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. 26Method 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 Stret, Augusta, ME 04333. (207) 287-2727 27Hach 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. 28Systea Easy (1-Reagent). “Systea Easy (1-Reagent) Nitrate Method,” February 4, 2009. Available at http://www.nemi.gov or from Systea Scientific, LLC., 900 JorieBlvd., Suite 35, Oak Brook, IL 60523. 29Mitchell 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. 30Mitchell 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. 31AMI 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. 32Orion 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. 33Hach 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.
SECTION 23.
NR 809.113 (2) Table B is amended to read: TABLE B Sample Preservation, Containers and Maximum Holding Times for Inorganic Parameters |
Parameter | Preservation1 | Container2 | Holding Time3 |
Aluminum | HNO3 | P or G | 6 months |
Antimony | HNO3 | P or G | 6 months |
Arsenic | Conc.HNO3 to pH<2 | P or G | 6 months |
Beryllium | HNO3 | P or G | 6 months |
Cadmium | HNO3 | P or G | 6 months |
Chromium | HNO3 | P or G | 6 months |
Manganese | HNO3 | P or G | 6 months |
Selenium | HNO3 | P or G | 6 months |
Thallium | HNO3 | P or G | 6 months |
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
Non-Chlorinated |
Cool, 4°C
Cool, 4°C
|
P or G
P or G
|
14 days
48 hours5
|
Nitrite (as N) | Cool, 4°C | P or G | 48 hours |
Nitrate + Nitrite6 | Conc. H2SO4 to pH<2 | P or G | 1428 days |
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 If HNO3 cannot be used because of shipping restrictions, sample may be initially preserved by icing and immediately shipping it to the laboratory. Upon receipt in the laboratory, the sample must be acidified with conc HNO3 to pH < 2. At time of analysis, sample container should be thoroughly rinsed with 1:1 HNO3; washings should be added to sample.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 °C 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. |
SECTION 24.
NR 809.113 (4) Table C is amended to read: 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 Electrode3, 4 | 0.05 |
| | UV, 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 | X10.1 | 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 |
| | Capillary Ion Electrophoresis | 0.076 |
Nitrite | 1 (as N) | Spectrophotometric | 0.01 |
| | Automated Cadmium Reduction | 0.05 |
| | Manual Cadmium Reduction | 0.01 |
| | 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 |
1MFL = million fibers per liter >10 µm.
2Using a 2X preconcentration step as noted in Method 200.7. Lower MDLs may be achieved when using a 4X preconcentration.
3Screening method for total cyanides.
4Measures “free” cyanides when distillation, digestion, or ligand exchange is omitted.
5Lower MDLs are reported using stabilized temperature graphite furnace atomic absorption.
6The MDL reported for EPA method 200.9 (Atomic Absorption; Platform—Stablized 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.
7Using selective ion monitoring, EPA Method 200.8 (ICP-MS) is capable of obtaining a MDL of 0.0001 mg/L.
8Measures total cyanides when UV-digestor is used, and “free” cyanides when UV-digestor is bypassed.
SECTION 25.
NR 809.115 (1) (d)is amended to read: NR 809.115 (1) (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.
SECTION 26.
NR 809.115 (2) (f) 2. is amended to read: NR 809.115 (2) (f) 2. A pubic 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.
SECTION 27.
NR 809.115 (3) (intro) and Title, (a), and (b) are amended to read:
NR 809.115 (3) monitoring frequency for MCLS 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, flouride, mercury, nickel, selenium and thallium at the following 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) 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) 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.
SECTION 28.
NR 809.117 (1) (f) is amended to read: NR 809.117 (1) (f) Pubic Public water systems remain out of compliance with the MCLs for nitrate, nitrite, or combined nitrate and nitrite until the results of 4 consecutive quarterly samples are less than do not exceed the MCL. The department may specify alternate means for returning to compliance with the MCLs for nitrate, nitrite, or combined nitrate and nitrite. Alternate compliance agreements shall be in writing.
SECTION 29.
NR 809.203 (1) and (2) are amended to read:
NR 809.203 (1) Detection Limits. Detection as used in this section shall be defined as greater than or equal to the following concentrations for each contaminant:
Contaminant | Detection Limit (mg/L) |
3. Aldicarb sulfoxide | 0.0005 |
4. Aldicarb sulfone | 0.0008 |
11. Dibromochloropropane | 0.00002 |
12. Di(2-ethylhexyl)adipate | 0.0060.0006 |
13. Di(2-ethylhexyl)phthalate | 0.0060.0006 |
18. Ethylene dibromide | 0.00001 |
21. Heptachlor epoxide | 0.00002 |
22. Hexachlorobenzene | 0.0001 |
23.Hexachlorocyclopentadiene | 0.0001 |
28.Polychlorinated biphenyls (PCBs as decachlorobiphenyls) | 0.0001 |
29. Pentachlorophenol | 0.00004 |
32. 2,3,7,8-TCDD (Dioxin) | 0.000000005 |
33. 2,4,5-TP (Silvex) | 0.0002 |
(2) analytical methods. Analysis for the synthetic organic contaminants listed in s. NR 809.20 shall be conducted using the methods prescribed in Table C CM. SECTION 30.
