(4) Carbonate: Carbonate interference is evidenced by noticeable effervescence upon acidification in the distillation flask, a reduction in the pH of the absorber solution, and incomplete cyanide spike recovery. When significant carbonate is present, adjust the pH to 12 using calcium hydroxide instead of sodium hydroxide. Allow the precipitate to settle and decant or filter the sample prior to analysis (also see Standard Method 4500−CN.B.3.d).
(5) Chlorine, hypochlorite, or other oxidant: Treat a sample known or suspected to contain chlorine, hypochlorite, or other oxidant as directed in footnote 57 For dissolved metals, filter grab samples within 15 minutes of collection and before adding preservatives. For a composite sample collected with an automated sampler, filter the sample within 15 minutes after completion of collection and before adding preservatives. If it is known or suspected that dissolved sample integrity will be compromised during collection of a composite sample collected automatically over time (e.g., by interchange of a metal between dissolved and suspended forms), collect and filter grab samples to be composited (footnote 2) in place of a composite sample collected automatically.
7 For dissolved metals, filter grab samples within 15 minutes of collection and before adding preservatives. For a composite sample collected with an automated sampler, filter the sample within 15 minutes after completion of collection and before adding preservatives. If it is known or suspected that dissolved sample integrity will be compromised during collection of a composite sample collected automatically over time (e.g., by interchange of a metal between dissolved and suspended forms), collect and filter grab samples to be composited (footnote 2) in place of a composite sample collected automatically.
8 Guidance applies to samples to be analyzed by GC, LC, or GC/MS for specific compounds.
9 If the sample is not adjusted to pH < 2, then the sample 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 (i.e., use all necessary preservatives and hold for the shortest time listed). When the analytes of concern fall within two or more chemical categories, the sample may be preserved by cooling to ≤ 6 °C, reducing residual chlorine with 0.008% sodium thiosulfate, storing in the dark, and adjusting the pH to 6-9; samples preserved in this manner may be held for seven days before extraction and for forty days after extraction. Exceptions to this optional preservation and holding time procedure are noted in footnote 5 (regarding the requirement for thiosulfate reduction), and footnotes 12, 13 (regarding the analysis of benzidine).
12 If 1,2-diphenylhydrazine is likely to be present, adjust the pH of the sample to 4.0 ± 0.2 to prevent rearrangement to benzidine.
13 Extracts may be stored up to 30 days at < 0 °C.
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 Place sufficient ice 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, immediately measure the temperature of the samples and confirm that the preservation temperature maximum has not been exceeded. In the isolated cases where it can be documented that this holding temperature cannot 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. Aqueous samples must not be frozen. Hand-delivered samples used on the day of collection do not need to be cooled to 0 to 6 °C prior to test initiation.
17 Samples collected for the determination of trace level mercury (<100 ng/L) using EPA Method 1631 must be collected in tightly-capped fluoropolymer or glass bottles and preserved with BrCl or HCl solution within 48 hours of sample collection. The time to preservation may be extended to 28 days if a sample is oxidized in the sample bottle. A sample collected for dissolved trace level mercury should be filtered in the laboratory within 24 hours of the time of collection. However, if circumstances preclude overnight shipment, the sample should be filtered in a designated clean area in the field in accordance with procedures given in Method 1669. If sample integrity will not be maintained by shipment to and filtration in the laboratory, the sample must be filtered in a designated clean area in the field within the time period necessary to maintain sample integrity. A sample that has been collected for determination of total or dissolved trace level mercury must be analyzed within 90 days of sample collection.
18 Aqueous samples must be preserved at ≤ 6 °C, and should not be frozen unless data demonstrating that sample freezing does not adversely impact sample integrity is maintained on file and accepted as valid by the regulatory authority. Also, for purposes of NPDES monitoring, the specification of “≤ 6 °C” is used in place of the “4 °C” and “< 4 °C” sample temperature requirements listed in some methods. It is not necessary to measure the sample temperature to three significant figures (1/100th of 1 degree); rather, three significant figures are specified so that rounding down to 6 °C may not be used to meet the ≤6 °C requirement. The preservation temperature does not apply to samples that are analyzed immediately (less than 15 minutes).
