6440 B D4657-92
13. Benzyl chloride......... .................. .................. ......... ................................. .................... Note 3,
p.130: Note
6, p. S102.
14. Benzyl butyl phthalate.. 606 625, 1625 ......... 6410 B .................... .............
15. Bis(2-chloroethoxy) 611 625, 1625 ......... 6410 B ....................
methane.
16. Bis(2-chloroethyl) ether 611 625, 1625 ......... 6410 B ....................
17. Bis (2-ethylhexyl) 606 625, 1625 ......... 6410 B, 6230 B ....................
phthalate.
18. Bromodichloromethane.... 601 624, 1624 ......... 6210 B, 6230 B ....................
19. Bromoform............... 601 624, 1624 ......... 6210 B, 6230 B ....................
20. Bromomethane............ 601 624, 1624 ......... 6210 B, 6230 B ....................
21. 4-Bromophenylphenyl 611 625, 1625 ......... 6410 B ....................
ether.
22. Carbon tetrachloride.... 601 624, 1624 ......... 6230 B, 6410 B .................... Note 3,
p.130.
23. 4-Chloro-3-methylphenol. 604 625, 1625 ......... 6410 B, 6420 B ....................
24. Chlorobenzene........... 601, 602 624, 1624 ......... 6210 B, 6220 B .................... Note 3,
6230 B p.130.
25. Chloroethane............ 601 624, 1624 ......... 6210 B, 6230 B ....................
26. 2-Chloroethylvinyl ether 601 624, 1624 ......... 6210 B, 6230 B .................... .............
27. Chloraform.............. 601 624, 1624 ......... 6210 B, 6230 B .................... Note, p.130.
28. Chloromethane........... 601 624, 1624 ......... 6210 B. 6230 B ....................
29. 2-Chloronaphthalene..... 612 625, 1625 ......... 6410 B ....................
30. 2-Chlorophenol.......... 604 625, 1625 ......... 6410 B, 6420 B ....................
31. 4-Chlorophenylphenyl 611 625, 1625 ......... 6410 B ....................
ether.
32. Chrysene................ 610 625, 1625 610 6410 B, 6440 B D4657-92
33. Dibenzo(a,h)anthracene.. 610 625, 1625 610 6410 B, 6440 B D4657-92
34. Dibromochloromethane.... 601 624, 1624 ......... 6210 B, 6230 B ....................
35. 1, 2-Dichlorobenzene.... 601,602,612 624,625,1625 ......... 6410 B, 6230 B, 6220 B ....................
36. 1, 3-Dichlorobenzene.... 601,602,612 624,625,1625 ......... 6410 B, 6230 B, 6220 B ....................
37. 1,4-Dichlorobenzene..... 601, 602, 612 624, 625, 1625 ......... 6410 B, 6220 B, 6230 B
38. 3, 3-Dichlorobenzidine.. .................. 625, 1625 605 6410 B ....................
39. Dichlorodifluoromethane. 601 .................. ......... 6230 B ....................
40. 1, 1-Dichloroethane..... 601 624, 1624 ......... 6230 B, 6210 B ....................
41. 1, 2-Dichloroethane..... 601 624, 1624 ......... 6230 B, 6210 B ....................
42. 1, 1-Dichloroethene..... 601 624, 1624 ......... 6230 B, 6210 B ....................
43. trans-1, 2- 601 624, 1624 ......... 6230 B, 6210 B ....................
Dichloroethene.
44. 2, 4-Dichlorophenol..... 604 625, 1625 ......... 6420 B, 6410 B ....................
45. 1, 2-Dichloropropane.... 601 624, 1624 ......... 6230 B, 6210 B ....................
46. cis-1, 3-Dichloropropene 601 624, 1624 ......... 6230 B, 6210 B ....................
47. trans-1, 3- 601 624, 1624 ......... 6230 B, 6210 B ....................
Dichloropropene.
48. Diethyl phthalate....... 606 625, 1625 ......... 6410 B ....................
49. 2, 4-Dimethylphenol..... 604 625, 1625 ......... 6420 B, 6410 B ....................