NR 809.203 (2) Table C is renumbered Table CM and as renumbered is amended to read: TABLE C CM
SDWA Approved Methodology for Synthetic Organic Contaminants
Contaminant | EPA Methods1 | SM9 | SM Online10 | ASTM | Other |
Synthetic Organic Chemicals | | | | | |
2,3,7,8-TCDD (dioxin) | 1613 | 16131 | | | |
2,4-D 2 (as acids, salts and esters) | 515.2, 555, 515.1, 515.3, 515.4 | | | D5317-93, 98 (Reapproved 2003) | |
2,4,5-TP 2 (Silvex) | 515.2, 555, 515.1, 515.3, 515.4 | 6640 B, | 6640 B-01, B-0611 | D5317-93, 98 (Reapproved 2003) | |
Alachlor | 507, 525.2, 525.32 508.1, 5058, 551.1 | | | | |
Atrazine 3 | 507, 525.2, 525.3 508.1, 5058, 551.1, 536 | | | | Syngenta4 AG-625 |
Benzo(a)pyrene | 525.2, 525.3, 550, 550.1 | | | | |
Carbofuran | 531.1, 531.2 | 66105. 6610 B | 6610 B-04 | | |
Chlordane | 508, 525.2, 525.3, 508.1, 505 | | | | |
Dalapon | 552.1 515.1, 552.2, 515.3, 515.4, 552.3, 557 | 6640 B | 6640 B-01, 06 | | |
Di(2-ethylhexyl)adipate | 506, 525.2, 525.3 | | | | |
Di(2-ethylhexyl)phthalate | 506, 525.2, 525.3 | | | | |
Dibromochloropropane (DBCP) | 504.1, 551.1, 524.39 | | | | |
Dinoseb | 515.2, 555, 515.1, 515.3, 515.4 | 6640 B | 6640 B-01, 06 | | |
Endrin | 508, 525.2, 525.3, 508.1, 505, 551.1 | | | | |
Ethylene dibromide (EDB) | 504.1, 551.1, 524.39 | | | | |
Glyphosate | 547 | 66516 6651 B | 6651 B-01, B-06 | | |
Heptachlor | 508, 525.2, 525.3, 508.1, 505, 551.1 | | | | |
Heptachlor Epoxide | 508, 525.2, 525.3, 508.1, 505, 551.1 | | | | |
Hexachlorobenzene | 508, 525.2, 525.3, 508.1, 505, 551.1 | | | | |
Hexachlorocyclopentadiene | 508, 525.2, 525.3, 508.1, 505, 551.1 | | | | |
Lindane | 508, 525.2, 525.3, 508.1, 505, 551.1 | | | | |
Methoxychlor | 508, 525.2, 525.3, 508.1, 505, 551.1 | | | | |
Oxamyl | 531.1, 531.2 | 66105 6610 B | 6610 B-04 | | |
PCBs (as decachlorobiphenyl) | 508A7 | | | | |
(as Aroclors) | 508.1, 508, 525.2, 525.3, 505 | | | | |
Pentachlorophenol | 515.2, 525.2, 525.3, 555, 515.1, 515.3, 515.4 | | | D5317-93, 98 (Reapproved 2003) | |
Picloram 2 | 515.2, 555, 515.1, 515.3, 515.4 | 6640 B | 6640 B-01 | D5317-93, 98 s(Reapproved 2003) | |
Simazine | 507, 525.2, 525.3, 523, 536, 508.1, 5058, 551.1 | | | | |
Toxaphene | 508, 508.1, 525.2, 525.3, 505 | | | | |
Aldicarb | 531.1, 531.2 | 66105 6610 B | 6610 B-04 | | |
Aldicarb sulfone | 531.1, 531.2 | 66105 6610 B | 6610 B-04 | | |
Aldicarb Sulfoxide | 531.1 , 531.2 | 66105 6610 B | 6610 B-04 | | |
Aldrin | 505, 508, 525.2, 525.3, 508.1 | | | | |
Butachlor | 507, 525.2, 525.3 | | | | |
Carbaryl | 531.1, 531.2 | 66105 6610 B | 6610 B-04 | | |
Dicamba | 515.1, 555, 515.2, 515.3, 515.4 | 6640 B | 6640 B-01, B-06 | | |
Dieldrin | 505, 508, 525.2, 525.3, 508.1 | | | | |
3-Hydroxcarbofuran | 531.1, 531.2 | 66105 6610 B | 6610 B-04 | | |
Methomyl | 531.1, 531.2 | 66105 6610 B | 6610 B-04 | | |
Metolachlor | 507, 525.2, 525.3, 508.1 | | | | |
Metribuzin | 507, 525.2, 525.3, 508.1 | | | | |
Propachlor | 507, 525.2, 525.3, 508.1 | | | | |
1 Method 1613, “Tetra− through Octa− Chlorinated Dioxins and Furans by Isotope Dilution. HRGC/HRMS, EPA−821/B−94/005, October 1994, Method 1613 can be used to measure 2, 3, 7, 8−TCDD (dioxin). This method is available from National Technical Information Service, NTIS PB95−104774EPA methods are available at http://epa.gov/safewater/methods/analyticalmethods_ogwdw.html. 2 Accurate determination of the chlorinated esters requires hydrolysis of the sample as described in EPA Methods 515.1, 515.2, 515.3, 515.4 and 555 and ASTM Method D 5317-93, 98 (Reapproved 2003).
