Wisconsin Legislature: NR 219.04 Text

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.

- See PDF for table

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 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 TextThe 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.

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NR 219.04 Text 1 For compounds that also appear in Table C, test methods listed in Table C may also be used.

NR 219.04 Text 2 EPA Methods 1666, 1667, and 1671 listed in the table above are published in the compendium titled Analytical Methods for the Determination of Pollutants in Pharmaceutical Manufacturing Industry Wastewaters (EPA 821-B-98-016).

NR 219.04 Text EPA Methods 502.2 and 524.2 have been incorporated by reference into 40 CFR 141.24 and are in Methods for the Determination of Organic Compounds in Drinking Water, EPA-600/4-88-039, December 1988, Revised, July 1991, and Methods for the Determination of Organic Compounds in Drinking Water-Supplement II, E PA-600/R-92-129, August 1992, respectively. These EPA test method compendia are available from the National Technical Information Service, NTIS PB91-231480 and PB92-207703, U.S. Department of Commerce, 5285 Port Royal Road, Springfield, Virginia 22161. The toll-free number is 800-553-6847. ASTM test methods D3371, D3695, and D4763 are available from the American Society for Testing and Materials, 100 Barr Harbor Drive, West Conshohocken, PA 19428-2959.

NR 219.04 Text 3 1624C: m-xylene 108-38-3, o,p-xylene E-14095 (Not a CAS number; this is the number provided in the Environmental Monitoring Methods Index (EMMI) database.); 1666: m,p-xylene 136777-61-2, o-xylene 95-47-6 - See PDF for table

NR 219.04 Text 1 “P" is for polyethylene; “FP" is fluoropolymer (polytetrafluoroethylene (PTFE); Teflon®), or other fluoropolymer, unless stated otherwise in this Table F; “G" is glass; “PA" is any plastic that is made of a sterilizable material (polypropylene or other autoclavable plastic); “ LDPE" is low density polyethylene; “HDPE” is high density polyethylene; “PE” is polyethylene; “PP” is polypropylene.

NR 219.04 Text 2 Except where noted in this table and the method for the parameter, preserve each grab sample within 15 minutes of collection. For a composite sample collected with an automated sample (e.g., using a 24-hour composite sampler, refrigerate the sample at ≤ 6 °C during collection unless specified otherwise in this table or in the method(s). For a composite sample to be split into separate aliquots for preservation and/or analysis, maintain the sample at ≤ 6 °C, unless specified otherwise in this table or in the method(s), until collection, splitting, and preservation is completed. Add the preservative to the sample container prior to sample collection when the preservative will not compromise the integrity of a grab sample, a composite sample, or aliquot split from a composite sample within 15 minutes of collection.

NR 219.04 Text The temperature of the samples shall be documented upon receipt at the laboratory. If the samples are shipped in crushed or cube ice (not “blue ice" packs) and solid ice is still present in the coole r, the lab may simply report the samples as “received on ice". If the ice has melted, the lab must report the either the temperature of the melt- water or of a temperature blank. A temperature blank is defined as an aliquot of deionized water, in an appropriate sample containe r, which is transported along with the samples. Since shipping simply with “blue ice" packs does not insure that samples are maintained at the appropriate temperatures, the sample collector must submit a temperature blank when using these ice packs for shipping.

NR 219.04 Text 3 When any sample is to be shipped by common carrier or sent via the U.S. Postal Service, 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 requirement, 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).

NR 219.04 Text 4 Samples should be analyzed as soon as possible after collection. The times listed are the maximum times that samples may be held before the start of 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 EPA Regional Administrator under s. NR219.05). For a grab sample, the holding time begins at the time of collection. For a composite sample collected with an automated sampler (e.g., using a 24-hour composite sampler); the holding time begins at the time of the end of collection of the composite sample. For a set of grab samples composited in the field or laboratory, the holding time begins at the time of collection of the last grab sample in the set. 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 it knows that a shorter time is necessary to maintain sample stability. See 40 CFR 136.3(e) for details.

NR 219.04 Text 5 ASTM D7365-09a specifies treatment options for samples containing oxidants (e.g.,chlorine). Also, Section 9060A of Standard Methods for the Examination of Water and Wastewater (20th and 21st editions) addresses dechlorination procedures.

NR 219.04 Text 6 Sample collection and preservation: Collect a volume of sample appropriate to the analytical method in a bottle of the material specified. If the sample can be analyzed within 48 hours and sulfide is not present, adjust the pH to >12 with sodium hydroxide solution (e.g., 5% w/v), refrigerate as specified, and analyze within 48 hours. Otherwise, to extend the holding time to 14 days and mitigate interferences, treat the sample immediately using any or all of the following techniques, as necessary, followed by adjustment of the sample pH to >12 and refrigeration as specified.

NR 219.04 Text There may be interferences that are not mitigated by approved procedures. Any procedure for removal or suppression of an interference may be employed, provided the laboratory demonstrates that it more accurately measures cyanide. Particulate cyanide (e.g., ferric ferrocyanide) or a strong cyanide complex (e.g., cobalt cyanide) are more accurately measured if the laboratory holds the sample at room temperature and pH >12 for a minimum of 4 hours prior to analysis, and performs UV digestion or dissolution under alkaline (pH=12) conditions, if necessary.

