Wis. Admin. Code Department of Natural Resources NR 809.113

Current through November 25, 2024

Section NR 809.113 - Sample collection and analytical requirements for inorganic contaminants

(1) ANALYTICAL METHODS. Analyses conducted to determine compliance with s. NR 809.11 shall be made in accordance with methods listed in Table A.

Table A

Approved Methodology for Inorganic Contaminants

Contaminant	Methodology¹³	EPA	ASTM³	SM⁴ (18th, 19^th Ed.)	SM⁴ (20^thEd.)	SM⁴ (21st, 22^nd Ed)	SM Online²¹	Other
1. Alkalinity	Titrimetric		D1067-92, 02 B D1067-06 B, 11B	2320 B	2320 B	2320 B	2320 B-97
	Electrometric titration						I-1030-85⁵
2. Antimony	Inductively Coupled Plasma (ICP) - Mass Spectrometry Hydride-Atomic Absorption	200.8²	D3697-92, 02 D3697-07
	Atomic Absorption; Platform	200.9²
	Atomic Absorption; Furnace			3113 B		3113 B	3113 B-99 3113 B-04
	Axially Viewed Inductively Coupled Plasma-Atomic Emission Spectrometry (AVICP-AES)	200.5, Revision 4.225
3. Arsenic¹⁴	ICP-Mass Spectrometry Atomic Absorption; Platform	200.8² 200.9²
	Atomic Absorption; Furnace		D2972-97, 03 C D2972-08 C	3113 B		3113 B	3113 B-99 3113 B-04, B-10
	Hydride Atomic Absorption Axially Viewed Inductively Coupled Plasma-Atomic Emission Spectrome-try (AVICP-AES)	200.5, Revision 4.2²⁵	D1972-97, 03 B D2972-08 B	3114 B		3114 B	3114 B-97 3114 B-09
4. Asbestos	Transmission Electron Microscopy Transmission Electron Microscopy	100.1⁹ 100.2¹⁰
5. Barium	Inductively Coupled Plasma ICP-Mass Spectrometry Atomic Absorption; Direct Aspiration Atomic Absorption; Furnace Axially Viewed Inductively Coupled Plasma-Atomic Emission Spectrometry (AVICP-AES)	200.72 200.8² 200.5, Revision 4.2²⁵		3120 B 3111D 3113 B	3120 B	3120 B 3111 D 3113 B	3120 B-99 3111 D-99 3113 B-99 3113 B-04, B-10
6. Beryllium	Inductively Coupled Plasma ICP-Mass Spectrometry Atomic Absorption; Platform	200.7² 200.8² 200.9²		3120 B	3120 B	3120 B	3120 B-99
	Atomic Absorption; Furnace Axially Viewed Inductively Coupled Plasma-Atomic Emission Spectrometry (AVICP-AES)	200.5, Revision 4.2²⁵	D3645-97, 03 B D3645-08 B	3113 B		3113 B	3113 B-99 3113 B-04, B-10
7. Cadmium	Inductively Coupled Plasma ICP-Mass Spectrometry Atomic Absorption; Platform Atomic Absorption; Furnace Axially Viewed Inductively Coupled Plasma-Atomic Emission Spectrometry (AVICP-AES)	200.7² 200.8² 200.9² 200.5, Revision 4.2²⁵		3113 B		3113 B	3113 B-99 3113 B-04, B-10
8. Calcium	EDTA titrimetric		D511-93, 03 A D511-09 A	3500-Ca D	3500-Ca B	3500-Ca B	3500-Ca B-97
	Atomic Absorption; Direct Aspiration		D511-93, 03 B D511-09 B	3111 B		3111 B	3111 B-99
	Inductively Coupled Plasma Ion Chromatography Axially Viewed Inductively Coupled Plasma-Atomic Emission Spectrometry (AVICP-AES)	200.7² 200.5, Revision 4.2²⁵	D6919-03 D6919-09	3120 B	3120 B	3120 B	3120 B-99
9. Chromium	Inductively Coupled Plasma ICP-Mass Spectrometry	200.7² 200.8²		3120 B	3120 B	3120 B	3120 B-99
	Atomic Absorption; Platform Atomic Absorption; Furnace Axially Viewed Inductively Coupled Plasma-Atomic Emission Spectrometry (AVICP-AES)	200.9² 200.5, Revision 4.2²⁵		3113 B		3113 B	3113 B-99 3113 B-04, B-10
