Chapter NR 219

NR 219.04 Text 56 QuikChem Method 10-204-00-1-X, Digestion and Distillation of Total Cyanide in Drinking and Wastewaters using MICRO DIST and Determination of Cyanide by Flow Injection Analysis. Revision 2.2, March 2005. Lachat Instruments. Available from Hach Company, P.O. Box 389, Loveland, CO 80537.

NR 219.04 Text 57 When using sulfide removal test procedures described in EPA Method 335.4-1, reconstitute particulate that is filtered with the sample prior to distillation.

NR 219.04 Text 58 Unless otherwise stated, if the language of this table specifies a sample digestion and/or distillation “followed by" analysis with a method, approved digestion and/or distillation are required prior to analysis.

NR 219.04 Text 59 Samples analyzed for available cyanide using OI Analytical method OIA-1677-09 or ASTM method D6888-09 that contain particulate matter may be filtered only after the ligand exchange reagents have been added to the samples, because the ligand exchange process converts complexes containing available cyanide to free cyanide, which is not removed by filtration. Analysts are further cautioned to limit the time between the addition of the ligand exchange reagents and sample filtration to no more than 30 minutes to preclude settling of materials in samples.

NR 219.04 Text 60 Analysts should be aware that pH optima and chromophore absorption maxima might differ when phenol is replaced by a substituted phenol as the color reagent in Berthelot Reaction (“phenol-hypochlorite reaction") colorimetric ammonium determination methods. For example when phenol is used as the color reagent, pH optimum and wavelength of maximum absorbance are about 11.5 and 635 nm, respectively—see, Patton, C.J. and S.R. Crouch. March 1977. Anal. Chem. 49:464-469. These reaction parameters increase to pH > 12.6 and 665 nm when salicylate is used as the color reagent—see, Krom, M.D. April 1980. The Analyst 105:305-316.

NR 219.04 Text 61 If atomic absorption or ICP instrumentation is not available, the aluminon colorimetric method detailed in the 19th Edition of Standard Methods may be used. This method has poorer precision and bias than the methods of choice.

NR 219.04 Text 62 Easy (1-Reagent) Nitrate Method, Revision November 12, 2011. Craig Chinchilla.

NR 219.04 Text 63 Hach Method 10360, Luminescence Measurement of Dissolved Oxygen in Water and Wastewater and for Use in the Determination of BOD5 and cBOD5. Revision 1.2, October 2011. Hach Company. This method may be used to measure dissolved oxygen when performing the methods approved in Table IB for measurement of biochemical oxygen demand (BOD) and carbonaceous biochemical oxygen demand (CBOD).

NR 219.04 Text 64 In-Situ Method 1002-8-2009, Dissolved Oxygen (DO) Measurement by Optical Probe. 2009. In-Situ Incorporated.

NR 219.04 Text 65 Mitchell Method M5331, Determination of Turbidity by Nephelometry. Revision 1.0, July 31, 2008. Leck Mitchell.

NR 219.04 Text 66 Mitchell Method M5271, Determination of Turbidity by Nephelometry. Revision 1.0, July 31, 2008. Leck Mitchell.

NR 219.04 Text 67 Orion Method AQ4500, Determination of Turbidity by Nephelometry. Revision 5, March 12, 2009. Thermo Scientific.

NR 219.04 Text 68 EPA Method 200.5, Determination of Trace Elements in Drinking Water by Axially Viewed Inductively Coupled Plasma-Atomic Emission Spectrometry, EPA/600/R-06/115. Revision 4.2, October 2003. US EPA.

NR 219.04 Text 69 Method 1627, Kinetic Test Method for the Prediction of Mine Drainage Quality, EPA-821-R-09-002. December 2011. US EPA.

NR 219.04 Text 70 Techniques and Methods Book 5-B1, Determination of Elements in Natural-Water, Biota, Sediment and Soil Samples Using Collision/Reaction Cell Inductively Coupled Plasma-Mass Spectrometry, Chapter 1, Section B, Methods of the National Water Quality Laboratory, Book 5, Laboratory Analysis, 2006. USGS.

NR 219.04 Text 71 Water-Resources Investigations Report 01-4132, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory—Determination of Organic Plus Inorganic Mercury in Filtered and Unfiltered Natural Water With Cold Vapor-Atomic Fluorescence Spectrometry, 2001. USGS.