NR 219.04 Text Sulfur: To remove elemental sulfur (S8), filter the sample immediately. If the filtration time will exceed 15 minutes, use a larger filter or a method that requires a smaller sample volume (e.g., EPA Method 335.4 or Lachat Method 01). Adjust the pH of the filtrate to >12 with NaOH, refrigerate the filter and filtrate, and ship or transport to the laboratory. In the laboratory, extract the filter with 100 mL of 5% NaOH solution for a minimum of 2 hours. Filter the extract and discard the solids. Combine the 5% NaOH-extracted filtrate with the initial filtrate, lower the pH to approximately 12 with concentrated hydrochloric or sulfuric acid, and analyze the combined filtrate. Because the detection limit for cyanide will be increased by dilution by the filtrate from the solids, test the sample with and without the solids procedure if a low detection limit for cyanide is necessary. Do not use the solids procedure if a higher cyanide concentration is obtained without it. Alternatively, analyze the filtrates from the sample and the solids separately, add the amounts determined (in ?g or mg), and divide by the original sample volume to obtain the cyanide concentration.

NR 219.04 Text (1) Sulfide: If the sample contains sulfide as determined by lead acetate paper, or if sulfide is known or suspected to be present, immediately con- duct one of the volatilization treatments or the precipitation treatment as follows: Volatilization—Headspace expelling. In a fume hood or well- ventilated area, transfer 0.75 liter of sample to a 4.4-L collapsible container (e.g., CubitainerTM). Acidify with concentrated hydrochloric acid to pH <2. Cap the container and shake vigorously for 30 seconds. Remove the cap and expel the headspace into the fume hood or open area by collapsing the container without expelling the sample. Refill the headspace by expanding the container. Repeat expelling a total of five headspace volumes. Adjust the pH to >12, refrigerate, and ship or transport to the laboratory. Scaling to a smaller or larger sample volume must maintain the air to sample volume ratio. A larger volume of air will result in too great a loss of cyanide (> 10%). Dynamic stripping: In a fume hood or well ventilated area, transfer 0.75 liter of sample to a container of the material specified and acidify with concentrated hydrochloric acid to pH <2. Using a calibrated air sampling pump or flowmeter, purge the acidified sample into the fume hood or open area through a fritted glass aerator at a flow rate of 2.25 L/min for 4 minutes. Adjust the pH to >12, refrigerate, and ship or transport to the laboratory. Scaling to a smaller or larger sample volume must maintain the air to sample volume ratio. A larger volume of air will result in too great a loss of cyanide (>10%). Precipitation: If the sample contains particulate matter that would be removed by filtration, filter the sample prior to treatment to assure that cyanide associated with the particulate matter is included in the measurement. Ship or transport the filter to the laboratory. In the laboratory, extract the filter with 100 mL of 5% NaOH solution for a minimum of 2 hours. Filter the extract and discard the solids. Combine the 5% NaOH-extracted filtrate with the initial filtrate, lower the pH to approximately 12 with concentrated hydrochloric or sulfuric acid, and analyze the combined filtrate. Because the detection limit for cyanide will be increased by dilution by the filtrate from the solids, test the sample with and without the solids procedure if a low detection limit for cyanide is necessary. Do not use the solids procedure if a higher cyanide concentration is obtained without it. Alternatively, analyze the filtrates from the sample and the solids separately, add the amounts determined (in µg or mg), and divide by the original sample volume to obtain the cyanide concentration. For removal of sulfide by precipitation, raise the pH of the sample to >12 with NaOH solution, then add approximately 1 mg of powdered cadmium chloride for each mL of sample. For example, add approximately 500 mg to a 500-mL sample. Cap and shake the container to mix. Allow the precipitate to settle and test the sample with lead acetate paper. If necessary, add cadmium chloride but avoid adding an excess. Finally, filter through 0.45 micron filter.

NR 219.04 Text Cool the sample as specified and ship or transport the filtrate and filter to the laboratory. In the laboratory, extract the filter with 100 mL of 5% NaOH solution for a minimum of 2 hours. Filter the extract and discard the solids. Combine the 5% NaOH-extracted filtrate with the initial filtrate, lower the pH to approximately 12 with concentrated hydrochloric or sulfuric acid, and analyze the combined filtrate. Because the detection limit for cyanide will be increased by dilution by the filtrate form the solids, test the sample with and without the solids procedure if a low detection limit for cyanide is necessary. Do not use the solids procedure if a higher cyanide concentration is obtained without it. Alternatively, analyze the filtrates from the sample and the solids separately, add the amounts determined (in g or mg), and divide by the original sample volume to obtain the cyanide concentration. If a ligand-exchange method is used (e.g., ASTM D6888), it may be necessary to increase the ligand exchange reagent to offset any excess of cadmium chloride.

NR 219.04 Text (2) Sulfite, thiosulfate, or thiocyanate: If sulfite, thiosulfate, or thiocyanate is known or suspected to be present, use UV digestion with a glass coil (Method Kelada-01) or ligand exchange (Method OIA–1677) to preclude cyanide loss or positive interference.

NR 219.04 Text (3) Aldehyde: If formaldehyde, acetaldehyde, or another water-soluble aldehyde is known or suspected to be present, treat the sample with 20 mL of 3.5% ethylenediamine solution per liter of sample.

NR 219.04 Text (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).

NR 219.04 Text (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.