10. Copper	Atomic Absorption; Furnace		D1688-95, 02 C D1688-07 C	3113 B		3113 B	3113 B-99 3113 B-04, B-10
	Atomic Absorption; Direct Aspiration		D1688-95, 02 A	3111 B		3111 B	3111 B-99
	Inductively Coupled Plasma ICP-Mass Spectrometry Atomic Absorption; Platform Axially Viewed Inductively Coupled Plasma-Atomic Emission Spectrometry (AVICP-AES)	200.7² 200.8² 200.9² 200.5, Revision 4.2²⁵		3120 B	3120 B	3120 B	3120 B-99
11. Conductivity	Conductance		D1125-95 (Reapproved 1999) A	2510 B	2510 B	2510 B	2510 B-97
12. Cyanide	Manual Distillation followed by		D2036-98 A D2036-06 A	4500-CN^-C	4500-CN^-C
	Spectrophotometric, Amenable		D2036-98 B D2036-06 B	4500-CN^-G	4500-CN^-G	4500-CN^-G	4500-CN^-G-9 9
	Spectrophotometric Manual Spectrophotometric Semi-automated	335.4⁶	D2036-98 A D2036-06 A	4500-CN^-E	4500-CN^-E	4500-CN^-E	4500-CN^-E-9 9	I-3300-85⁵
	Selective Electrode U V, Distillation, Spectrophotometric Micro Distillation, Flow Injection, Spectrophotometric Ligand Exchange and Amperometry²⁰ Gas Chromatography/ Mass Spectrometry Headspace		D6888-04	4500-CN^-F	4500-CN^-F	4500-CN^-F	4500-CN^-F-99	Kelada-01¹⁶ QuikChem 10-204-00-1- X¹⁷ OIA-1677, DW¹⁹ MME355.01²⁶
13. Fluoride	Ion Chromatography	300.0⁶, 300.1¹⁸	D4327-97, 03	4110 B	4110 B		4110 B-00
	Manual Distill.; Color. SPADNS			4500-F^-B, D	4500-F^-B, D	4500-F^-B, D	4500-F^-B, D-97
	Manual Electrode		D1179-93, 99 B D1179-04, 10 B	4500-F^-C	4500-F^-C	4500-F^-C	4500-F^-C-97
	Automated Electrode							380-75WE¹¹
	Automated Alizarin			4500-F^-E	4500-F^-E	4500-F^-E	4500-F^-E-97	129-71W¹¹
	Capillary Ion Electrophoresis							D6508, Rev. 2²²
	Arsenite-Free Colorimetric SPADNS							Hach SPADNS 2 Method 10225²⁷
14. Lead	Atomic Absorption; Furnace		D3559-96, 03 D D3559-08 D	3113 B		3113 B	3113 B-99 3113 B-04, B-10
	ICP-Mass spectrometry	200.8²
	Atomic Absorption; Platform	200.9²
	Differential Pulse							Method 1001¹⁵
	Anodic Stripping Voltametry
	Axially Viewed	200.5,
	Inductively Coupled	Revision
	Plasma-Atomic	4.2²⁵
	Emission Spectrometry (AVICP-AES)
15. Magnesium	Atomic Absorption		D511-93, 03 B D511-09 B	3111 B		3111 B	3111 B-99
	ICP	200.7²		3120 B	3120 B	3120 B	3120 B-99
	Complexation Titrimetric Methods		D511-93, 03 A	3500-Mg E	3500-Mg B	3500-Mg B	3500-Mg B-97
			D511-09 A
	Ion Chromatography		D6919-03
			D6919-09
	Axially Viewed	200.5,
	Inductively Coupled	Revision
	Plasma-Atomic	4.2²⁵
	Emission Spectrometry (AVICP-AES)
16. Mercury	Manual, Cold Vapor	245.1²	D3223-97, 02	3112 B		3112 B	3112 B-99 3112 B-09
	Automated, Cold Vapor	245.2¹
	ICP-Mass Spectrometry	200.8²
17. Nickel	Inductively Coupled Plasma	200.7²		3120 B	3120 B	3120 B	3120 B-99
	ICP-Mass Spectrometry	200.8²
	Atomic Absorption; Platform	200.9²
	Atomic Absorption; Direct			3111 B		3111 B	3111 B-99
	Atomic Absorption; Furnace			3113 B		3113 B	3113 B-99 3113 B-04
	Axially Viewed Inductively Coupled Plasma-Atomic Emission Spectrometry (AVICP-AES)	200.5, Revision 4.2²⁵
18. Nitrate	Ion Chromatography	300.0⁶30 0.1¹⁸	D4327-97, 03 D4327-11	4110 B	4110 B	41410 B	4110 B-00	B-1011⁸