50. Dimethyl phthalate...... 606 625, 1625 ......... 6410 B ....................
51. Di-n-butyl phthalate.... 606 625, 1625 ......... 6410 B ....................
52. Di-n-octyl phthalate.... 606 625, 1625 ......... 6410 B ....................
53. 2,4-Dinitrophenol....... 604 625, 1625 ......... 6420 B, 6410 B ....................
54. 2,4-Dinitrotoluene...... 609 625, 1625 ......... 6410 B
55. 2, 6-Dinitrotoluene..... 609 625, 1625 ......... 6410 B ....................
[[Page 18]]
56. Epichlorohydrin......... .................. .................. ......... ................................. .................... Note 3, p.130
Note 6,
p.S102.
57. Ethylbenzene............ 602 624, 1624 ......... 6220 B, 6210 B ....................
58. Fluoranthene............ 610 625, 1625 610 6410 B, 6440 B D4657-92
59. Fluorene................ 610 625, 1625 610 6410 B, 6440 B D4657-92
60. 1,2,3,4,6,7,8- .................. 1613 .........
Heptachlorodibenzofuran.
61. 1,2,3,4,7,8,9- .................. 1613 .........
Heptachlorodibenzofuran.
62. 1,2,3,4,6,7,8- .................. 1613 .........
Heptachlorodibenzo-p-dioxin.
63. Hexachlorobenzene....... 612 625, 1625 ......... 6410 B
64. Hexachlorobutadiene..... 612 625, 1625 ......... 6410 B
65. 612 625, 1625 \5\ ......... 6410 B
Hexachlorocyclopentadiene.
66. 1,2,3,4,7,8- .................. 1613 .........
Hexachlorodibenzofuran.
67. 1,2,3,6,7,8- .................. 1613 .........
Hexachlorodibenzofuran.
68. 1,2,3,7,8,9- .................. 1613 .........
Hexachlorodibenzofuran.
69. 2,3,4,6,7,8- .................. 1613 .........
Hexachlorodibenzofuran.
70. 1,2,3,4,7,8- .................. 1613 .........
Hexachlorodibenzo-p-dioxin.
71. 1,2,3,6,7,8- .................. 1613 .........
Hexachlorodibenzo-p-dioxin.
72. 1,2,3,7,8,9- .................. 1613 .........
Hexachlorodibenzo-p-dioxin.
73. Hexachloroethane........ 616 625, 1625 ......... 6410 B
74. Ideno(1,2,3-cd)pyrene... 610 625, 1625 610 6410 B, 6440 B D4657-87
75. Isophorone.............. 609 625, 1625 ......... 6410 B
76. Methylene chloride...... 601 624, 1624 ......... 6230 B Note 3, p.
130.
77. 2-Methyl-4,6- 604 625, 1625 ......... 6420 B, 6410 B
dinitrophenol.
78. Naphthalene............. 610 625, 1625 610 6410 B, 6440 B
79. Nitrobenzene............ 609 625, 1625 ......... 6410 B D4657-87
80. 2-Nitrophenol........... 604 625, 1625 ......... 6410 B, 6420 B
81. 4-Nitrophenol........... 604 625, 1625 ......... 6410 B, 6420 B
82. N-Nitrosodimethylamine.. 607 625, 1625 ......... 6410 B
83. N-Nitrosodi-n- 607 625, 1625 \5\ ......... 6410 B
propylamine.
84. N-Nitrosodiphenylamine.. 607 625, 1625 \5\ ......... 6410 B
85. Octachlorodibenzofuran.. .................. 1613 .........
86. Octachlorodibenzo-p- .................. 1613 .........
dioxin.
87. 2,2-Oxybis(1- 611 625, 1625 ......... 6410 B
chloropropane).
88. PCB-1016................ 608 625 ......... 6410 B Note 3, p.
43.
89. PCB-1221................ 608 625 ......... 6410 B Note 3, p.
43.
90. PCB-1232................ 608 625 ......... 6410 B Note 3, p.
43.
91. PCB 1242................ 608 625 ......... 6410 B Note 3, p.
43.
92. PCB-1248................ 608 625 .........
93. PCB-1254................ 608 625 ......... 6410 B Note 3, p.
43.
94. PCB-1260................ 608 625 ......... 6410 B, 6630 B Note 3, p.
43.