19 An aqueous sample may be collected and shipped without acid preservation. However, acid must be added at least 24 hours before analysis to dissolve any metals that adsorb to the container walls. If the sample must be analyzed within 24 hours of collection, add the acid immediately (see footnote 2). Soil and sediment samples do not need to be preserved with acid. The allowances in this footnote supersede the preservation and holding time requirements in the approved metals methods.
20 To achieve the 28-day holding time, use the ammonium sulfate buffer solution specified in EPA Method 218.6. The allowance in this footnote supersedes preservation and holding time requirements in the approved hexavalent chromium methods, unless this supersession would compromise the measurement, in which case requirements in the method must be followed.
21 Holding time is calculated from time of sample collection to elution for samples shipped to the laboratory in bulk and calculated from the time of sample filtration to elution for samples filtered in the field.
22 Sample analysis should begin as soon as possible after receipt; sample incubation must be started no later than 8 hours from time of collection.
23 For fecal coliform samples for sewage sludge (biosolids) only, the holding time is extended to 24 hours for the following sample types using either EPA Method 1680 (LTB-EC) or 1681 (A-1): Class A composted, Class B aerobically digested, and Class B anaerobically digested.
24 The immediate filtration requirement in orthophosphate measurement is to assess the dissolved or bio-available form of orthophosphorus (i.e.,that which passes through a 0.45-micron filter), hence the requirement to filter the sample immediately upon collection (i.e.,within 15 minutes of collection).
SECTION 13. NR 219.04 Table G is created to read:
Table G—Test Methods for Pesticide Active Ingredients
EPA survey code | Pesticide name | CAS No. | EPA analytical method No.(s) 3 |
8 | Triadimefon | 43121-43-3 | 1656, 507, 633, 525.1, 525.2 |
12 | Dichlorvos | 62-73-7 | 1657, 507, 525.1, 525.2, 622 |
16 | 2,4-D; 2,4-D Salts and Esters [2,4-Dichloro-phenoxyacetic acid] | 94-75-7 | 1658, 515.1, 515.2, 555, 615 |
17 | 2,4-DB; 2,4-DB Salts and Esters [2,4-Dichlorophenoxybutyric acid] | 94-82-6 | 1658, 515.1, 515.2, 555, 615 |
22 | Mevinphos | 7786-34-7 | 1657, 507, 525.1, 525.2, 622 |
25 | Cyanazine | 21725-46-2 | 507, 629 |
26 | Propachlor | 1918-16-7 | 1656, 508, 608.1, 525.1, 525.2 |
27 | MCPA; MCPA Salts and Esters [2-Methyl-4-chlorophenoxyacetic acid] | 94-74-6 | 1658, 555, 615 |
30 | Dichlorprop; Dichlorprop Salts and Esters [2-(2,4-Dichlorophenoxy) propionic acid] | 120-36-5 | 1658, 515.1, 515.2, 555, 615 |
