NR 809.11 History
History: CR 09-073: cr.
Register November 2010 No. 659, eff. 12-1-10;
CR 15-049: am. (2), (3) (a), (d), (4) (a)
Register March 2016 No. 723, eff. 4-1-16.
NR 809.113
NR 809.113 Sample collection and analytical requirements for inorganic contaminants.
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.
3 Annual 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.
4 Standard Methods for the Examination of Water and Wastewater, 18th edition (1992), 19th edition (1995), 20th edition (1998), 21st 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-ìm In Length In Drinking Water," EPA/600/R–94/134, June 1994. Available at NTIS, PB94–201902.
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 ìL 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.
NR 809.113 Note
Note: A 450–W UV lamp may be used in this method instead of the 550–W 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 FilterTrak Method 10133, “Determination of Turbidity by Laser Nephelomemtry," January 2000, Revision 2.0. Available from Hach Co., P.O. Box389, Loveland, CO 80539-0389.
NR 809.113(2)
(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.
-
See PDF for table 
NR 809.113(3)
(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.
NR 809.113(3)(a)
(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.
NR 809.113(3)(b)
(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:
-
See PDF for table NR 809.113(4)
(4) Composite sampling. Composite sampling for inorganic contaminants shall meet the following requirements:
NR 809.113(4)(a)
(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.
NR 809.113(4)(c)
(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.
NR 809.113(4)(d)
(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.
NR 809.113(4)(e)
(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:
1 MFL = million fibers per liter >10 µm.
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.
NR 809.113 History
History: CR 09-073: cr.
Register November 2010 No. 659, eff. 12-1-10;
CR 15-049: am. (1) Table A, (4) Table C
Register March 2016 No. 723, eff. 4-1-16.
NR 809.115
NR 809.115 Monitoring requirements for inorganic contaminants. NR 809.115(1)(1)
General. Water suppliers shall conduct monitoring for the contaminants listed in s.
NR 809.11 (2) for the purpose of determining compliance with the maximum contaminant levels shall be conducted as follows:
NR 809.115(1)(a)
(a) Groundwater sources shall be sampled under normal operating conditions at every entry point to the distribution system which is representative of each well being used after treatment, beginning in the initial compliance period. Each sample shall be taken at the same location unless conditions make another location more representative of each source or treatment plant.
NR 809.115(1)(b)
(b) Surface water sources or combined surface water and groundwater sources shall be sampled under normal operating conditions, at every entry point to the distribution system after any application of treatment or in the distribution system at a point which is representative of each source after treatment, beginning in the initial compliance period. Each sample shall be taken at the same location unless conditions make another location more representative of each source or treatment plant.
NR 809.115(1)(c)
(c) If a public water system draws water from more than one source and the sources are combined before distribution, the public water system shall be sampled at an entry point to the distribution system during periods of normal operating conditions when water is representative of all sources being used.
NR 809.115(1)(d)
(d) Water suppliers for all new public water systems or for public water systems that use a new source of water that begin operation after January 22, 2004 shall demonstrate compliance with the MCLs specified in s.
NR 809.11 (2) in accordance with the requirements in this section. The water supplier shall also comply with the initial and routine sampling frequencies specified by the department to ensure a water supplier can demonstrate that the public water supply is in compliance with the MCLs. Routine and increased monitoring frequencies shall be conducted in accordance with the requirements of this section.
NR 809.115(2)
(2) Monitoring frequency for asbestos. Water suppliers shall monitor public water systems to determine compliance with the maximum contaminant level for asbestos specified in s.
NR 809.11 (2) at the following frequencies:
NR 809.115(2)(a)
(a) Initial and routine monitoring. Each community and non-transient, non-community water system shall monitor for asbestos during the first 3-year compliance period of each 9-year compliance cycle beginning in the compliance period starting January 1, 1993, unless a waiver is granted under par.
(d).
NR 809.115(2)(b)
(b) Waiver request. If the water supplier believes the public water system it is not vulnerable to either asbestos contamination in its source water or due to corrosion of asbestos-cement pipe, or both, the water supplier may apply to the department for a waiver of the monitoring requirement in par.
(a).
NR 809.115(2)(c)
(c) Waiver evaluation. The department may grant a waiver based on a consideration of all the following factors:
NR 809.115(2)(d)
(d) Waiver conditions. The department may grant a waiver if the conditions in par.
(b) and
(c) are satisfied. A waiver remains in effect until the completion of the 3-year compliance period. Water suppliers for public water systems that do not receive a waiver shall monitor in accordance with the provisions of par.
(a).
NR 809.115(2)(e)
(e) Monitoring frequency with waiver. If the department grants the waiver, the water supplier is not required to monitor under par.
(a).
NR 809.115(2)(f)1.1. A public water system vulnerable to asbestos contamination due solely to corrosion of asbestos-cement pipe shall be sampled once at a tap served by asbestos-cement pipe and under conditions where asbestos contamination is most likely to occur.
