Chapter NR 219

NR 219.037(3) (3) Bacteria tests in wastewater effluent and sludges,

NR 219.037(4) (4) pH,

NR 219.037(5) (5) Chlorine residual,

NR 219.037(6) (6) Specific conductance,

NR 219.037(7) (7) Physical properties of soils and sludges,

NR 219.037(8) (8) Nutrient tests of soils and sludges,

NR 219.037(9) (9) Flow measurements.

NR 219.037 History History: Cr. Register, April, 1986, No. 364, eff. 8-28-86; renum. from NR 219.07 and am. (intro.) Register, November, 1992, No. 443, eff. 7-1-93; am. Register February, 1996, No. 482, eff. 3-1-96; correction in (intro.) made under s. 13.93 (2m) (b) 6., Stats., Register November 2004 No. 587; CR 13-112: renum. from 219.06 Register May 2015 No. 713, eff. 6-1-15.

NR 219.04 NR 219.04 Identification of test procedures.

NR 219.04(1) (1)  Analytical test procedures. Parameters or pollutants, for which wastewater analytical methods are approved, are listed together with test procedure descriptions and references in tables A to H. Parameters or pollutants, for which sludge analytical methods are approved, are listed together with test procedure descriptions and references in table EM. The discharge values for the listed parameters shall be determined by one of the standard analytical test procedures identified in a table under this subsection or by an alternate test procedure established under ss. NR 219.033 and 149.42.

NR 219.04 Note Note: The laboratory performing the analyses on any samples will be certified for the applicable PFAS compounds in aqueous, sludge (biosolids), and tissue matrices in accordance with s. NR 149.41 by the Wisconsin Laboratory Certification Program established under s. 299.11, Stats. If the EPA Office of Water publishes a final approved 1600 series isotope dilution method for the analysis of PFAS in aqueous, sludge (biosolids), and tissue matrices, the department recommends use of the final approved EPA method.

NR 219.04(2) (2)  Sample preservation procedures. Sample preservation techniques, container materials, and maximum allowable holding times for parameters identified in tables A to H are prescribed in table F. Sludge samples shall be preserved at the time of collection by cooling to less than or equal to 6°C where required. All samples requiring thermal preservation at less than or equal to 6°C shall be cooled immediately after collection, and the required temperature maintained during shipping. Any person may apply for a variance from the prescribed preservation procedures applicable to samples taken from a specific discharge. Applications for variances may be made by letters to the regional administrator and shall provide sufficient data to assure that the variance does not adversely affect the integrity of the sample. The regional administrator will make a decision on whether to approve or deny a variance within 90 days of receipt of the application.

NR 219.04(3) (3)  Temperature reporting procedures. Samples cooled with ice packs or not in direct contact with ice during shipping shall be cooled to less than or equal to 6° C prior to shipping, and a temperature blank shall be submitted with the samples. Samples cooled during shipping with ice packs may not be recorded as received on ice. Samples may be recorded as received on ice only if solid ice is present in the cooler at the time the samples are received. If the samples are not received on ice, the laboratory shall record one of the following at the time of receipt:

NR 219.04(3)(a) (a) The temperature of an actual sample.

NR 219.04(3)(b) (b) The temperature of a temperature blank shipped with the samples.

NR 219.04(3)(c) (c) The temperature of the melt water in the shipping container.

NR 219.04(4) (4)  Incorporation by reference. The materials in this section are incorporated by reference for the purposes of the permit program under ch. 283, Stats.

NR 219.04 Note Note: Copies of the publications referenced in Tables A-H are available for inspection at the offices of the department of natural resources and the legislative reference bureau. Many of these materials are also available through inter-library loan.