31 | MCPP; MCPP Salts and Esters [2-(2-Methyl-4-chlorophenoxy) propionic acid] | 93-65-2 | 1658, 555, 615 |
35 | TCMTB [2-(Thiocyanomethylthio) benzo-thiazole] | 21564-17-0 | 637 |
39 | Pronamide | 23950-58-5 | 507, 525.1, 525.2, 633.1 |
41 | Propanil | 709-98-8 | 1656, 632.1 |
45 | Metribuzin | 21087-64-9 | 1656, 507, 525.1, 525.2, 633 |
52 | Acephate | 30560-19-1 | 1656, 1657 |
53 | Acifluorfen | 50594-66-6 | 515.1, 515.2, 555 |
54 | Alachlor | 15972-60-8 | 1656, 505, 507, 525.1, 525.2, 645 |
58 | Ametryn | 834-12-8 | 507, 525.2, 619 |
60 | Atrazine | 1912-24-9 | 1656, 505, 507, 525.1, 525.2, 619 |
68 | Bromacil; Bromacil Salts and Esters | 314-40-9 | 1656, 507, 525.1, 525.2, 633 |
69 | Bromoxynil | 1689-84-5 | 1625, 1661 |
69 | Bromoxynil octanoate | 1689-99-2 | 1656 |
70 | Butachlor | 23184-66-9 | 1656, 507, 525.1, 525.2, 645 |
75 | Carbaryl [Sevin] | 63-25-2 | 531.1, 553, 632 |
76 | Carbofuran | 1563-66-2 | 531.1, 632 |
80 | Chloroneb | 2675-77-6 | 1656, 508, 525.1, 525.2, 608.1 |
82 | Chlorothalonil | 1897-45-6 | 1656, 508, 525.1, 525.2, 608.2 |
84 | Stirofos | 961-11-5 | 1657, 507, 525.1, 525.2, 622 |
86 | Chlorpyrifos | 2921-88-2 | 1657, 508, 622 |
90 | Fenvalerate | 51630-58-1 | 1660 |
103 | Diazinon | 333-41-5 | 1657, 507, 525.2, 614, 622 |
107 | Parathion methyl | 298-00-0 | 1657, 614, 622 |
110 | DCPA [Dimethyl 2,3,5,6-tetrachloro-terephthalate] | 1861-32-1 | 1656, 508, 525.1, 525.2, 515.1 2, 515.2 2, 608.2 |
112 | Dinoseb | 88-85-7 | 1658, 515.1, 515.2, 555, 615 |
113 | Dioxathion | 78-34-2 | 1657, 614.1 |
118 | Nabonate [Disodium cyanodithioimidocarbonate] | 138-93-2 | 630.1 |
119 | Diuron | 330-54-1 | 553, 632 |
123 | Endothall | 145-73-3 | 548, 548.1 |
124 | Endrin | 72-20-8 | 1656, 505, 508, 525.1, 525.2, 608, 617 |
125 | Ethalfluralin | 55283-68-6 | 1656, 627 See footnote 1 |
126 | Ethion | 563-12-2 | 1657, 614, 614.1 |
127 | Ethoprop | 13194-48-4 | 1657, 507, 525.1, 525.2, 622 |
132 | Fenarimol | 60168-88-9 | 1656, 507, 525.1, 525.2, 633.1 |
133 | Fenthion | 55-38-9 | 1657, 622 |
138 | Glyphosate [N-(Phosphonomethyl) glycine] | 1071-83-6 | 547 |
140 | Heptachlor | 76-44-8 | 1656, 505, 508, 525.1, 525.2, 608, 617 |
144 | Isopropalin | 33820-53-0 | 1656, 627 |
148 | Linuron | 330-55-2 | 553, 632 |
150 | Malathion | 121-75-5 | 1657, 614 |
154 | Methamidophos | 10265-92-6 | 1657 |
156 | Methomyl | 16752-77-5 | 531.1, 632 |
158 | Methoxychlor | 72-43-5 | 1656, 505, 508, 525.1, 525.2, 608.2, 617 |
172 | Nabam | 142-59-6 | 630, 630.1 |
173 | Naled | 300-76-5 | 1657, 622 |
175 | Norflurazon | 27314-13-2 | 1656, 507, 525.1, 525.2, 645 |
178 | Benfluralin | 1861-40-1 | 1656, 627 See footnote 1 |
182 | Fensulfothion | 115-90-2 | 1657, 622 |