95. 1,2,3,7,8- .................. 1613 .........
Pentachlorodibenzofuran.
96. 2,3,4,7,8- .................. 1613 .........
Pentachlorodibenzofuran.
97. 1,2,3,7,8- .................. 1613 .........
Pentachlorodibenzo-p-dioxin.
[[Page 19]]
98. Pentachlorophenol 604 625, 1625 ......... 6410 B, 6630 B Note 3, p.
140.
99. Phenanthrene............ 610 625, 1625 610 6410 B, 6440 B D4657-87
100. Phenol................. 604 625, 1625 ......... 6420 B, 6410 B
101. Pyrene................. 610 625, 1625 610 6410 B, 6440 B D4657-87
102. 2,3,7,8- .................. 1613 .........
Tetrachlorodibenzofuran.
103. 2,3,7,8- .................. 613, 1613 \5\ .........
Tetrachlorodibenzo-p-dioxin.
104. 1,1,2,2- 601 624, 1624 ......... 6230 B, 6210 B Note 3, p.
Tetrachloroethane. 130.
105. Tetrachloroethene...... 601 624, 1624 ......... 6230 B, 6410 B Note 3, p.
130.
106. Toluene................ 602 624, 1624 ......... 6210 B, 6220 B
107. 1,2,4-Trichlorobenzene. 612 625, 1625 ......... 6410 B Note 3, p.
130.
108. 1,1,1-Trichloroethane.. 601 624, 1624 ......... 6210 B, 6230 B
109. 1,1,2-Trichloroethane.. 601 624, 1624 ......... 6210 B, 6230 B Note 3, p.
130.
110. Trichloroethene........ 601 624, 1624 ......... 6210 B, 6230 B
111. Trichlorofluoromethane. 601 624 ......... 6210 B, 6230 B
112. 2,4,6-Trichlorophenol.. 604 625, 1625 ......... 6410 B, 6240 B
113. Vinyl chloride......... 601 624, 1624 ......... 6210 B, 6230 B
--------------------------------------------------------------------------------------------------------------------------------------------------------
Table 1C notes:
\1\ All parameters are expressed in micrograms per liter (g/L) except for Method 1613 in which the parameters are expressed in picograms per
liter (pg/L).
\2\ The full text of Methods 601-613, 624, 625, 1624, and 1625, are given at appendix A, ``Test Procedures for Analysis of Organic Pollutants,'' of this
part 136. The full text of Method 1613 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 Procedures 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 1624.
\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, or Method 1625, are preferred methods for these compounds.
5a 625, Screening only.
\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 601-603, 624,
625, 1624, and 1625 (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 1624 and 1625) 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.
Table ID.--List of Approved Test Procedures for Pesticides 1
--------------------------------------------------------------------------------------------------------------------------------------------------------
Parameter Method EPA \2\ \7\ Standard methods 18th Ed. ASTM Other
--------------------------------------------------------------------------------------------------------------------------------------------------------
1. Aldrin........................ GC 608 6630 B & C............... D3086-90................ Note 3, p. 7; note 4, p.
30; 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.
6. Azinphos methyl............... GC ........... ......................... ........................ Note 3, p. 25; Note 6,
p. S51.
7. Barban........................ TLC ........... ......................... ........................ Note 3, p. 104; Note 6,
p. S64.
8. -BHC................. GC 608 6630 B & C............... D3086-90................ Note 3, p. 7; note 8.
GC/MS \5\ 625 6410 B................... ........................ ........................
[[Page 20]]
9. -BHC................. GC 608 6630 C................... D3086-90................ Note 8.
GC/MS \5\ 625 6410 B................... ........................ ........................
10. -BHC................ GC 608 6630 C................... D3086-90................ Note 8.
GC/MS \5\ 625 6410 B................... ........................ ........................
11. -BHC (Lindane)...... GC 608 6630 B & C............... D3086-90................ Note 3, p. 7; note 4, p.
30; 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. 30; Note 6,
p. S73.
15. Chlordane.................... GC 608 6630 B & C............... D3086-90................ Note 3, p. 7; 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. 35.