NR 219.04 Text 72 Quality control requirements for low level mercury are found in s. NR 106.145 (9) and (10), Wis. Adm. Code. Low-level mercury methods are performance based so some method modifications are allowable, provided quality control requirements are met. If an atomic absorption detector is substituted for atomic fluorescence detector, the appropriate method citation is 245.1 (manual) or 245.2 (automated). If method 1631E is modified to eliminate the purge and trap step, the appropriate method citation is 245.7.

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NR 219.04 Text 1 All parameters are expressed in micrograms per liter (µg/L) except for Method 1613B, in which the parameters are expressed in picograms per liter (pg/L).

NR 219.04 Text 2 The full text of Methods 601-613, 624, 625, 1613B, 1624B, and 1625B are provided at Appendix A, Test Procedures for Analysis of Organic Pollutants, of 40 CFR Part 136. The standardized test procedure to be used to determine the method detection limit (MDL) for these test procedures is given at 40 CFR Part136, Appendix B, Definition and Procedure for the Determination of the Method Detection Limit.

NR 219.04 Text 3 Methods for Benzidine: Chlorinated Organic Compounds, Pentachlorophenol and Pesticides in Water and Wastewater. September 1978. U.S. EPA.

NR 219.04 Text 4 Method 624 may be used for quantitative determination of acrolein and acrylonitrile, provided that the laboratory has documentation to substantiate the ability to detect and quantify these analytes at levels necessary to comply with any associated regulations. In addition, the use of sample introduction techniques other than simple purge-and-trap may be required. QC acceptance criteria from Method 603 should be used when analyzing samples for acrolein and acrylonitrile in the absence of such criteria in Method 624.

NR 219.04 Text 5 Method 625 may be extended to include benzidine, hexachlorocyclopentadiene, N-nitrosodimethylamine, N-nitrosodi-n-propylamine, and N-nitrosodiphenylamine. However, when they are known to be present, Methods 605, 607, and 612, or Method 1625B, are preferred methods for these compounds.

NR 219.04 Text 5a Method 625, screening only.

NR 219.04 Text 6 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. American Public Health Association (APHA).

NR 219.04 Text 7 Each analyst must make an initial, one-time demonstration of their ability to generate acceptable precision and accuracy with Methods 601-603, 624, 625, 1624B, and 1625B in accordance with procedures each in Section 8.2 of each of these Methods. Additionally, each laboratory, on an on-going basis must spike and analyze 10% (5% for Methods 624 and 625 and 100% for methods 1624B and 1625B) of all samples to monitor and evaluate laboratory data quality in accordance with Sections 8.3 and 8.4 of these methods. When the recovery of any parameter falls outside the warning limits, the analytical results for that parameter in the unspiked sample are suspect. The results should be reported, but cannot be used to demonstrate regulatory compliance. These quality control requirements also apply to the Standard Methods, ASTM Methods, and other methods cited.

NR 219.04 Text 8 Organochlorine Pesticides and PCBs in Wastewater Using EmporeTMDisk. Revised October 28, 1994. 3M Corporation.

NR 219.04 Text 9 Method O-3116-87 is in Open File Report 93-125, Methods of Analysis by U.S. Geological Survey National Water Quality Laboratory—Determination of Inorganic and Organic Constituents in Water and Fluvial Sediments. 1993. USGS.

NR 219.04 Text 10 Analysts may use Fluid Management Systems, Inc. Power-Prep system in place of manual cleanup provided the analyst meets the requirements of Method 1613B (as specified in Section 9 of the method) and permitting authorities. Method 1613, Revision B, Tetra- through Octa-Chlorinated Dioxins and Furans by Isotope Dilution HRGC/HRMS. Revision B, 1994. U.S. EPA. The full text of this method is provided in Appendix A to 40 CFR Part 136 and at http://water.epa.gov/scitech/methods/cwa/index.cfm.

NR 219.04 Text 11 Method 1650, Adsorbable Organic Halides by Adsorption and Coulometric Titration. Revision C, 1997. U.S. EPA. Method 1653, Chlorinated Phenolics in Wastewater by In Situ Acetylation and GCMS. Revision A, 1997. U.S. EPA. The full text for both of these methods is provided at Appendix A, “Methods 1650 and 1653", in Part 430, The Pulp, Paper, and Paperboard Point Source Category. Also available on-line at http:/www.gpo.gov/.