NR 809.115(2)(f)2.
2. A public water system vulnerable to asbestos contamination due both to its source water supply and corrosion of asbestos-cement pipe shall be sampled once at a tap served by asbestos-cement pipe and under conditions where asbestos contamination is most likely to occur.
NR 809.115(2)(g)
(g) Sample frequency for public water systems with vulnerable source water. A public water system vulnerable to asbestos contamination due solely to source water shall be monitored in accordance with the provisions in par.
(a).
NR 809.115(2)(h)
(h) Monitoring when an MCL is exceeded. A public water system which exceeds the MCL as determined in s.
NR 809.117 shall be monitored quarterly beginning in the next quarter after the violation occurred. The department may decrease the quarterly monitoring requirement to one sample as specified in par.
(a) if the department has determined that the public water system is reliably and consistently below the maximum contaminant level. In no case may the department make this determination unless a groundwater system takes a minimum of 2 quarterly samples and a surface water system or a combined surface water and groundwater system takes a minimum of 4 quarterly samples.
NR 809.115(2)(i)
(i) Grandfathered data. If monitoring data collected after January 1, 1990 is generally consistent with the requirements of this subsection, then the department may allow water suppliers for public water systems to use that data to satisfy the monitoring requirement for the initial compliance period beginning January 1, 1993.
NR 809.115(3)
(3) Monitoring frequency for MCLs other than asbestos, nitrate, and nitrite. The water supplier shall conduct monitoring for each community and non-transient, non-community water system to determine compliance with the MCLs specified in s.
NR 809.11 (2) for antimony, arsenic, barium, beryllium, cadmium, chromium, cyanide, mercury, nickel, selenium and thallium at the frequencies specified in this subsection. The water supplier shall conduct monitoring for each community water system to determine compliance with the MCL in s.
NR 809.11 (2) for fluoride at the frequencies specified in this subsection:
NR 809.115(3)(a)
(a) Initial monitoring. New community public water systems or community public water systems with new sources shall demonstrate compliance with the MCLs listed under s.
NR 809.11 (2) for antimony, arsenic, barium, beryllium, cadmium, chromium, cyanide, fluoride, mercury, nickel, selenium and thallium prior to initiating water service. New non-transient non-community public water systems or non-transient non-community public water systems with new sources shall take one sample for each contaminant listed in s.
NR 809.11 (2) beginning with the year the public water system initiates service or the new water source is put into service. If a waiver from cyanide monitoring has been granted under par.
(c) cyanide is not required to be sampled for in the initial monitoring.
NR 809.115(3)(b)
(b) Routine monitoring. Groundwater sources shall be sampled at each sampling point during each compliance period as determined by the department. Water suppliers for public water systems having surface water sources or combined surface water and groundwater sources shall take one sample annually at each sampling point. If a waiver from cyanide monitoring has been granted under par.
(c), cyanide is not required to be sampled for routine monitoring.
NR 809.115(3)(c)
(c) Waiver request. The water supplier may apply to the department for a waiver from the monitoring frequencies specified in par.
(b). Public water systems that use a new water source are not eligible for a waiver until monitoring from the new source has been conducted in at least three compliance periods except that the department may grant a waiver for monitoring of cyanide beginning with initial monitoring, provided the public water system is not vulnerable to contamination because there is no industrial source of cyanide present.
NR 809.115(3)(d)
(d) Waiver evaluation. In determining the appropriate reduced monitoring frequency, the department shall consider all of the following:
NR 809.115(3)(d)3.
3. Other factors which may affect contaminant concentrations such as changes in groundwater pumping rates, changes in the public water system's configuration, changes in the public water system's operating procedures, or changes in stream flows or characteristics.
NR 809.115(3)(e)
(e)
Waiver conditions. The department may grant a waiver if surface water systems have been monitored annually for at least 3 years and groundwater systems have been monitored in at least three compliance periods. At least one of the 3 samples shall have been taken since January 1, 1990. Water suppliers for both surface and groundwater systems shall demonstrate that all previous analytical results were less than the maximum contaminant level. Public water systems that use a new water source are not eligible for a waiver until monitoring from the new source has been conducted in at least three compliance periods. A condition of the waiver shall be the collection of a minimum of one sample while the waiver is effective. The term during which the waiver is effective may not exceed 9 years.
NR 809.115(3)(f)
(f) Monitoring frequency when an MCL has been exceeded. Public water systems which exceed the MCLs in s.
NR 809.11 (2) shall be monitored quarterly beginning in the next quarter after the violation occurred. The department may decrease the quarterly monitoring requirement to the frequencies specified in pars.
(a) and
(b) if the department has determined that the public water system is reliably and consistently below the maximum contaminant level. In no case may the department make this determination unless a groundwater system takes a minimum of 2 quarterly samples and a surface water system takes a minimum of 4 quarterly samples.