18. 4,4'-DDD..................... GC 608 6630 B & C............... D3086-90................ Note 3, p. 7; note 4, p.
30; 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.
30; 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.
30; 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. 30; Note 6, p. S51.
24. Dicamba...................... GC ........... ......................... ........................ Note 3, p. 115.
25. Dichlofenthion............... GC ........... ......................... ........................ Note 4, p. 30; Note 6,
p. S73.
26. Dichloran.................... GC ........... 6630 B & C............... ........................ Note 3, p. 7.
27. Dicofol...................... GC ........... ......................... D3086-90................ ........................
28. Dieldrin..................... GC 608 6630 B & C............... ........................ Note 3, p. 7; note 4, p.
30; note 8.
GC/MS 625 6410 B................... ........................ ........................
29. Dioxathion................... GC ........... ......................... ........................ Note 4, p. 30; 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 8.
GC/MS \5\ 625 6410 B................... ........................ ........................
33. Endosulfan II................ GC 608 6630 B & C............... D3086-90............... Note 3, p. 7; note 8.
GC/MS \5\ 625 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.
30; note 8.
GC/MS \5\ 625 6410 B................... ........................ ........................
36. Endrin aldehyde.............. GC 608 ......................... ........................ Note 8.
GC/MS 625 ......................... ........................ ........................
[[Page 21]]
37. Ethion....................... GC ........... ......................... ........................ Note 4, p. 30; 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............... D3086-90................ Note 3, p. 7; note 4, p.
30; note 8.
GC/MS 625 6410 B................... ........................ ........................
41. Heptachlor epoxide........... GC 608 6630 B & C............... D3086-90................ Note 3, p. 7; note 4, p.
30; note 6, p. S73;
note 8.
GC/MS 625 6410 B................... ........................ ........................
42. Isodrin...................... GC ........... ......................... ........................ Note 4, p. 30; 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. 30; 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.
30; note 8.
47. Mexacarbate.................. TLC ........... ......................... ........................ Note 3, p. 94; Note 6,
p. S60.
48. Mirex........................ GC ........... 6630 B & C............... ........................ Note 3, p. 7.
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. 30.
53. Parathion ethyl.............. GC ........... 6630 C................... ........................ Note 3, p. 25.
54. PCNB......................... GC ........... 6630 B & C............... ........................ Note 3, p. 7.
55. Perthane..................... GC ........... ......................... D3086-90................ ........................
56. Prometron.................... GC ........... ......................... ........................ Note 3, p. 83; Note 6,
p. S68.
57. Prometryn.................... GC ........... ......................... ........................ Note 3, p. 83; Note 6,
p. S68.
58. Propazine.................... GC ........... ......................... ........................ Note 3, p. 83; Note 6,
p. S68.
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.
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. 35.
67. 2,4,5-TP (Silvex)............ GC ........... 6640 B................... ........................ Note 3, p. 115
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.
30; note 8.
GC/MS 625 6410 B................... ........................ ........................
70. Trifluralin.................. GC ........... 6630 B................... ........................ Note 3, p. 7.
--------------------------------------------------------------------------------------------------------------------------------------------------------
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 -BHC, -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).
[[Page 22]]
\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-
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 EmporeTM Disk'', 3M Corporation, Revised 10/28/94.
Table IE.--List of Approved Radiologic Test Procedures
--------------------------------------------------------------------------------------------------------------------------------------------------------
Reference (method number or page)
---------------------------------------------------------------------------------------------
Parameter and units Method Standard methods
EPA\1\ 18th 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 counter.... 900.0................. 7110 B D1890-90 pp. 75 and 78.\3\
4. Beta-Counting error, pCi..... Proportional counter.... Appendix B............ 7110 B D1890-90 p. 79.
5. (a) Radium Total pCi per Proportional counter.... 903.0................. 7500Ra B D2460-90
liter.
(b)Ra, pCi per liter.......... Scintillation counter... 903.1................. 7500Ra C D3454-91 p. 81.
--------------------------------------------------------------------------------------------------------------------------------------------------------
Table IE 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 23]]
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 .... 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 Office of the Federal Register, 800 North Capitol Street, NW.,
Suite 700, Washington, DC.