	Automated Cadmium Reduction	353.2⁶	D3867-90 A	4500-NO3^-F	4500-NO3^-F	4500-NO3^-F	4500-NO3^-F- 00
	Ion Selective Electrode			4500-NO3^-D	4500-NO3^-D	4500-NO3^-D	4500-NO3^-D- 00	601⁷
	Manual Cadmium Reduction		D3867-90 B	4500-NO3^-E	4500-NO3^-E	4500-NO3^-E	4500-NO3^-E- 00
	Capillary Ion Electrophoresis							D6508, Rev. 2²²
	Reduction/Colorimet-ric							Systea Easy (1-Reagent)²⁸
19. Nitrite	Ion Chromatography	300.0⁶ 30 0.1¹⁸	D4327-97, 03	4110 B	4110 B	4110 B	4110 B-00	B-1011⁸
	Automated Cadmium Reduction	353.2⁶	D3867-90 A	4500-NO3^-F	4500-NO3^-F	4500-NO3^-F	4500-NO3^-F- 00
	Manual Cadmium Reduction		D3867-90 B	4500-NO3^-E	4500-NO3^-E	4500-NO3^-E	4500-NO3^-E- 00
	Spectrophotometric Capillary Ion Electrophoresis Reduction/Colorimetric			4500-NO2^-B	4500-NO2^-B	4500-NO2^-B	4500-NO2^-B- 00	D6508, Rev. 2²² Systea Easy (1-Reagent)²⁸
20. Ortho-phosphate¹²	Colorimetric, Automated, Ascorbic Acid	365.1⁶		4500-P F	4500-P F	4500-P F	4500-P F-99
	Colorimetric, ascorbic acid, single reagent Colorimetric Phosphomolybdate; Automated-segmented flow; Automated Discrete		D515-88 A	4500-P E	4500-P E	4500-P E		I-1601-85⁵I-2601-90⁵I-2598-85⁵
	Ion Chromatography Capillary Ion Electro-phoresis	300.0⁶ 300.1¹⁸	D4327-97, 03	4110 B	4110 B		4110 B-00	D6508, Rev. 2²²
21. pH	Electrometric	150.1, 150.2¹	D1293-95, 99 D1293-12	4500-H⁺B	4500-H⁺B	4500-H⁺B	4500-H⁺B-00
22. Selenium	Hydride-Atomic Absorption		D3859-98, 03 A	3114 B		3114 B	3114 B-97 3114 B-09
	ICP-Mass Spectrometry	200.8²
	Atomic Absorption; Platform	200.9²
	Atomic Absorption; Furnace		D3859-98, 03 B D3859-08 B	3113 B		3113 B	3113 B-99 3113 B-04
	Axially Viewed Inductively Coupled Plasma-Atomic Emission Spectrometry (AVICP-AES)	200.5, Revision 4.2²⁵
23. Silica	Colorimetric, Molybdate Blue							I-1700-85⁵
	Automated-segmented Flow Colorimetric		D859-94, 00 D859-05, 10					I-2700-85⁵
	Molybdosilicate			4500-Si D	4500-SiO2 C	4500-SiO2 C	4500-SiO2 C-97
	Heteropoly blue			4500-Si E	4500-SiO2 D	4500-SiO2 D	4500-SiO2 D-97
	Automated for Molybdate-reactive Silica			4500-Si F	4500-SiO2 E	4500-SiO2 E	4500-SiO2 E-97
	Inductively Coupled Plasma	200.7²		3120 B	3120 B	3120 B	3120 B-99
	Axially Viewed Inductively Coupled Plasma-Atomic Emission Spectrometry (AVICP-AES)	200.5, Revision 4.2²⁵
24. Sodium	Inductively Coupled Plasma	200.7²
	Atomic Absorption; Direct Aspiration			3111 B		3111 B	3111 B-99
	Ion Chromatography		D6919-03 D6919-09
	Axially Viewed Inductively Coupled Plasma-Atomic Emission Spectrometry (AVICP-AES)	200.5, Revision 4.2²⁵
25. Temperature	Thermometric			2550	2550	2550	2550-00 2550-10
26. Thallium	ICP-Mass Spectrometry	200.8²
	Atomic Absorption; Platform	200.9²
27. Turbidity	Nephelometric	180.1²³		2130 B		2130 B	2130 B-01
	Great Lakes Instrument							Instruments Method 2²⁴
	Laser Nephelometry (on-line)							Mitchell M5271²⁹
	LED Nephelometry (on-line)							Mitchell M5331³⁰
	LED Nephelometry (on-line)							AMI Turbi-well³¹
	LED Nephelometry (portable)							Orion AQ4500³²
	Hach FilterTrak							10133³³

