[Title 40 CFR 136]
[Code of Federal Regulations (annual edition) - July 1, 1996 Edition]
[Title 40 - PROTECTION OF ENVIRONMENT]
[Chapter I - ENVIRONMENTAL PROTECTION AGENCY (CONTINUED)]
[Part 136 - GUIDELINES ESTABLISHING TEST PROCEDURES FOR THE ANALYSIS OF POLLUTANTS]
[From the U.S. Government Publishing Office]
40
PROTECTION OF ENVIRONMENT
10
1996-07-01
1996-07-01
false
GUIDELINES ESTABLISHING TEST PROCEDURES FOR THE ANALYSIS OF POLLUTANTS
136
PART 136
PROTECTION OF ENVIRONMENT
ENVIRONMENTAL PROTECTION AGENCY (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, and IE. The full text of the referenced test
procedures are incorporated by reference into Tables IA, IB, IC, ID, and
IE. The references and the sources from which they 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 the standard analytical test procedures
incorporated by reference and described in Tables IA, IB, IC, ID, and
IE, or by any alternate test procedure which has been approved by the
Administrator under the provisions of
[[Page 6]]
paragraph (d) of this section and Secs. 136.4 and 136.5 of this part
136. Under certain circumstances (Sec. 136.3 (b) or (c) 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-NH3 B................ ............................. ......................... 973.49.\3\
pH 9.5),\6\ followed by.
Nesslerization............ 350.2 4500-NH3 C................ D1426-93(A).................. I-3520-85................ 973.49.\3\
Titration................. 350.2 4500-NH3 E
Electrode................. 350.3 4500-NH3 F or G........... D1426-93(B)
Automated phenate, or..... 350.1 4500-NH3 H................ ............................. 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. Cyanide amenable to
chlorination,mg/L:
Manual distillation with 335.1 4500-CN G................. D2036-91(B)
MgCl2 followed by
titrimetric or
Spectrophotometric.
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
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
[[Page 11]]
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-NH3 B or C........... D3590-89(A).................. ......................... .....................
followed by:.
Titration................. 351.3 4500-NH3 E................ D3590-89(A).................. ......................... 973.483.
Nesslerization............ 351.3 4500-NH3 C................ D3590-89(A).................. ......................... .....................
Electrode................. 351.3 4500-NH3 F 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................ 977.22.\3\
Automated................. 245.2
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
[[Page 12]]
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
recoverable, mg/L:
Gravimetric (extraction).. 413.1 5520 B \38\
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.
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:
[[Page 13]]
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
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.
[[Page 14]]
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-2 E................ ............................. I-3840-85
Colorimetric (methylene 376.2 4500-S-2 D
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
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.
[[Page 15]]
(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.
\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.
[[Page 16]]
\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.
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
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.
[[Page 17]]
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, 3-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 ....................
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. Hexachlorobenzene....... 612 625, 1625 ......... 6410 B ....................
61. Hexachlorobutadiene..... 612 625, 1625 ......... 6410 B ....................
62. 612 \5\ 625, 1625 ......... 6410 B ....................
Hexachlorocyclopentadiene.
63. Hexachloroethane........ 616 625, 1625 ......... 6410 B ....................
64. Ideno(1,2,3-cd) pyrene.. 610 625, 1625 610 6410 B, 6440 B D4657-92
65. Isophorone.............. 609 625, 1625 ......... 6410 B ....................
66. Methylene chloride...... 601 624, 1624 ......... 6230 B .................... Note 3,
p.130.
67. 2-Methyl-4,6- 604 625, 1625 ......... 6420 B, 6410 B
dinitrophenol.
68. Naphthalene............. 610 625, 1625 610 6410 B, 6440 B ....................
[[Page 18]]
69. Nitrobenezene........... 609 625, 1625 ......... 6410 B
70. 2-Nitrophenol........... 604 625, 1625 ......... 6410 B, 6420 B ....................
71. 4-Nitrophenol........... 604 625, 1625 ......... 6410 B, 6420 B ....................
72. N-Nitrosodimethylamine.. 607 625, 1625 ......... 6410 B ....................
73. N-Nitrosodi-n- 607 \5\625, 1625 ......... 6410 B ....................
propylamine.
74. N-Nitrosodiphenylamine.. 607 \5\625, 1625 ......... 6410 B ....................
75. 2,2-Oxybis(1- 611 625, 1625 ......... 6410 B ....................
chloropropane).
76. PCB-1016................ 608 625 ......... 6410 B .................... Note 3, p.
43; note 8.
77. PCB-1221................ 608 625 ......... 6410 B .................... Note 3, p.
43; note 8.
78. PCB-1232................ 608 625 ......... 6410 B .................... Note 3, p.
43; note 8.
79. PCB-1242................ 608 625 ......... 6410 B .................... Note 3, p.
43; note 8.
80. PCB-1248................ 608 625 ......... ................................. .................... Note 3, p.
43; note 8.