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-600/4-79-020, 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
[[Page 24]]
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. Standard Methods for
the Examination of Water and Wastewater. 18th Edition. Amer. Publ. Hlth.
Assoc., 1015 15th Street NW, Washington, DC 20005. Cost: $160.00. Table
IA, Note 4.
(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 in 40 CFR 136.3,
Tables 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 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
[[Page 25]]
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.
Method available from 3M Corporation. Table IC, Note 8 and Table ID,
Note 8.
(34) USEPA. 1993. Methods for Measuring the Acute Toxicity of
Effluents to Freshwater and Marine Organisms.
[[Page 26]]
Fourth Edition, December 1993. Environmental Monitoring Systems
Laboratory, U.S. Environmental Protection Agency, Cincinnati, Ohio (EPA/
600/4-90/027F). Available from: National Technical Information Service,
5285 Port Royal Road, Springfield, Virginia 22161, Publ. No. PB-91-
167650. Cost: $31.00. Table IA, Note 17. See changes in the manual,
listed in Part V of this rule.
(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. 1994. Short-term Methods for Estimating the Chronic
Toxicity of Effluents and Receiving Waters to Freshwater Organisms.
Third Edition. July 1994. Environmental Monitoring Systems Laboratory,
U.S. Environmental Protection Agency, Cincinnati, Ohio. (EPA/600/4-91/
002). Available from: National Technical Information Service, 5285 Port
Royal Road, Springfield, Virginia 22161, Publ. No. PB-92-139492. Cost:
$31.00. Table IA, Note 8.
(39) USEPA. 1994. Short-term Methods for Estimating the Chronic
Toxicity of Effluents and Receiving Waters to Marine and Estuarine
Organisms. Second Edition, July 1994. Environmental Monitoring Systems
Laboratory, U.S. Environmental Protection Agency, Cincinnati, Ohio. EPA/
600/4-91/003. Available from: National Technical Information Service,
5285 Port Royal Road, Springfield, Virginia 22161, Publ. No. PB-92-
139484. Cost: $45.00. Table IA, Note 9.
(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.
Editorial Note: At 64 FR 30434, June 8, 1999, the following
paragraph (40) was added, effective July 8, 1999; however paragraph (40)
was previously added to the 1999 volume.
(40) USEPA. 1999. Method 1631, Revision B, ``Mercury in Water by
Oxidation, Purge and Trap, and Cold Vapor Atomic Fluorescence
Spectrometry.'' May 1999. Office of Water, U.S. Environmental Protection
Agency (EPA 821-R-99-005). Available from: National Technical
Information Service, 5285 Port Royal Road, Springfield, Virginia 22161.
Publication No. PB99-131989. Cost: $25.50. Table IB, Note 43.
(41) USEPA, January 1999 Errata for the Effluent and Receiving Water
Testing Manuals: Acute Toxicity of Effluents and Receiving Waters to
Freshwater and Marine Organisms; Short-Term Methods for Estimating the
Chronic Toxicity of Effluents and Receiving Waters to Freshwater
Organisms; and Short-Term Methods for Estimating the Chronic Toxicity of
Effluents and Receiving Waters to Marine and Estuarine Organisms. U.S.
Environmental Protection Agency, Office of Research and Development,
Duluth, MN. EPA-600/R-98/182.
[[Page 27]]
(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.
(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:
1-4 Coliform, fecal and total. P,G.............. Cool, 4C, 0.008% Na2S2O3 5...... 6 hours.
5 Fecal streptococci.......... P,G.............. Cool, 4C, 0.008% Na2S2O3 5...... 6 hours.
Table IA--Aquatic Toxicity
Tests:
6-10 Toxicity, acute and P,G.............. Cool, 4 deg.C 16............... 36 hours.
chronic.
Table IB--Inorganic Tests:
1. Acidity.................... P, G............. Cool, 4C........................ 14 days.
2. Alkalinity................. P, G............. ......do........................ Do.
4. Ammonia.................... P, G............. Cool, 4C, H2SO4 to pH<2......... 28 days.
9. Biochemical oxygen demand.. P, G............. Cool, 4C........................ 48 hours.
10. Boron..................... P, PFTE, or HNO3 TO pH2..................... 6 months.
Quartz.