NR 219.04 History History: Cr. Register, June, 1986, No. 366, eff. 7-1-86; r. and recr. Tables B and E, Register, April, 1988, No. 388, eff. 5-1-88; am.; r. and recr. Tables A to F, Register, November, 1992, No. 443, eff. 12-1-92; am. (1), am. Tables A to F, Register, April, 1994, No. 460, eff. 5-1-94; am. (1) and (2), Tables A to F, cr. (3), Register, February, 1996, No. 482, eff. 3-1-96; CR 02-019: am. Table B Register October 2002 No. 562, eff. 11-1-02; CR 04-033: r. and recr. Table A, Table B, Table BM, Table C, Table D, Table E, Table EM, and Table F, cr. Table ES Register November 2004 No. 587, eff. 12-1-04; CR 04-101: am. Table A Note 29 Register May 2005 No. 593, eff. 6-1-05; CR 08-076: am. (2) and (3) (intro.), cr. (4), r. and recr. Table A, B, C to EM and F Register May 2009 No. 641, eff. 6-1-09; correction to Table B Parameter No. 41 made under s. 13.92 (4) (b) 7., Stats., Register September 2009 No. 645; correction to Table B Parameter No. 15 made under s. 13.92 (4) (b) 7., Stats., Register April 2010 No. 652; CR 13-112: am. (1) and (2), r. and recr. Table A, B, r. Table BM, r. and recr. Table C to F, cr. Tables G and H, Register May 2015 No. 713, eff. 6-1-15; correction in Table C footnote 11 made under s. 13.92 (4) (b) 6., Stats., Register July 2015 No. 715, eff. 8-1-15; CR 19-014: r. and recr. Table A and Notes, am. Table EM, r. and recr. Table EM Notes 8, 11, cr. Table EM Notes 16 to 23, r. and recr. Table H and Notes Register April 2020 No. 772, eff. 5-1-20; correction in (2) made under s. 35.17, Stats., Register July 2020 No. 775; CR 17-046: am. (1) Register February 2021 No. 782, eff. 6-29-21; republished to correct an error in transcription in Table F Note 1 Register January 2022 No. 793; correction in (2), Table EM Note 1 made under s. 35.17, Stats., Register June 2022 No. 798; CR 21-083: am. Table F Register July 2022 No. 799, eff. 8-1-22; correction in Table EM Note 1 made under s. 35.17, Stats., Register July 2022 No. 799. - See PDF for table - See PDF for table

NR 219.04 Text 1 The method must be specified when results are reported.

NR 219.04 Text 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.

NR 219.04 Text 3 Microbiological Methods for Monitoring the Environment, Water, and Wastes, EPA/600/8-78/017. 1978. U.S. EPA.

NR 219.04 Text 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.

NR 219.04 Text 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.

NR 219.04 Text 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.

NR 219.04 Text 7 When the MF method has 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.

NR 219.04 Text 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.

NR 219.04 Text 9 Annual Book of ASTM Standards-Water and Environmental Technology, Section 11.02. 2000, 1999, 1996. ASTM International.

NR 219.04 Text 10 Official Methods of Analysis of AOAC International. 16th Edition, 4th Revision, 1998. AOAC International.

NR 219.04 Text 11 Recommended for enumeration of target organism in sewage sludge.

NR 219.04 Text 12 The multiple-tube fermentation test is used in 9221B.2-2014. 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.

NR 219.04 Text 13 These tests are collectively known as defined enzyme substrate tests.

NR 219.04 Text 14 After prior enrichment in a presumptive medium for total coliform using 9221B.2-2014, 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-2014. Commercially available EC-MUG media or EC media supplemented in the laboratory with 50 µg/mL of MUG may be used.

NR 219.04 Text 15 Method 1680: Fecal Coliforms in Sewage Sludge (Biosolids) by Multiple-Tube Fermentation Using Lauryl-Tryptose Broth (LTB) and EC Medium, EPA-821-R-14-009. September 2014. U.S. EPA.

NR 219.04 Text 16 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®, Quanti-Tray®/2000 and the MPN calculated from the table provided by the manufacturer.

NR 219.04 Text 17 Colilert-18® is an optimized formulation of the Colilert® for the determination of total coliforms and E. coli that 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.

NR 219.04 Text 18 Descriptions of the Colilert®, Colilert-18®, Quanti-Tray®, and Quanti-Tray®/2000 may be obtained from IDEXX Laboratories, Inc.

NR 219.04 Text 19 A description of the mColiBlue24® test, is available from Hach Company.

NR 219.04 Text 20 Method 1681: Fecal Coliforms in Sewage Sludge (Biosolids) by Multiple-Tube Fermentation using A-1 Medium, EPA-821-R-06-013. July 2006. U.S. EPA.

NR 219.04 Text 21 Method 1603: Escherichia coli (E. coli) in Water by Membrane Filtration Using Modified Membrane-Thermotolerant Escherichia coli Agar (modified mTEC), EPA-821-R-14-010. September 2014. U.S. EPA.

NR 219.04 Text 22 Method 1682: Salmonella in Sewage Sludge (Biosolids) by Modified Semisolid Rappaport-Vassiliadis (MSRV) Medium, EPA-821-R-14-012. September 2014. U.S. EPA.

NR 219.04 Text 23 A description of the Enterolert® test may be obtained from IDEXX Laboratories Inc.