81. PCB-1254................ 608 625 ......... 6410 B .................... Note 3, p.
43; note 8.
82. PCB-1260................ 608 625 ......... 6410 B, 6630 B .................... Note 3, p.
43; note 8.
83. Pentachlorophenol....... 604 625, 1625 ......... 6410 B, 6630 B .................... Note 3,
p.140.
84. Phenanthrene............ 610 625, 1625 610 6410 B, 6440 B D4657-92
85. Phenol.................. 604 625, 1625 ......... 6420 B, 6410 B ....................
86. Pyrene.................. 610 625, 1625 610 6410 B, 6440 B D4675-92
87. 2,3,7,8- .................. 5a 613 ......... ................................. ....................
Tetrachlorodibenzo-p-dioxin.
88. 1,1,2,2- 601 624, 1624 ......... 6230 B, 6210 B .................... Note 3,
Tetrachloroethane. p.130.
89. Tetrachloroethene....... 601 624, 1624 ......... 6230 B, 6210 B .................... Note 3,
p.130.
90. Toluene................. 602 624, 1624 ......... 6210 B, 6220 B ....................
91. 1,2,4-Trichlorobenzene.. 612 625, 1625 ......... 6410 B .................... Note 3,
p.130.
92. 1,1,1-Trichloroethane... 601 624, 1624 ......... 6210 B, 6230 B ....................
93. 1,1,2-Trichloroethane... 601 624, 1624 ......... 6210 B, 6230 B .................... Note 3,
p.130.
94. Trichloroethene......... 601 624, 1624 ......... 6210 B, 6230 B ....................
95. Trichlorofluoromethane.. 601 624 ......... 6210 B, 6230 B ....................
96. 2,4,6-Trichlorophenol... 604 625, 1625 ......... 6410 B, 6240 B ....................
97. Vinyl chloride.......... 601 624, 1624 ......... 6210 B, 6230 B ....................
--------------------------------------------------------------------------------------------------------------------------------------------------------
Table 1C notes:
\1\ All parameters are expressed in micrograms per liter (g/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 standardized test procedure to be used to determine the method detection limit (MDL) for these test procedures is given at appendix B,
``Definition and Procedure for the Determination of the Method Detection Limit'' of this part 136.
\3\ ``Methods for Benzidine: Chlorinated Organic Compounds, Pentachlorophenol and Pesticides in Water and Wastewater,'' U.S. Environmental Protection
Agency, September, 1978.
\4\ Method 624 may be extended to screen samples for Acrolein and Acrylonitrile. However, when they are known to be present, the preferred method for
these two compounds is Method 603 or Method 1624.
[[Page 19]]
\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................... ........................ ........................
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.
[[Page 20]]
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 ......................... ........................ ........................
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.
[[Page 21]]
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).
\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.
[[Page 22]]
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]]
(b) The full texts of the methods from the following references
which are cited in Tables IA, IB, IC, ID, and IE 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 Environmental Monitoring
Systems 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, room 8301,
1110 L Street, NW., Washington, DC 20408.
References, Sources, Costs, and Table Citations:
(1) The full text of Methods 601-613, 624, 625, 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 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.
[[Page 24]]
(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 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.
[[Page 25]]
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. 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.
(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
[[Page 26]]
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, 4C \16\................... 6 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 pH<2.................... 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.................... 6 months.
3, 5-8, 12, 13, 19, 20, 22,
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 pH<2.
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.
[[Page 27]]
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, Telflon-lined Cool, 4C, 0.008% Na2S2O3.\5\.... 14 days.
39-43, 45-47, 56, 66, 88, 89, septum.
92-95, 97. Purgeable
Halocarbons.
6, 57, 90. Purgeable aromatic ......do......... Cool, 4C, 0.008% Na2S2O3\5\, HC1 Do.
hydrocarbons. to pH2\9\.
3, 4, Acrolein and ......do......... Cool, 4C, 0.008% Na2S2O3\5\; Do.
acrylonitrile. Adjust pH to 4-5 \10\.
23, 30, 44, 49, 53, 67, 70, G, Teflon-lined Cool, 4C, 0.008% Na2S2O3\5\..... 7 days until extraction,
71, 83, 85, 96. Phenols \11\. cap. 40 days after
extraction.
7, 38. Benzidines11........... ......do......... ......do........................ 7 days until
extraction.13
14, 17, 48, 50-52. Phthalate ......do......... Cool, 4C........................ 7 days until extraction;
esters11. 40 days after
extraction.
72-74. Nitrosamines11,14...... ......do......... Cool, 4C, store in dark, 0.008% Do.
Na2S2O35.
76-82. PCBs11 acrylonitrile... ......do......... Cool, 4C........................ Do.
54, 55, 65, 69. Nitroaromatics ......do......... Cool, 4C, 0.008% Na2S2O35 store Do.
and isophorone11. in dark.