183 | Disulfoton | 298-04-4 | 1657, 507, 525,2, 614, 622 |
185 | Phosmet | 732-11-6 | 1657, 622.1 |
186 | Azinphos Methyl | 86-50-0 | 1657, 614, 622 |
192 | Organo-tin pesticides | 12379-54-3 | 200.7, 200.9, Ind-01 |
197 | Bolstar | 35400-43-2 | 1657, 622 |
203 | Parathion | 56-38-2 | 1657, 614 |
204 | Pendimethalin | 40487-42-1 | 1656 |
205 | Pentachloronitrobenzene | 82-68-8 | 1656, 608.1, 617 |
206 | Pentachlorophenol | 87-86-5 | 1625, 515.2, 555, 515.1, 525.1, 525.2, 625 |
208 | Permethrin | 52645-53-1 | 1656, 1660, 508, 525.1, 525.2, 608.2 |
212 | Phorate | 298-02-2 | 1657, 622 |
218 | Busan 85 [Potassium dimethyldithiocarbamate] | 128-03-0 | 630, 630.1 |
219 | Busan 40 [Potassium N-hydroxymethyl-N-methyldithiocarbamate] | 51026-28-9 | 630, 630.1 |
220 | KN Methyl [Potassium N-methyl-dithiocarbamate] | 137-41-7 | 630, 630.1 |
223 | Prometon | 1610-18-0 | 507, 525.2, 619 |
224 | Prometryn | 7287-19-6 | 507, 525.1, 525.2, 619 |
226 | Propazine | 139-40-2 | 1656, 507, 525.1, 525.2, 619 |
230 | Pyrethrin I | 121-21-1 | 1660 |
232 | Pyrethrin II | 121-29-9 | 1660 |
236 | DEF [S,S,S-Tributyl phosphorotrithioate] | 78-48-8 | 1657 |
239 | Simazine | 122-34-9 | 1656, 505, 507, 525.1, 525.2, 619 |
241 | Carbam-S [Sodium dimethyldithio-carbamate] | 128-04-1 | 630, 630.1 |
243 | Vapam [Sodium methyldithiocarbamate] | 137-42-8 | 630, 630.1 |
252 | Tebuthiuron | 34014-18-1 | 507, 525.1, 525.2 |
254 | Terbacil | 5902-51-2 | 1656, 507, 525.1, 525.2, 633 |
255 | Terbufos | 13071-79-9 | 1657, 507, 614.1, 525.1, 525.2 |
256 | Terbuthylazine | 5915-41-3 | 1656, 619 |
257 | Terbutryn | 886-50-0 | 507, 525.1, 525.2, 619 |
259 | Dazomet | 533-74-4 | 1659, 630, 630.1 |
262 | Toxaphene | 8001-35-2 | 1656, 505, 508, 525.1, 525.2, 608, 617 |
263 | Merphos [Tributyl phosphorotrithioate] | 150-50-5 | 1657, 507, 525.1, 525.2, 622 |
264 | Trifluralin 1 | 1582-09-8 | 1656, 508, 525.2, 617, 627 |
268 | Ziram [Zinc dimethyldithiocarbamate] | 137-30-4 | 630, 630.1 |
1 Monitor and report as total Trifluralin.
2 Applicable to the analysis of DCPA degradates.
3 EPA Methods 608.1 through 645, 1645 through 1661, and Ind-01 are available in Methods For The Determination of Nonconventional Pesticides In Municipal and Industrial Wastewater, Volume I, EPA 821-R-93-010A, Revision I, August 1993, U.S. EPA. EPA Methods 200.9 and 505 through 555 are available in Methods For The Determination of Nonconventional Pesticides In Municipal and Industrial Wastewater, Volume II, EPA 821-R-93-010B, August 1993, U.S. EPA. The full text of Methods 608, 625 and 1625 are provided at Appendix A of this Part 136. The full text of Method 200.7 is provided at appendix C of this part 136.