Copies of the documents may be obtained from the sources listed below. Information regarding obtaining these documents can be obtained from the Safe Drinking Water Hotline at 800-426-4791, or go to: http://www.archives.gov/federal_register/code_of_federal_regulations/ibr_locations.html.

¹ "Methods for Chemical Analysis of Water and Wastes," EPA/600/4-79/020, March 1983. Available at NTIS, PB84-128677.

² "Methods for the Determination of Metals in Environmental Samples-Supplement I," EPA/600/R-94/111, May 1994. Available at NTIS, PB95-125472.

³Annual Book of ASTM Standards, 1994, 1996, 1999, or 2003, Vols. 11.01 and 11.02, ASTM International; any year containing the cited version of the method may be used. The previous versions of D1688-95A, D1688-95C (copper), D3559-95D (lead), D1293-95 (pH), D1125-91A (conductivity) and D859-94 (silica) are also approved. These previous versions D1688-90A, C; D3559-90D, D1293-84, D1125-91A and D859-88, respectively are located in the Annual Book of ASTM Standards, 1994, Vol. 11.01. Copies may be obtained from ASTM International, 100 Barr Harbor Drive, West Conshohocken, PA 19428.

⁴Standard Methods for the Examination of Water and Wastewater, 18th edition (1992), 19th edition (1995), 20th edition (1998), 21 st edition (2005), or 22 nd edition (2012). American Public Health Association, 1015 Fifteenth Street, NW., Washington, DC 20005. The cited methods published in any of these three editions may be used, except that the versions of 3111 B, 3111 D, 3113 B and 3114 B in the 20th edition may not be used.

⁵ Method I-2601-90, Methods for Analysis by the U.S. Geological Survey National Water Quality Laboratory-Determination of Inorganic and Organic Constituents in Water and Fluvial Sediment, Open File Report 93-125, 1993; For Methods I-1030-85; I-1601-85; I-1700- 85; I-2598-85; I-2700-85; and I-3300-85 See Techniques of Water Resources Investigation of the U.S. Geological Survey, Book 5, Chapter A-1, 3rd edition., 1989; Available from Information Services, U.S. Geological Survey, Federal Center, Box 25286, Denver, CO 80225-0425.

⁶ "Methods for the Determination of Inorganic Substances in Environmental Samples," EPA/600/R-93/100, August 1993. Available at NTIS, PB94-120821.

⁷ The procedure shall be done in accordance with the Technical Bulletin 601 " Standard Method of Test for Nitrate in Drinking Water," July 1994, PN 221890-001, Analytical Technology, Inc. Copies may be obtained from ATI Orion, 529 Main Street, Boston, MA 02129.

⁸ Method B-1011, "Waters Test Method for Determination of Nitrite/Nitrate in Water Using Single Column Ion Chromatography," August 1987. Copies may be obtained from Waters Corporation, Technical Services Division, 34 Maple Street, Milford, MA 01757, Telephone: 508/482-2131, Fax: 508/482-3625.

⁹ Method 100.1, "Analytical Method For Determination of Asbestos Fibers in Water," EPA/600/4-83/043, EPA, September 1983. Available at NTIS, PB83-260471.