1, 2, 5, 8-12, 32, 33, 58, 59, ......do......... ......do........................ Do.
64, 68, 84, 86. Polynuclear
aromatic hydrocarbons.\1\\1\.
15, 16, 21, 31, 75. ......do......... Cool, 4C, 0.008% Na2S2O35....... Do.
Haloethers11.
29, 35-37, 60-63, 91. ......do......... Cool, 4C........................ Do.
Chlorinated hydrocarbons\11\.
87. TCDD\11\.................. ......do......... Cool, 4C, 0.008% Na2S2O35....... Do.
Table ID--Pesticides Tests:
1-70. Pesticides\11\.......... ......do......... Cool, 4C, pH 5-915.............. Do.
Table IE--Radiological Tests:
1-5. Alpha, beta and radium... P, G............. HNO3 to pH<2.................... 6 months.
----------------------------------------------------------------------------------------------------------------
Table II Notes
\1\ Polyethylene (P) or glass (G). For microbiology, plastic sample containers must be made of sterilizable
materials (polypropylene or other autoclavable plastic).
2 Sample preservation should be performed immediately upon sample collection. For composite chemical samples
each aliquot should be preserved at the time of collection. When use of an automated sampler makes it
impossible to preserve each aliquot, then chemical samples may be preserved by maintaining at 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.
[[Page 28]]
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]
Sec. 136.4 Application for alternate test procedures.
(a) Any person may apply to the Regional Administrator in the Region
where the discharge occurs for approval of an alternative test
procedure.
(b) When the discharge for which an alternative test procedure is
proposed occurs within a State having a permit program approved pursuant
to section 402 of the Act, the applicant shall submit his application to
the Regional Administrator through the Director of the State agency
having responsibility for issuance of NPDES permits within such State.
(c) Unless and until printed application forms are made available,
an application for an alternate test procedure may be made by letter in
triplicate. Any application for an alternate test procedure under this
paragraph (c) shall:
(1) Provide the name and address of the responsible person or firm
making the discharge (if not the applicant) and the applicable ID number
of the existing or pending permit, issuing agency, and type of permit
for which the alternate test procedure is requested, and the discharge
serial number.
(2) Identify the pollutant or parameter for which approval of an
alternate testing procedure is being requested.
(3) Provide justification for using testing procedures other than
those specified in Table I.
(4) Provide a detailed description of the proposed alternate test
procedure, together with references to published studies of the
applicability of the alternate test procedure to the effluents in
question.
(d) An application for approval of an alternate test procedure for
nationwide use may be made by letter in triplicate to the Director,
Environmental Monitoring and Support Laboratory, Cincinnati, Ohio 45268.
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
[[Page 29]]
performance of the approved test procedures.
[38 FR 28760, Oct. 16, 1973, as amended at 41 FR 52785, Dec. 1, 1976]
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 Environmental Monitoring
and Support Laboratory, Cincinnati.
(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 Environmental Monitoring and Support Laboratory,
Cincinnati.
(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 Environmental Monitoring and
Support Laboratory, Cincinnati. A copy of all approval and rejection
notifications will be forwarded to the Director, Environmental
Monitoring and Support Laboratory, Cincinnati, for the purposes of
national coordination.
(e) Approval for nationwide use. (1) Within 60 days of the receipt
by the Director of the Environmental Monitoring Systems Laboratory--
Cincinnati (EMSL-CI) of an application for an alternate test procedure
for nationwide use, the Director of EMSL-CI 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 90 days of the receipt of a complete package: EMSL-CI
shall perform any analysis necessary to determine whether the alternate
method satisfies the applicable requirements of this part; and the
Director of EMSL-CI 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]
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:
[[Page 30]]
------------------------------------------------------------------------
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.
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
[[Page 31]]
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 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).
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6.1.2 A water purification system (Millipore Super-Q or equivalent)
may be used to generate reagent water.
6.1.3 Reagent water may also be prepared by boiling water for 15
min. Subsequently, while maintaining the temperature at 90 deg.C,
bubble a contaminant-free inert gas through the water for 1 h. While
still hot, transfer the water to a narrow mouth screw-cap bottle and
seal with a Teflon-lined septum and cap.
6.2 Sodium thiosulfate--(ACS) Granular.
6.3 Trap Materials:
6.3.1 Coconut charcoal--6/10 mesh sieved to 26 mesh, Barnabey
Cheney, CA-580-26 lot M-2649 or equivalent.
6.3.2 2,6-Diphenylene oxide polymer--Tenax, (60/80 mesh),
chromatographic grade or equivalent.
6.3.3 Methyl silicone packing--3% OV-1 on Chromosorb-W (60/80 mesh)
or equivalent.
6.3.4 Silica gel--35/60 mesh, Davison, grade-15 or equivalent.
6.4 Methanol--Pesticide quality or equivalent.
6.5 Stock standard solutions--Stock standard solutions may be
prepared from 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 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.
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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