SECTION 14. NR 219.04 Table H is created to read:
Table H—List of Approved Microbiological Methods for Ambient Water
Parameter and units | Method 1 | EPA | Standard methods | AOAC, ASTM, USGS | Other |
1. Coliform (fecal), number per 100 mL or number per gram dry weight | Most Probable Number (MPN), 5 tube, 3 dilution, or | p. 132 3 | 9221 C E-2006 | | |
| Membrane filter (MF) 2, single step | p. 124 3 | 9222 D-1997 | B-0050-85 4 | |
2. Coliform (fecal) in presence of chlorine, number per 100 mL | MPN, 5 tube, 3 dilution, or | p. 132 3 | 9221 C, E-2006 | | |
| MF 2, single step 5 | p. 124 3 | 9222 D-1997 | | |
3. Coliform (total), number per 100 mL | MPN, 5 tube, 3 dilution, or | p. 114 3 | 9221 B-2006 | | |
| MF 2, single step or two step | p. 108 3 | 9222 B-1997 | B-0025-85 4 | |
4. Coliform (total), in presence of chlorine, number per 100 mL | MPN, 5 tube, 3 dilution, or | p. 114 3 | 9221 B-2006 | | |
| MF 2 with enrichment | p. 111 3 | 9222 (B+B.5c)-1997 | | |
5.E. coli,number per 100 mL | MPN 6, 8, 14, multiple tube, or | | 9221 B.1-2006/ 9221 F-2006 11, 13 | | |
| Multiple tube/multiple well, or | | 9223 B-2004 12 | 991.15 10 | Colilert® 12, 16 Colilert-18® 12, 15, 16 |
| MF 2, 5, 6, 7, 8, two step, or | 1103.1 19 | 9222 B-1997/ 9222 G-1997 18 9213 D-2007 | D5392-93 9 | |
| Single step | 1603 20, 1604 21 | | | mColiBlue-24®17 |
6. Fecal streptococci, number per 100 mL | MPN, 5 tube, 3 dilution, or | p. 139 3 | 9230 B-2007 | | |
| MF 2, or | p. 136 3 | 9230 C-2007 | B-0055-85 4 | |
7. Enterococci, number per 100 mL | MPN 6, 8, multiple tube/multiple well, or | | | D6503-99 9 | Enterolert® 12,,22 |
| MF 2, 5, 6, 7, 8 two step, or | 1106.1 23 | 9230 C-2007 | D5259-92 9 | |
| Single step, or | 1600 24 | 9230 C-2007 | | |
8.Cryptosporidium | Filtration/IMS/FA | 1622 25 1623 26 | | 8.Cm | |
9.Giardia | Filtration/IMS/FA | 1623 26 | | | |
1 The method must be specified when results are reported.
2 A 0.45-µm 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 Microbiological Methods for Monitoring the Environment, Water, and Wastes. EPA/600/8-78/017. 1978. US EPA.
4 U.S. Geological Survey Techniques of Water-Resource Investigations, Book 5, Laboratory Analysis, Chapter A4, Methods for Collection and Analysis of Aquatic Biological and Microbiological Samples. 1989. USGS.
5 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.
6 Tests must be conducted to provide organism enumeration (density). Select the appropriate configuration of tubes/filtrations and dilutions/volumes to account for the quality, character, consistency, and anticipated organism density of the water sample.
7 When the MF method has not been used previously to test waters with high turbidity, large numbers of noncoliform bacteria, or samples that may contain organisms stressed by chlorine, a parallel test should be conducted with a multiple-tube technique to demonstrate applicability and comparability of results.
8 To assess the comparability of results obtained with individual methods, it is suggested that side-by-side tests be conducted across seasons of the year with the water samples routinely tested in accordance with the most current Standard Methods for the Examination of Water and Wastewater or EPA alternate test procedure (ATP) guidelines.
9 Annual Book of ASTM Standards—Water and Environmental Technology. Section 11.02. 2000, 1999, 1996. ASTM International.
10 Official Methods of Analysis of AOAC International, 16th Edition, Volume I, Chapter 17. 1995. AOAC International.
11 The multiple-tube fermentation test is used in 9221B.1-2006. Lactose broth may be used in lieu of lauryl tryptose broth (LTB), if at least 25 parallel tests are conducted between this broth and LTB using the water samples normally tested, and this comparison demonstrates that the false-positive rate and false-negative rate for total coliform using lactose broth is less than 10 percent. No requirement exists to run the completed phase on 10 percent of all total coliform-positive tubes on a seasonal basis.
12 These tests are collectively known as defined enzyme substrate tests, where, for example, a substrate is used to detect the enzyme β-glucuronidase produced byE. coli.
13 After prior enrichment in a presumptive medium for total coliform using 9221B.1-2006, all presumptive tubes or bottles showing any amount of gas, growth or acidity within 48 h ± 3 h of incubation shall be submitted to 9221F-2006. Commercially available EC-MUG media or EC media supplemented in the laboratory with 50 µg/mL of MUG may be used.