¹⁰ Method 100.2, "Determination of Asbestos Structure Over 10-m In Length In Drinking Water," EPA/600/R-94/134, June 1994. Available at NTIS, PB942-01902.

¹¹ Industrial Method No. 129-71W, "Fluoride in Water and Wastewater," December 1972, and Method No. 380-75WE, "Fluoride in Water and Wastewater," February 1976, Technicon Industrial Systems. Copies may be obtained from Bran & Luebbe, 1025 Busch Parkway, Buffalo Grove, IL 60089.

¹² Unfiltered, no digestion or hydrolysis.

¹³ Because MDLs reported in EPA Methods 200.7 and 200.9 were determined using a 2x preconcentration step during sample digestion, MDLs determined when samples are analyzed by direct analysis ( i.e., no sample digestion) will be higher. For direct analysis of cadmium and arsenic by Method 200.7, and arsenic by Method 3120 B, sample preconcentration using pneumatic nebulization may be required to achieve lower detection limits. Preconcentration may also be required for direct analysis of antimony, lead, and thallium by Method 200.9; antimony and lead by Method 3113 B; and lead by Method D3559-90D, unless multiple in-furnace depositions are made.

¹⁴ If ultrasonic nebulization is used in the determination of arsenic by Methods 200.7, 200.8, or SM 3120 B, the arsenic must be in the pentavalent state to provide uniform signal response. For Methods 200.7 and 3120 B, both samples and standards must be diluted in the same mixed acid matrix concentration of nitric and hydrochloric acid with the addition of 100 L of 30% hydrogen peroxide per 100 mL of solution. For direct analysis of arsenic with Method 200.8 using ultrasonic nebulization, samples and standards must contain 1 mg/L of sodium hypochlorite.

¹⁵ The description for Method Number 1001 for lead is available from Palintest, LTD, 21 Kenton Lands Road, P.O. Box 18395, Erlanger, KY 41018. Or from the Hach Company, P.O. Box 389, Loveland, CO 80539.

¹⁶ The description for the Kelada-01 Method, "Kelada Automated Test Methods for Total Cyanide, Acid Dissociable Cyanide, And Thiocyanate," Revision 1.2, August 2001, EPA # 821-B-01-009 for cyanide is available from the National Technical Information Service (NTIS), PB 2001-108275, 5285 Port Royal Road, Springfield, VA 22161. The toll free telephone number is 800-553-6847.

Note: A 450W UV lamp may be used in this method instead of the 550W lamp specified if it provides performance within the quality control (QC) acceptance criteria of the method in a given instrument. Similarly, modified flow cell configurations and flow conditions may be used in the method, provided that the QC acceptance criteria are met.

¹⁷ The description for the 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 2.1, November 30, 2000, for cyanide is available from Lachat Instruments, 6645 W. Mill Rd., Milwaukee, WI 53218. Telephone: 414-358-4200.

¹⁸ "Methods for the Determination of Organic and Inorganic Compounds in Drinking Water," Vol. 1, EPA 815-R-00-014, August 2000. Available at NTIS, PB2000-106981.

¹⁹ Method OIA-1677, DW "Available Cyanide by Flow Injection, Ligand Exchange, and Amperometry," January 2004. EPA-821-R-04-001, Available from ALPKEM, A Division of OI Analytical, P.O. Box 9010, College Station, TX 77842-9010.

²⁰ Sulfide levels below those detected using lead acetate paper may produce positive method interferences. Test samples using a more sensitive sulfide method to determine if a sulfide interference is present, and treat samples accordingly.

²¹ Standard Methods Online are available at http://www.standardmethods.org. The year in which each method was approved by the Standard Methods Committee is designated by the last two digits in the method number. The methods listed are the only online versions that may be used.

²² Method D6508, Rev. 2, "Test Method for Determination of Dissolved Inorganic Anions in Aqueous Matrices Using Capillary Ion Electrophoresis and Chromate Electrolyte," available from Waters Corp, 34 Maple St, Milford, MA, 01757, Telephone: 508/482-2131, Fax: 508/482- 3625.

²³ "Methods for the Determination of Inorganic Substances in Environmental Samples", EPA-600/R-93-100, August 1993, Available at NTIS, PB94-121811

²⁴ GLI Method 2, "Turbidity", November 2, 1992, Great Lakes Instruments, Inc., 8855 North 55th Street, Milwaukee, Wisconsin 53223.