11. Bromide................... P, G............. None required................... 28 days.
14. Biochemical oxygen demand, P, G............. Cool, 4C........................ 48 hours.
carbonaceous.
15. Chemical oxygen demand.... P, G............. Cool, 4C, 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, 4C........................ 48 hours.
23-24. Cyanide, total and P, G............. Cool, 4C, NaOH to pH>12, 0.6g 14 days.6
amenable to chlorination. 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, 4C, H2SO4 to pH<2......... 28 days.
nitrogen.
Metals:7
18. Chromium VI............... P, G............. Cool, 4C........................ 24 hours.
35. Mercury................... P, G............. HNO3 to pH<2.................... 28 days.
[[Page 28]]
3, 5-8, 12, 13, 19, 20, 22, P, G............. ......do........................ 6 months.
26, 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.
38. Nitrate................... P, G............. Cool, 4C........................ 48 hours.
39. Nitrate-nitrite........... P, G............. Cool, 4C, H2SO4 to pH<2......... 28 days.
40. Nitrite................... P, G............. Cool, 4C........................ 48 hours.
41. Oil and grease............ G................ Cool to 4C, HCl or H2SO4 to pH<2 28 days.
42. Organic Carbon............ P, G............. Cool to 4 deg.C HC1 or H2SO4 or 28 days.
H3PO4, to pH2.
44. Orthophosphate............ P, G............. Filter immediately, Cool, 4C.... 48 hours.
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, 4C, H2SO4 to pH<2......... 28 days.
49. Phosphorus (elemental).... G................ Cool, 4C........................ 48 hours.
50. Phosphorus, total......... P, G............. Cool, 4C, H2SO4 to pH<2......... 28 days.
53. Residue, total............ P, G............. Cool, 4C........................ 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, 4C add zinc acetate plus 7 days.
sodium hydroxide to pH>9.
67. Sulfite................... P, G............. None required................... Analyze immediately.
68. Surfactants............... P ,G............. Cool, 4C........................ 48 hours.
69. Temperature............... P, G............. None required................... Analyze.
73. Turbidity................. P, G............. Cool, 4C........................ 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.
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, pH9, 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, 4C, 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
[[Page 29]]
\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 4C 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 4C, 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.
[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]
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.
[[Page 30]]
(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, 401 M Street,
SW., 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 parameter(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, 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
[[Page 31]]
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
------------------------------------------------------------------------
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 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.
[[Page 32]]
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.
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
[[Page 33]]
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-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+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 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 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, chloromethane,
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 g/
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
[[Page 34]]
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
L of one or more secondary dilution standards to 100, 500, or
1000 L of reagent water. A 25-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.
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 g/mL of each internal standard compound.
The addition of 10 L of this standard to 5.0 mL of sample or
calibration standard would be equivalent to 30 g/L.
7.4.3 Analyze each calibration standard according to Section 10,
adding 10 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
[[Page 35]]
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
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 g/L of each
parameter by adding 200 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 g/L, and the
standard deviation of the recovery (s) in 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.
[[Page 36]]
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 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
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 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 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) 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 halocarbons. A combination of bromochloromethane,
2-bromo-1-
[[Page 37]]
chloropropane, and 1,4-dichlorobutane 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
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/L. Add 10 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 analysis, the analyst should fill a
second syringe at this time to protect against possible loss of data.
Add 10.0 L of the surrogate spiking solution (Section 8.7) and
10.0 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.
[[Page 38]]
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 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 concentration
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.
12.2 This method is recommended for use in the concentration range
from the MDL to 1000 x MDL. 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 8.0 to 500 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 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.
[[Page 39]]
Table 1--Chromatographic Conditions and Method Detection Limits
----------------------------------------------------------------------------------------------------------------
Retention time (min) Method detection
Parameter ------------------------------------ limit (g/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 C for 3
min then programmed at 8 C/min to 220 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 C for 3 min then
programmed at 6 C/min to 170 C and held for 4 min.
nd=not determined.
Table 2--Calibration and QC Acceptance Criteria--Method 601 a
----------------------------------------------------------------------------------------------------------------
Limit for s
Parameter Range for Q (g/ Range for X Range P,
(g/L) L) (g/L) Ps (%)
----------------------------------------------------------------------------------------------------------------
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 g/L.