NR 219.04 Text 24 Method 1600: Enterococci in Water by Membrane Filtration Using membrane-Enterococcus Indoxyl-b-D-Glucoside Agar (mEI), EPA-821-R-14-011. September 2014. U.S. EPA.

NR 219.04 Text 25 Standard Methods for the Examination of Water and Wastewater, Joint Editorial Board, American Public Health Association, American Water Works Association, and Water Pollution Control Federation, 23rd Edition (2017), 22nd Edition (2012), 21st Edition (2005), 20th Edition (1998), 19th Edition (1995), and 18th Edition (1992).

NR 219.04 Text 26 Standard Methods for the Analysis of Water and Wastewater. With the promulgation of Federal Register /Vol. 77, No. 97 / Friday, May 18, 2012, the EPA lists only the most recently EPA-approved version of a Standard Method (regardless of the printed or online edition) in 40 CFR Part 136, with few exceptions, to identify the method with the year of Standard Methods approval or adoption designated by the last four digits in the method number (e.g., Standard Method 3113B–2004). This approach clearly identifies the version of the standard method approved under Part 136 and no longer ties it to a particular compendium printing or edition of Standard Methods. Methods can be purchased at www.standardmethods.org.

NR 219.04 Text 27 Compliance monitoring must be performed in accordance with the specifications in the “ State of Wisconsin Aquatic Life Toxicity Testing Methods Manual, 2nd Edition,” Wisconsin Department of Natural Resources, 2004. This publication is available for inspection at the offices of the Department of Natural Resources and the Legislative Reference Bureau. Copies are available from the Department of Natural Resources, Bureau of Science Services, P.O. Box 7921, Madison, WI 53707.

NR 219.04 Text 28 To use Colilert-18® to assay for fecal coliforms, the incubation temperature is 44.5 ± 0.2 °C, and a water bath incubator is used.

NR 219.04 Text 29 On a monthly basis, at least ten blue colonies from positive samples must be verified using lauryl tryptose broth and EC broth, followed by count adjustment based on these results; and representative non-blue colonies should be verified using lauryl tryptose broth. Where possible, verifications should be done from randomized sample sources.

NR 219.04 Text 30 On a monthly basis, at least ten sheen colonies from positive samples must be verified using lauryl tryptose broth and brilliant green lactose bile broth, followed by count adjustment based on these results; and representative non-sheen colonies should be verified using lauryl tryptose broth. Where possible, verifications should be done from randomized sample sources.

NR 219.04 Text 31 Subject coliform positive samples determined by 9222 B-2015 or other membrane filter procedure to 9222 I-2015 using NA-MUG media.

NR 219.04 Text 32 Verification of colonies by incubation of BHI agar at 10 ± 0.5 °C for 48 ± 3 h is optional. As per the Errata to the 23rd Edition of Standard Methods for the Examination of Water and Wastewater, “Growth on a BHI agar plate incubated at 10 ± 0.5 °C for 48 ± 3 h is further verification that the colony belongs to the genus Enterococcus.”

NR 219.04 Text 33 9221 F. 2-2014: This procedure allows for simultaneous detection of E. coli and thermotolerant coliforms by adding inverted vials to EC-MUG; the inverted vials collect gas produced by thermotolerant coliforms. - See PDF for table

NR 219.04 Text 1 Methods for Chemical Analysis of Water and Wastes, EPA-600/4-79-020. Revised March 1983 and 1979, where applicable. U.S. EPA. Available from: National Technical Information Service, 5285 Port Royal Road, Springfield, Virginia 22161.

NR 219.04 Text 2 Methods for Analysis of Inorganic Substances in Water and Fluvial Sediments, Techniques of Water-Resource Investigations of the U.S. Geological Survey, Book 5, Chapter A1., unless otherwise stated. 1989. USGS.

NR 219.04 Text 3 Official Methods of Analysis of the Association of Official Analytical Chemists, Methods Manual, Sixteenth Edition, 4th Revision, 1998. AOAC International.

NR 219.04 Text 4 For the determination of total metals (which are equivalent to total recoverable metals) the sample is not filtered before processing. A digestion procedure is required to solubilize analytes in suspended material and to break down organic-metal complexes (to convert the analyte to a detectable form for colorimetric analysis).

NR 219.04 Text For non-platform graphite furnace atomic absorption determinations a digestion using nitric acid (as specified in Section 4.1.3 of Methods for the Chemical Analysis of Water and Wastes) is required prior to analysis. The procedure used should subject the sample to gentle, acid refluxing and at no time should the sample be taken to dryness.