²⁵ EPA Method 200.5 Revision 4.2. "Determination of Trace Elements in Drinking Water by Axially Viewed Inductively Coupled Plasma-Atomic Emission Spectrometry." 2003. EPA/600/R-06/115. Available at http:/www.epa.gov/nerlcwww/ordmeth.htm.

²⁶ Method ME355.01, Revision 1.0. "Determination of Cyanide in Drinking Water by GC/MS Headspace." May 26, 2009. Available at http://www.nemi.gov or from James Eaton, H & E Testing Laboratory, 221 State Street, Augusta, ME 04333. (207) 287-2727

²⁷ Hach Company Method, "Hach Company SPADNS 2 (Arsenite - free) Fluoride Method 10255-Spectrophotometric Measurement of Fluoride in Water and Wastewater," January 2011. 5600 Lindbergh Drive, P.O. Box 389, Loveland, Colorado 80539. Available at http://www.hach.com.

²⁸ Systea Easy (1-Reagent). "Systea Easy (1-Reagent) Nitrate Method," February 4, 2009. Available at http://www.nemi.gov or from Systea Scientific, LLC., 900 Jorie Blvd., Suite 35, Oak Brook, IL 60523.

²⁹ Mitchell Method M5271, Revision 1.1." Determination of Turbidity by Laser Nephelometry," March 5, 2009. Available at http://www.nemi.gov or from Leck Mitchell, PhD, PE, 656 Independence Valley Dr., Grand Junction, CO 81507.

³⁰ Mitchell Method M5331, Revision 1.1. "Determination of Turbidity by LED Nephelometry," March 5, 2009. Available at http://www.nemi.gov or from Leck Mitchell, PhD, PE, 656 Independence Valley Dr., Grand Junction, CO 81507.

³¹ AMI Turbiwell. "Continuous Measurement of turbidity Using a SWAN AMI Turbiwell Turbidimeter," August 2009. Available at http://www.nemi.gov or from Markus Bernasconi, SWAN Analytische Instrumente AG, Studbachstrasse 13, CH-8340 Hinwil, Switzerland.

³² Orion Method AQ4500, Revision 1.0. "Determination of Turbidity by LED Nephelometry," May 8, 2009. Available at http://www.nemi.gov or from Thermo Scientific, 166 Cummings Center, Beverly, MA 0`9`5, http://www.thermo.com.

³³ Hach Filter Trak Method 10133, "Determination of Turbidity by Laser Nephelomemtry," January 2000, Revision 2.0. Available from Hach Co., P.O. Box389, Loveland, CO 80539-0389.

(2) SAMPLE COLLECTION. Sample collection for the inorganic contaminants under s. NR 809.11(2) shall be conducted using the sample preservation, containers and maximum holding time procedures specified in Table B. In all cases, samples should be analyzed as soon after collection as possible.

Table B

Sample Preservation, Containers and Maximum Holding Times for Inorganic Parameters

Parameter	Preservation¹	Container²	Holding Time³
METALS
Aluminum	HNO₃	P or G	6 months
Antimony	HNO₃	P or G	6 months
Arsenic	HNO₃	P or G	6 months
Barium	HNO₃	P or G	6 months
Beryllium	HNO₃	P or G	6 months
Cadmium	HNO₃	P or G	6 months
Copper	HNO₃	P or G	6 months
Chromium	HNO₃	P or G	6 months
Iron	HNO₃	P or G	6 months
Lead	HNO₃	P or G	6 months
Manganese	HNO₃	P or G	6 months
Mercury	HNO₃	P or G	28 days
Nickel	HNO₃	P or G	6 months
Selenium	HNO₃	P or G	6 months
Silver	HNO₃	P or G	6 months
Thallium	HNO₃	P or G	6 months
Zinc	HNO₃	P or G	6 months
OTHER PARAMETERS
Asbestos	Cool, 4°C	P or G	48 hours⁴
Bromate	Ethylenediamine	P or G	28 days
Chloride	None	P or G	28 days
Chlorite	50 mg/L EDA, Cool to 4°C	P or G	14 days
Color	Cool, 4°C	P or G	48 hours
Cyanide	Cool, 4°C+NaOH to pH>12	P or G	14 days
Fluoride	None	P or G	28 days
Foaming Agents	Cool, 4°C	P or G	48 hours
Nitrate (as N) Chlorinated	Cool, 4°C	P or G	14 days
Non-Chlorinated	Cool, 4°C	P or G	48 hours⁵
Nitrite (as N)	Cool, 4°C	P or G	48 hours
Nitrate + Nitrite⁶	Conc. H₂SO₄ to pH<2	P or G	28 days
Odor	Cool, 4°C	G	48 hours
pH	None	P or G	Analyze Immediately
Solids (TDS)	Cool, 4°C	P or G	7 days
Sulfate	Cool, 4°C	P or G	28 days
Turbidity	Cool, 4°C	P or G	48 hours