[[Page 40]]
Q=Concentration measured in QC check sample, in g/L (Section 7.5.3).
s=Standard deviation of four recovery measurements, in g/L (Section 8.2.4).
X=Average recovery for four recovery measurements, in 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' (g/L) m>g/L) (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 g/L.
sn'=Expected single analyst standard deviation of measurements at an average concentration found of X, in g/L.
S\1\=Expected interlaboratory standard deviation of measurements at an average concentration found of X, in
g/L.
C=True value for the concentration, in g/L.
X=Average recovery found for measurements of samples containing a concentration of C, in g/L.
a Estimates based upon the performance in a single laboratory.\10\
[[Page 41]]
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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 46]]
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: 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
concentrations 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).
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.
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-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:
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6.4.1 2,6-Diphenylene oxide polymer--Tenax, (60/80 mesh),
chromatographic grade or equivalent.
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 standard 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-dichlorobenzene,
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.
6.6.1 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-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 g/
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
L of one or more secondary dilution standards to 100, 500, or
1000 mL of reagent water. A 25-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, ,,,-
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 g/mL of each internal standard compound.
The addition of 10 l of this
[[Page 48]]
standard to 5.0 mL of sample or calibration standard would be equivalent
to 30 g/L.
7.4.3 Analyze each calibration standard according to Section 10,
adding 10 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
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 g/L of each
parameter by adding 200 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 g/L, and the
standard deviation of the recovery (s) in 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 49]]
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 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
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 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) plus-minus 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 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 50]]
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. , , ,-
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 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/L. Add 10
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 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 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 L of the surrogate spiking solution (Section 8.7) and
10.0 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 51]]
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 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 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 52]]
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 (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 C for 2 min then programmed at 6 C/min to 90 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 C for 2 min then programmed at 2 C/min to 100 C
for a final hold.
Table 2--Calibration and QC Acceptance Criteria--Method 602 a
----------------------------------------------------------------------------------------------------------------
Range for X
Range for Q Limit for s (g/ Range for
Parameter (g/ (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 g/L (Section 7.5.3).
s=Standard deviation of four recovery measurements, in g/L (Section 8.2.4).
X=Average recovery for four recovery measurements, in 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 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
(g/L) (g/L) (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 g/L.
S=Expected single analyst standard deviation of measurements at an average concentration found of X, in X g/L.
S=Expected interlaboratory standard deviation of measurements at an average concentration found of X, in g/L.
C=True value for the Concentration, in g/L.
X=Average recovery found for measurements of samples containing a concentration of C, in g/L.
[[Page 53]]
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[[Page 57]]
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 58]]
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-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 59]]
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-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 g/
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
L of one or more secondary dilution standards to 100, 500, or
1000 mL of reagent water. A 25-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 g/mL of each internal standard compound.
The addition of 10 L of this standard to 5.0 mL of sample or
calibration standard would be equivalent to 30 g/L.
7.4.3 Analyze each calibration standard according to Section 10,
adding 10 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 60]]
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
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 g/L of each
parameter by adding 200 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 g/L, and the
standard deviation of the recovery (s) in 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 61]]
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 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
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 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 62]]
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 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 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 63]]
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 1,000 x MDL. Direct aqueous injection techniques should be
used to measure concentration levels above 1,000 x MDL.
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 (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 C for 1.5 min
(during desorption), then heated as rapidly as possible to 150 C and
held for 20 min; column bakeout at 190 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
----------------------------------------------------------------------------------------------------------------
Average Standard
Sample Spike conc. recovery deviation Average
Parameter matrix (g/ (g/ (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\
----------------------------------------------------------------------------------------------------------------
Range for Q Limit for S Range for X
Parameter (g/ (g/ (g/ Range for
L) L) L) P, Ps (%)
----------------------------------------------------------------------------------------------------------------
Acrolein................................................. 45.9-54.1 4.6 42.9-60.1 88-118
[[Page 64]]
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 g/L.9
Q=Concentration measured in QC check sample, in g/L (Section 7.5.3).
s=Standard deviation of four recovery measurements, in g/L (Section 8.2.4).