NR 219.04 Text 12 EPA Method 1668A may be used to test for all PCB congeners. If this method is employed, all PCB congeners shall be delineated. Non-detects shall be treated as zero. The values that are between the limit of detection and the limit of quantitation shall be used when calculating the total value of all congeners. All results shall be added together and the total PCB concentration reported. It is recognized a number of congeners will co-elute with others, so there will not be 209 results to sum.

NR 219.04 Text 13 If congener specific analysis is performed, the list of congeners tested shall include at least congener numbers 5, 18, 31, 44, 52, 66, 87, 101, 110, 138, 141, 151, 153, 170, 180, 183, 187, and 206 plus any other additional congeners which might be reasonably expected to occur in the particular sample. If Aroclor analysis is performed, clean up steps of the extract shall be performed as necessary to remove interference. If congener specific analysis is done, clean up steps of the extract shall be performed as necessary to remove interference. If desired limits of detection cannot be achieved after using the appropriate clean up techniques, a reporting limit that is achievable for the Aroclors or each congener for sample shall be determined. This report limit should be reported and qualified indicating the presence of an interference. The laboratory conducting the analysis shall perform as many the following methods as necessary to remove interference:

NR 219.04 Text Florisil, Gel Permeation, Silica Gel, Alumina, Sulfur Clean Up, Sulfuric Acid Clean Up.

NR 219.04 Text 14 “Method 1668A, Revision A: Chlorinated Biphenyl Congeners in Wate r, Soil, Sediment, and Tissue by HRGC/HRMS", EPA-821-R-00-002, Environmental Protection Agency, Office of Water, Washington, D.C., December 1999. Available from: the National Technical Information Service, 5285 Port Royal Road, Springfield, Vi rginia 22161.

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NR 219.04 Text 1 Pesticides are listed in this table by common name for the convenience of the reader. Additional pesticides may be found under Table C, where entries are listed by chemical name.

NR 219.04 Text 2 The standardized test procedure to be used to determine the method detection limit (MDL) for these test procedures is given at 40 CFR Part 136, Appendix B, Definition and Procedure for the Determination of the Method Detection Limit.

NR 219.04 Text 3 Methods for Benzidine, Chlorinated Organic Compounds, Pentachlorophenol and Pesticides in Water and Wastewater. September 1978. U.S. EPA. This EPA publication includes thin-layer chromatography (TLC) methods.

NR 219.04 Text 4 Methods for the Determination of Organic Substances in Water and Fluvial Sediments, Techniques of Water-Resources Investigations of the U.S. Geological Survey, Book 5, Chapter A3. 1987. USGS.

NR 219.04 Text 5 The method may be extended to include á-BHC, ã-BHC, endosulfan I, endosulfan II, and endrin. However, when they are known to exist, Method 608 is the preferred method.

NR 219.04 Text 6 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. American Public Health Association (APHA).

NR 219.04 Text 7 Each analyst must make an initial, one-time, demonstration of their ability to generate acceptable precision and accuracy with Methods 608 and 625 in accordance with procedures given in Section 8.2 of each of these methods. Additionally, each laboratory, on an on-going basis, must spike and analyze 10% of all samples analyzed with Method 608 or 5% of all samples analyzed with Method 625 to monitor and evaluate laboratory data quality in accordance with Sections 8.3 and 8.4 of these methods. When the recovery of any parameter falls outside the warning limits, the analytical results for that parameter in the unspiked sample are suspect. The results should be reported, but cannot be used to demonstrate regulatory compliance. These quality control requirements also apply to the Standard Methods, ASTM Methods, and other methods cited.

NR 219.04 Text 8 Organochlorine Pesticides and PCBs in Wastewater Using Empore TM Disk. Revised October 28, 1994. 3M Corporation.

NR 219.04 Text 9 Method O-3106-93 is in Open File Report 94-37, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory—Determination of Triazine and Other Nitrogen-Containing Compounds by Gas Chromatography With Nitrogen Phosphorus Detectors. 1994. USGS.