¹ For cyanide determinations samples must be adjusted with sodium hydroxide to pH 12 at the time of collection. When chilling is indicated the sample must be shipped and stored at 4 5C or less. Acidification of nitrate or metals samples may be done with a concentrated acid or a dilute (50% by volume) solution of the applicable concentrated acid. Acidification of samples for metals analysis is encouraged and allowed at the laboratory rather than at the time of sampling provided the shipping time and other instructions in Section 8.3 of EPA Methods 200.7 or 200.8 or 200.9 are followed.

² P = plastic, hard or soft. G = glass, hard or soft.

³ In all cases, samples should be analyzed as soon after collection as possible.

⁴ Instructions for containers, preservation procedures and holding times as specified in Method 100.2 must be adhered to for all compliance analyses including those conducted with Method 101.1.

⁵ If the sample is chlorinated, the holding time for an unacidified sample kept at 4°C is extended to 14 days.

⁶ Nitrate-nitrite refers to a measurement of total nitrate.

(3) LABORATORY CERTIFICATION. Analyses under this section shall only be conducted by laboratories that have received certification under ch. NR 149 or approval by EPA.

(a) To receive certification to conduct analyses for antimony, arsenic, asbestos, barium, beryllium, cadmium, cyanide, fluoride, mercury, nickel, nitrate, nitrite, selenium and thallium, a laboratory shall carry out annual analyses of performance evaluation samples approved by the department or EPA.

(b) For each contaminant that has been included in the performance evaluation sample and for each method for which a laboratory desires certification, the laboratory shall achieve quantitative results that are within the following acceptance limits:

Contaminant	Acceptance limit
Antimony	±30% at >=0.006 mg/L
Arsenic	±30% at >=0.003 mg/L
Asbestos	2 standard deviations based on study statistics
Barium	±15% at >=0.15 mg/L
Beryllium	±15% at >=0.001 mg/L
Cadmium	±20% at >=0.002 mg/L
Chromium	±15% at >=0.01 mg/L
Cyanide	±25% at >=0.1 mg/L
Fluoride	±10% at >=1 to 10 mg/L
Mercury	±30% at >=0.0005 mg/L
Nickel	±15% at >=0.01 mg/L
Nitrate	±10% at >=0.4 mg/L
Nitrite	±15% at >=0.4 mg/L
Selenium	±20% at >=0.01 mg/L
Thallium	±30% at >=0.002 mg/L

(4) COMPOSITE SAMPLING. Composite sampling for inorganic contaminants shall meet the following requirements:

(a) The department may reduce the total number of samples a public water system is required to analyze by allowing the use of compositing. Compositing shall only be permitted for entry points within a single public water system. Composite samples from a maximum of 5 entry points are allowed, provided that the detection limit of the method used for analysis is less than one-fifth of the MCL.

(b) Compositing of samples shall be done in the laboratory.

(c) If the concentration in the composite sample is greater than or equal to one-fifth of the MCL of any inorganic contaminant, a follow-up sample shall be taken from each entry point included in the composite and analyzed within 14 days. These samples shall be analyzed for the contaminants which exceeded one-fifth of the MCL in the composite sample.

(d) If duplicates of the original sample taken from each entry point used in the composite are available and the holding time listed in sub. (2) Table B has not been exceeded, the water supplier may use these instead of resampling. The duplicates shall be analyzed and the results reported to the department within 14 days of the composite analysis.