NR 219.04 Text For direct aspiration flame atomic absorption determinations (FLAA) a combination acid (nitric and hydrochloric acids) digestion is preferred prior to analysis. The approved total recoverable digestion is described as Method 200.2 in Supplement I of “Methods for the Determination of Metals in Environmental Samples" EPA/600R-94/111, May, 1994, and is reproduced in EPA Methods 200.7, 200.8, and 200.9 from the same Supplement. However, when using the gaseous hydride technique or for the determination of certain elements such as antimony, arsenic, selenium, silver, and tin by non-EPA graphite furnace atomic absorption methods, mercury by cold vapor atomic absorption, the noble metals and titanium by FLAA, a specific or modified sample digestion procedure may be required and in all cases the referenced method write-up should be consulted for specific instruction and/or cautions.

NR 219.04 Text For analyses using inductively coupled plasma-atomic emission spectrometry (ICP-AES), the direct current plasma (DCP) technique or the EPA spectrochemical techniques (platform furnace AA, ICP-AES, and ICP-MS) use EPA Method 200.2 or an approved alternate procedure (e.g., CEM microwave digestion, which may be used with certain analytes as indicated in Table IB); the total recoverable digestion procedures in EPA Methods 200.7, 200.8, and 200.9 may be used for those respective methods. Regardless of the digestion procedure, the results of the analysis after digestion procedure are reported as “total" metals.

NR 219.04 Text 5 Copper sulfate or other catalysts that have been found suitable may be used in place of mercuric sulfate.

NR 219.04 Text 6 Manual distillation is not required if comparability data on representative effluent samples are on file to show that this preliminary distillation step is not necessary: however, manual distillation will be required to resolve any controversies. In general, the analytical method should be consulted regarding the need for distillation. If the method is not clear, the laboratory may compare a minimum of 9 different sample matrices to evaluate the need for distillation. For each matrix, a matrix spike and matrix spike duplicate are analyzed both with and without the distillation step. (A total of 36 samples, assuming 9 matrices). If results are comparable, the laboratory may dispense with the distillation step for future analysis. Comparable is defined as < 20% RPD for all tested matrices). Alternatively the two populations of spike recovery percentages may be compared using a recognized statistical test.

NR 219.04 Text 7 Industrial Method Number 379-75 WE Ammonia, Automated Electrode Method, Technicon Auto Analyzer II. February 19, 1976. Bran & Luebbe Analyzing Technologies Inc.

NR 219.04 Text 8 The approved method is that cited in Methods for Determination of Inorganic Substances in Water and Fluvial Sediments, Techniques of Water-Resources Investigations of the U.S. Geological Survey, Book 5, Chapter A1. 1979. USGS.

NR 219.04 Text 9 American National Standard on Photographic Processing Effluents. April 2, 1975. American National Standards Institute (ANSI), 25 West 43rd St., New York, NY 10036.

NR 219.04 Text 10 In-Situ Method 1003-8-2009, Biochemical Oxygen Demand (BOD) Measurement by Optical Probe. 2009. In-Situ Incorporated.

NR 219.04 Text 11 The use of normal and differential pulse voltage ramps to increase sensitivity and resolution is acceptable.

NR 219.04 Text 12 Carbonaceous biochemical oxygen demand (CBOD5) must not be confused with the traditional BOD5test method which measures “total BOD." The addition of the nitrification inhibitor is not a procedural option, but must be included to report the CBOD5parameter. A discharger whose permit requires reporting the traditional BOD5may not use a nitrification inhibitor in the procedure for reporting the results. Only when a discharger's permit specifically states CBOD5is required can the permittee report data using a nitrification inhibitor.

NR 219.04 Text 13 OIC Chemical Oxygen Demand Method. 1978. Oceanography International Corporation. 512 West Loop, P.O. Box 2980, College Station, TX 77840.

NR 219.04 Text 14 Method 8000, Chemical Oxygen Demand, Hach Handbook of Water Analysis, 1979. Hach Company. P.O. Box 389, Loveland, CO 80537. Available on-line at http:/www.hach.com.

NR 219.04 Text 15 The back titration method will be used to resolve controversy.

NR 219.04 Text 16 Orion Research Instruction Manual, Residual Chlorine Electrode Model 97-70. Thermo Scientific, 81 Wyman Street, Waltham, MA 02454. 1977. Orion Research Incorporated. The calibration for the Orion residual chlorine method must be derived using at least three standard solutions, prepared from a 0.00281 N potassium iodate solution.