NR 219.04 Text 10 EPA Methods 608.1, 608.2, 614, 614.1, 615, 617, 619, 622, 622.1, 627, and 632 are found in Methods for the Determination of Nonconventional Pesticides in Municipal and Industrial Wastewater, EPA 821-R-92-002, April 1992, U.S. EPA.

NR 219.04 Text The full text of Methods 608 and 625 are provided at 40 CFR Part 136, Appendix A, Test Procedures for Analysis of Organic Pollutants.

NR 219.04 Text EPA Methods 505, 507, 508, 525.1, 531.1 and 553 are in Methods for the Determination of Nonconventional Pesticides in Municipal and Industrial Wastewater, Volume II, EPA 821-R-93-010B, 1993, U.S. EPA.

NR 219.04 Text EPA Method 525.2 is in Determination of Organic Compounds in Drinking Water by Liquid-Solid Extraction and Capillary Column Gas Chromatography/Mass Spectrometry, Revision 2.0, 1995, U.S. EPA.

NR 219.04 Text EPA methods 1656 and 1657 are in Methods For The Determination of Nonconventional Pesticides In Municipal and Industrial Wastewater, Volume I, EPA 821-R-93-010A, 1993, U.S. EPA.

NR 219.04 Text 11 Method O-1126-95 is in Open-File Report 95-181, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory—Determination of pesticides in water by C-18 solid-phase extraction and capillary-column gas chromatography/mass spectrometry with selected-ion monitoring. 1995. USGS.

NR 219.04 Text 12 Method O-2060-01 is in Water-Resources Investigations Report 01-4134, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory—Determination of Pesticides in Water by Graphitized Carbon-Based Solid-Phase Extraction and High-Performance Liquid Chromatography/Mass Spectrometry. 2001. USGS.

NR 219.04 Text 13 Method O-2002-01 is in Water-Resources Investigations Report 01-4098, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory—Determination of moderate-use pesticides in water by C-18 solid-phase extraction and capillary-column gas chromatography/mass spectrometry. 2001. USGS.

NR 219.04 Text 14 Method O-1121-91 is in Open-File Report 91-519, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory—Determination of organonitrogen herbicides in water by solid-phase extraction and capillary-column gas chromatography/mass spectrometry with selected-ion monitoring. 1992. USGS. - See PDF for table

NR 219.04 Text 1 Prescribed Procedures for Measurement of Radioactivity in Drinking Water, EPA-600/4-80-032 (1980), U.S. Environmental Protection Agency, August 1980.

NR 219.04 Text 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).

NR 219.04 Text 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."

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NR 219.04 Text 1 “Test Methods for Evaluating Solid Waste, Physical/Chemical Methods," SW–846, Environmental Protection Agency, Office of Solid Waste and Emergency Response, 401 M Street, S.W., Washington D.C. 20460, September 1986 (Third edition), including July 1992 (Update I), September 1994 (Update II), August 1993 (Update IIA), January 1995 (Update IIB), December 1996 (Update III), April 1998 (Update IIIA), November 2004 (Update IIIB), February 2007 (Update IV) updates. Available from: The Superintendent of Documents, U.S. Government Printing Office, Room 190, Federal Building, P.O. Box 371954, Pittsburgh, PA 15250–7954. Available online at https://www.epa.gov/hw-sw846/sw-846-compendium.

NR 219.04 Text 2 If an alternative digestion procedure is specified in the analytical method, the digestion in this table shall be used. In all cases, consult the analytical method for special requirements and cautions. SW–846 method 3051A is an acceptable alternate digestion procedure to SW–846 method 3050B.

NR 219.04 Text 3 “Methods for the Determination of Metals in Environmental Samples", EPA-600/4-91-010, Environmental Protection Agency, Environmental Monitoring Systems Laboratory, Cincinnati, OH 45268, June 1991. Available from: the National Technical Information Service (NTIS), 5258 Port Royal Road, Springfield, Virginia 22161.

NR 219.04 Text 4 “Sample Preparation Procedure for Spectrochemical Determination of Total Recoverable Elements", Method 200.2, Revision 2.8, Environmental Protection Agency, Environmental Monitoring Systems Laboratory, Cincinnati, OH 45268, 1994. Available from: the National Technical Information Service (NTIS), 5258 Port Royal Road, Springfield, Virginia 22161.