(e) The detection limits in Table C, are the detection limits that laboratories shall use for each analytical method and MCLs for inorganic contaminants specified in this section and s. NR 809.11:

TABLE C

Detection Limits for Inorganic Contaminants

Contaminant	MCL (mg/l)	Methodology	Detection limit (mg/l)
Antimony	0.006	Atomic Absorption; Furnace	0.003
		Atomic Absorption; Platform	0.0008⁵
		ICP-Mass Spectrometry	0.0004
		Hydride-Atomic Absorption	0.001
Arsenic	0.010	Atomic Absorption; Furnace	0.001
		Atomic Absorption; Platform-Stabilized Temperature	0.0005⁶
		Atomic Absorption; Gaseous Hydride	0.001
		ICP-Mass Spectrometry	0.0014⁷
Asbestos	7 MFL¹	Transmission Electron Microscopy	0.01 MFL
Barium	2	Atomic Absorption; furnace technique	0.002
		Atomic Absorption; direct aspiration	0.1
		Inductively Coupled Plasma	0.002 (0.001)
Beryllium	0.004	Atomic Absorption; Furnace	0.0002
		Atomic Absorption; Platform	0.00002⁵
		Inductively Coupled Plasma²	0.0003
		ICP-Mass Spectrometry	0.0003
Cadmium	0.005	Atomic Absorption; furnace technique	0.0001
		Inductively Coupled Plasma	0.001
Chromium	0.1	Atomic Absorption; furnace technique	0.001
		Inductively Coupled Plasma	0.007 (0.001)
Cyanide	0.2	Distillation, Spectrophotometric³	0.02
		Distillation, Automated, Spectrophotometric³	0.005
		Distillation, Amenable, Spectrophotometric⁴	0.02
		Distillation, Selective Electrode^3,⁴	0.05
		U V, Distillation, Spectrophotometric⁹	0.0005
		Micro Distillation, Flow Injection, Spectrophotometric³	0.0006
		Ligand Exchange with Amperometry⁴	0.0005
Mercury	0.002	Manual Cold Vapor Technique	0.0002
		Automated Cold Vapor Technique	0.0002
Nickel	0.1	Atomic Absorption; Furnace	0.001
		Atomic Absorption; Platform	0.0006⁵
		Inductively Coupled Plasma²	0.005
		ICP-Mass Spectrometry	0.0005
Nitrate	10 (as N)	Manual Cadmium Reduction	0.01
		Automated Hydrazine Reduction	0.01
		Automated Cadmium Reduction	0.05
		Ion Selective Electrode	1
		Ion Chromatography	0.01
		Capillary Ion Electrophoresis	0.076
Nitrite	1 (as N)	Spectrophotometric	0.01
		Automated Cadmium Reduction	0.05
		Manual Cadmium Reduction	0.01
		Ion Chromatography	0.004
		Capillary Ion Electrophoresis	0.103
Selenium	0.05	Atomic Absorption; furnace	0.002
		Atomic Absorption; gaseous hydride	0.002
Thallium	0.002	Atomic Absorption; Furnace	0.001
		Atomic Absorption; Platform	0.0007⁵
		ICP-Mass Spectrometry	0.0003

¹ MFL = million fibers per liter >10 mm.

² Using a 2X preconcentration step as noted in Method 200.7. Lower MDLs may be achieved when using a 4X preconcentration.

³ Screening method for total cyanides.

⁴ Measures "free" cyanides when distillation, digestion, or ligand exchange is omitted.

⁵ Lower MDLs are reported using stabilized temperature graphite furnace atomic absorption.

⁶ The MDL reported for EPA method 200.9 (Atomic Absorption; Platform-Stabilized Temperature) was determined using a 2x concentration step during sample digestion. The MDL determined for samples analyzed using direct analyses ( i.e., no sample digestion) will be higher. Using multiple depositions, EPA 200.9 is capable of obtaining MDL of 0.0001 mg/L.

⁷ Using selective ion monitoring, EPA Method 200.8 (ICP-MS) is capable of obtaining a MDL of 0.0001 mg/L.

⁸ Measures total cyanides when UV-digestor is used, and "free" cyanides when UV-digestor is bypassed.

Wis. Admin. Code Department of Natural Resources NR 809.113

CR 09-073: cr. Register November 2010 No. 659, eff. 12-1-10.

Amended by, CR 15-049: am. (1) Table A, (4) Table C Register March 2016 No. 723, eff.4/1/2016