NR 219.04 Text 17 Method 245.7, Mercury in Water by Cold Vapor Atomic Fluorescence Spectrometry, EPA-821-R-05-001. Revision 2.0, February 2005. US EPA., available from the U.S. EPA Sample Control Center (operated by CSC), 6101 Stevenson Avenue, Alexandria, VA 22304.

NR 219.04 Text 18 National Council of the Paper Industry for Air and Stream Improvement (NCASI) Technical Bulletin 253, December 1971.

NR 219.04 Text 19 Method 8506, Biocinchoninate Method for Copper, Hach Handbook of Water Analysis. 1979. Hach Company. P.O. Box 389, Loveland, CO 80537. Available on-line at http:/www.hach.com.

NR 219.04 Text 20 When using a method with block digestion, this treatment is not required.

NR 219.04 Text 21 Industrial Method Number 378-75WA, Hydrogen ion (pH) Automated Electrode Method, Bran & Luebbe (Technicon) Autoanalyzer II. October 1976. Bran & Luebbe Analyzing Technologies. Elmsford, NY 10523.

NR 219.04 Text 22 Method 8008, 1,10-Phenanthroline Method using FerroVer Iron Reagent for Water. 1980. Hach Company P.O. Box 389, Loveland, CO 80537. Available on-line at http:/www.hach.com.

NR 219.04 Text 23 Method 8034, Periodate Oxidation Method for Manganese, Hach Handbook of Wastewater Analysis. 1979. Hach Company Loveland, CO 80537. Available on-line at http:/www.hach.com.

NR 219.04 Text 24 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, (1972 Revised 1987) p. 14. 1987. USGS. Available from: U.S. Geological Surve y, 604 S. Pickett Street, Alexandria, VA 22304.

NR 219.04 Text 25 Method 8507, Nitrogen, Nitrite-Low Range, Diazotization Method for Water and Wastewater. 1979. Hach Company P.O. Box 389, Loveland, CO 80537. Available on-line at http:/www.hach.com.

NR 219.04 Text 26 Just prior to distillation, adjust the sulfuric-acid-preserved sample to pH 4 with 1 + 9 NaOH.

NR 219.04 Text 27 The colorimetric reaction must be conducted at a pH of 10.0 ± 0.2.

NR 219.04 Text 28 Addison, R.F., and R.G. Ackman. 1970. Direct Determination of Elemental Phosphorus by Gas-Liquid Chromatography, Journal of Chromatography, 47(3):421-426. 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.

NR 219.04 Text 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 Na 2S2O3 and NaOH. Standards should be prepared in the same manner. For levels of silver below 1 mg/L the approved method is satisfactory.

NR 219.04 Text 30 The use of EDTA decreases method sensitivity. Analysts may omit EDTA or replace with another suitable complexing reagent provided that all method specified quality control acceptance criteria are met.

NR 219.04 Text 31 For samples known or suspected to contain high levels of silver (e.g., in excess of 4 mg/L), cyanogen iodide should be used to keep the silver in solution for analysis. Prepare a cyanogen iodide solution by adding 4.0 mL of concentrated NH4OH, 6.5 g of KCN, and 5.0 mL of a 1.0 N solution of I2 to 50 mL of reagent water in a volumetric flask and dilute to 100.0 mL. After digestion of the sample, adjust the pH of the digestate to >7 to prevent the formation of HCN under acidic conditions. Add 1 mL of the cyanogen iodide solution to the sample digestate and adjust the volume to 100 mL with reagent water (NOT acid). If cyanogen iodide is added to sample digestates, then silver standards must be prepared that contain cyanogen iodide as well. Prepare working standards by diluting a small volume of a silver stock solution with water and adjusting the pH>7 with NH4OH. Add 1 mL of the cyanogen iodide solution and let stand 1 hour. Transfer to a 100-mL volumetric flask and dilute to volume with water.

NR 219.04 Text 32 “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. USGS. Available from: U.S. Geological Survey, 604 S. Pickett Street, Alexandria, VA 22304.

NR 219.04 Text 33 Method 8009, Zincon Method for Zinc, Hach Handbook of Water Analysis, 1979. Hach Company. Loveland, CO 80537. Available on-line at http:/www.hach.com.

NR 219.04 Text 34 Method AES0029, Direct Current Plasma (DCP) Optical Emission Spectrometric Method for Trace Elemental Analysis of Water and Wastes. 1986-Revised 1991. Thermo Jarrell Ash Corporation. Available from: Thermo Scientific, 81 Wyman Street, Waltham, MA 02454.