14 Samples shall be enumerated by the multiple-tube or multiple-well procedure. Using multiple-tube procedures, employ an appropriate tube and dilution configuration of the sample as needed and report the Most Probable Number (MPN). Samples tested with Colilert® may be enumerated with the multiple-well procedures, Quanti-Tray® or Quanti-Tray®/2000, and the MPN calculated from the table provided by the manufacturer.
15 Colilert-18® is an optimized formulation of the Colilert® for the determination of total coliforms andE. colithat provides results within 18 h of incubation at 35 °C, rather than the 24 h required for the Colilert® test, and is recommended for marine water samples.
16 Descriptions of the Colilert®, Colilert-18®, Quanti-Tray®, and Quanti-Tray®/2000 may be obtained from IDEXX Laboratories Inc.
17 A description of the mColiBlue24® test may be obtained from Hach Company.
18 Subject total coliform positive samples determined by 9222B-1997 or other membrane filter procedure to 9222G-1997 using NA-MUG media.
19 Method 1103.1:Escherichia coli(E. coli) in Water by Membrane Filtration Using membrane-ThermotolerantEscherichia coliAgar (mTEC), EPA-821-R-10-002. March 2010. US EPA.
20 Method 1603:Escherichia coli(E. coli) in Water by Membrane Filtration Using Modified membrane-ThermotolerantEscherichia coliAgar (Modified mTEC), EPA-821-R-09-007. December 2009. US EPA.
21 Preparation and use of MI agar with a standard membrane filter procedure is set forth in the article, Brenner et al. 1993. New Medium for the Simultaneous Detection of Total Coliform andEscherichia coliin Water. Appl. Environ. Microbiol. 59:3534-3544 and in Method 1604: Total Coliforms andEscherichia coli(E. coli) in Water by Membrane Filtration by Using a Simultaneous Detection Technique (MI Medium), EPA 821-R-02-024, September 2002, US EPA.
22 A description of the Enterolert® test may be obtained from IDEXX Laboratories Inc.
23 Method 1106.1: Enterococci in Water by Membrane Filtration Using membrane-Enterococcus-Esculin Iron Agar (mE-EIA), EPA-821-R-09-015. December 2009. US EPA.
24 Method 1600: Enterococci in Water by Membrane Filtration Using membrane-Enterococcus Indoxyl-β-D-Glucoside Agar (mEI), EPA-821-R-09-016. December 2009. US EPA.
25 Method 1622 uses a filtration, concentration, immunomagnetic separation of oocysts from captured material, immunofluorescence assay to determine concentrations, and confirmation through vital dye staining and differential interference contrast microscopy for the detection ofCryptosporidium.Method 1622:Cryptosporidiumin Water by Filtration/IMS/FA, EPA-821-R-05-001. December 2005. US EPA.
26 Method 1623 uses a filtration, concentration, immunomagnetic separation of oocysts and cysts from captured material, immunofluorescence assay to determine concentrations, and confirmation through vital dye staining and differential interference contrast microscopy for the simultaneous detection ofCryptosporidiumandGiardiaoocysts and cysts. Method 1623.CryptosporidiumandGiardiain Water by Filtration/IMS/FA. EPA-821-R-05-002. December 2005. US EPA
SECTION 15. NR 219.05 and 219.06 are renumbered NR 219.033 and NR 219.037.
SECTION 16. NR 233.40(2) is amended to read:
NR 233.40 (2) Except as provided in s. NR 219.05 219.033, the discharge parameter values required under the clean water act shall be determined by one of the analytical methods cited in Table 7. SECTION 17. EFFECTIVE DATE. This rule shall take effect on the first day of the month following publication in the Wisconsin administrative register as provided in s. 227.22 (2) (intro.), Stats. SECTION 18. BOARD ADOPTION. This rule was approved and adopted by the State of Wisconsin Natural Resources Board on April 9, 2014.
Dated at Madison, Wisconsin ______________________________.
STATE OF WISCONSIN
DEPARTMENT OF NATURAL RESOURCES
By ______________________________
Cathy Stepp, Secretary
(SEAL)