NR 219.04 Text 5 High levels of chromium, copper, mercury, silver, cobalt, or molybdenum may interfere with the analysis. Consult Method 3 114, of “Standard Methods for the Examination of Water and Wastewater", 18th, 19th, 20th, or 21st edition, for more information.

NR 219.04 Text 6 Concentrations of lead in municipal sludge may exceed the working range of graphite furnace.

NR 219.04 Text 7 1993 Annual Book of ASTM Standards, Section 11.02, Water and Environmental Technology", American Society for Testing and Materials, 1993, 1916 Race Street, Philadelphia, PA 19103. Available from: the American Society for Testing and Materials, 1916 Race Street, Philadelphia, PA 19103.

NR 219.04 Text 8 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), 21 st Edition (2005), 20th Edition (1998), 19th Edition (1995), and 18th Edition (1992).

NR 219.04 Text 9 “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, 2006. On-line subscription service available at http:/www.standardmethods.org.

NR 219.04 Text 10 “Occurrence of Pathogens in Distribution and Marketing Municipal Sludges", EPA 600/1–87–014, Environmental Protection Agency, 1987. Available from: the National Technical Information Service, order # PB 88–154273/AS, 5285 Port Royal Road, Springfield, Virginia 22161.

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

NR 219.04 Text 12 Analysts may use Fluid Management Systems, Inc. PowerPrep system in place of manual cleanup provided that the analysis meet the requirements of Method 1613B (as specified in Section 9 of the method) and permitting authorities.

NR 219.04 Text 13 EPA Method 1668A may be used to test for all PCB congeners. If this method is employed, all PCB congeners shall be delineated. Non-detects shall be treated as zero. The values that are between the limit of detection and the limit of quantitation shall be used when calculating the total value of all congeners. All results shall be added together and the total PCB concentration by dry weight reported. It is recognized that a number of the congeners will co-elute with others, so there will not be 209 results to sum.

NR 219.04 Text 14 EPA Method 8082A shall be used for PCB-Aroclor analysis and may be used for congener specific analysis as well. If congener specific analysis is performed using Method 8082A, the list of congeners tested shall include at least congener numbers 5, 18, 31, 44, 52, 66, 87, 101, 110, 138, 141, 151, 153, 170, 180, 183, 187, and 206 plus any other additional congeners which might be reasonably expected to occur in the particular sample. For either type of analysis, the sample shall be extracted using Soxhlet extraction Method 3540C or Pressurized Fluid Extraction Method 3545A. If Aroclor analysis is performed using Method 8082A, clean up steps of the extract shall be performed as necessary to remove interference and achieve as close to a limit of detection of 0.11 mg/kg as possible. If congener specific analysis is done using Method 8082A, clean up steps of the extract shall be performed as necessary to remove interference and to achieve as close to a limit of detection of 0.003 mg/kg as possible for each congener. If the aforementioned limits of detection cannot be achieved after using the appropriate clean up techniques, a reporting limit that is achievable for the Aroclors or each congener for sample shall be determined. This report limit should be reported and qualified indicating the presence of an interference. The laboratory conducting the analysis shall perform as many the following methods as necessary to remove interference:

NR 219.04 Text 3620C - Florisil

NR 219.04 Text 3640A – Gel Permeation

NR 219.04 Text 3630C - Silica Gel

NR 219.04 Text 3611B - Alumina

NR 219.04 Text 3660B - Sulfur Clean Up

NR 219.04 Text 3665A – Sulfuric Acid Clean Up.

NR 219.04 Text 15 “Method 1668A, Revision A: Chlorinated Biphenyl Congeners in Wate r, Soil, Sediment, and Tissue by HRGC/HRMS", EPA-821-R-00-002, Environmental Protection Agency, Office of Water, Washington, D.C., December 1999. Available from: the National Technical Information Service, 5285 Port Royal Road, Springfield, Vi rginia 22161.

NR 219.04 Text 16 Microbiological Methods for Monitoring the Environment, Water, and Wastes, EPA/600/8-78/017. 1978. U.S. EPA.

NR 219.04 Text 17 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 18 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 19 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 20 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 21 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 22 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.