X=Average recovery for four recovery measurements, in 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 65]]
[GRAPHIC] [TIFF OMITTED] TC02JY92.009
[[Page 66]]
[GRAPHIC] [TIFF OMITTED] TC02JY92.010
[[Page 67]]
[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 68]]
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 69]]
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 (-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 g/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 70]]
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 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 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 (g/L).
Cs=Concentration of the parameter to be measured (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 71]]
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 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
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 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 g/L, and the
standard deviation of the recovery (s) in 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.
[[Page 72]]
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 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 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 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 the
nature of the samples. Field duplicates
[[Page 73]]
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 74]]
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 L of the sample extract or standard
into the gas chromatograph using the solvent-flush
technique.11 Smaller (1.0 L) volumes may be injected
if automatic devices are employed. Record the volume injected to the
nearest 0.05 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 75]]
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 L of the column fractions into the gas
chromatograph using the solvent-flush technique. Smaller (1.0
L) volumes can be injected if automatic devices are employed.
Record the volume injected to the nearest 0.05 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 (L).
Vt=Volume of total extract (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
(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 (L).
Vt=Total volume of column eluate or combined fractions from
which Vi was taken (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 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 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 76]]
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
detection
Parameter Retention limit
time (min) (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 C at injection,
programmed immediately at 8 C/min to 150 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) (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 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 77]]
Table 3--QC Acceptance Criteria--Method 604
----------------------------------------------------------------------------------------------------------------
Range for X
Test conc. Limit for s (g/ Range for
Parameter (g/ (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 g/L (Section 8.2.4).
X--Average recovery for four recovery measurements, in 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'
(g/L) (g/L) (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 g/L.
sr'=Expected single analyst standard deviation of measurements at an average concentration found of X, in g/L.
S'=Expected interlaboratory standard deviation of measurements at an average concentration found of X, in g/L.
C=True value for the concentration, in g/L.
X=Average recovery found for measurements of samples containing a concentration of C, in g/L.
[[Page 78]]
[GRAPHIC] [TIFF OMITTED] TC02JY92.012
[[Page 79]]
[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 80]]
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 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 that are inherent in the extraction step are 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 Some dye plant effluents contain large amounts of components
with retention 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 81]]
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--Bioanalytical 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 g/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 82]]
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 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 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 (g/L).
Cs=Concentration of the parameter to be measured (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 83]]
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 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 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 g/L, and the
standard deviation of the recovery (s) in 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 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 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
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 84]]
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 85]]
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 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 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 86]]
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 (L).
Vt=Volume of total extract (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
(g).
Vo=Volume of water extracted (L).
13.2 Report results in 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 7 x MDL to 3000 x MDL.\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 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 87]]
Table 1--Chromatographic Conditions and Method Detection Limits
------------------------------------------------------------------------
Method
Column detection
Parameter Retention capacity limit
time (min) factor (k) (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
cm x 4.6 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
----------------------------------------------------------------------------------------------------------------
Range for X
Test conc. Limit for s (g/ Range for
Parameter (g/ (g/ L) P, Ps
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 g/L (Section 8.2.4).
X=Average recovery for four recovery measurements, in 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
recovery, Single analyst Overall
Parameter X(g/ precision, sr precision, S
L) (g/L) (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 g/L.
sr=Expected single analyst standard deviation of measurements at an average concentration found of X, in g/L.
S=Expected interlaboratory standard deviation of measurements at an average concentration found of X, in g/L.
C=True value for the concentration, in g/L.
X=Average recovery found for measurements of samples containing a concentration of C, in g/L.
[[Page 88]]
[GRAPHIC] [TIFF OMITTED] TC02JY92.014
[[Page 89]]
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 90]]
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 91]]
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 g/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 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 92]]
7.3.2 Using injections of 2 to 5 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 (g/L).
Cs=Concentration of the parameter to be measured (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 g/mL; bis(2-ethylhexyl)
phthalate, 50 g/mL; di-n-octyl phthalate, 50 g/mL; any
other phthlate, 25 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 g/L, and the
standard deviation of the recovery (s) in g/L, for each
parameter using the four results.
[[Page 93]]
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 (P