3 Substitution of the detector specified in Method 505, 507, 508, or 508.1 for the purpose of achieving lower detection limits is allowed as follows: Either an electron capture or nitrogen phosphorus detector may be used provided all regulatory requirements and quality control criteria are met.
4 This method may not be used for the analysis of atrazine in any system where chlorine dioxide is used for drinking water treatment. In samples from all other systems, any result generated by Method AG-625 that is greater than one-half the maximum contaminant level (MCL) (in other words, greater than 0.0015 mg/L or 1.5 μg/L) must be confirmed using another approved method for this contaminant and should use additional volume of the original sample collected for compliance monitoring. In instances where a result from Method AG-625 triggers such confirmatory testing, the confirmatory result is to be used to determine compliance.
5 Method 6610 shall be followed in accordance with the “Supplement to the 18th edition of Standard Methods for the Examination of Water and Wastewater”, 1994, or with the 19th edition of Standard Methods for the Examination of Water and Wastewater, 1995, APHA; either publication may be used. This incorporation by reference was approved by the Director of the Federal Register in accordance with 5 U.S.C. 552 (a) and 1 CFR Part 51. Copies may be obtained from the American Public Health Association, 1015 Fifteenth Street, N.W., Washington, D.C., 2005. Other required analytical test procedures germane to conducting these analyses are contained in Technical Notes on Drinking Water Methods, EPA/600/R-94-173, October 1994, NTIS PB95-104766. 6 Method 6651 shall be followed in accordance with the “Standard Methods for the Examination of Water and Wastewater”, 18th Edition, 1992, and 19th edition, 1995, American Public Health Association. This incorporation by reference was approved by the Director of the Federal Register in accordance with 5 U.S.C. 552 (a) and 1 CFR Part 51. Copies may be obtained from the American Public Health Association, 1015 Fifteenth Street, N.W., Washington, D.C., 20005. 7 Method 505 or 508 can be used as a screen for PCBs. Method 508A shall be used to quantitate PCBs as decachlorobiphenyl if detected in Method 505 or 508. PCBs are qualitatively identified as Aroclors and measured for compliance purposes as decachlorobiphenyl
8 A nitrogen−phosphorus detector should be substituted for the electron capture detector in Method 505 (or a different approved method should be used) to determine alachlor, atrazine and simizine simazine, if lower detection limits are required.
9 EPA Method 524.3, Version 1.0. “Measurement of Purgeable Organic Compounds in Water by Capillary Column Gas Chromatography/Mass Spectrometry,” June 2009. EPA 815–B–09–009. http://epa.gov/safewater/methods/analyticalmethods_ogwdw.html. Standard Methods for the Examination of Water and Wastewater, 18th edition (1992), 19th edition (1995), 20th edition (1998), 21st edition (2005), 22nd edition (2012). Available from American Public Health Association, 800 I Street, NW., Washington, DC, 20001-3710. 10.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. SECTION 31.
NR 809.203(3)(a) is amended to read:(3) PCB analysis. Analysis for PCBs shall be conducted as follows:
(a) Each water supplier that monitors for PCBs shall have each sample analyzed by a laboratory certified under ch. NR 149 using Method 505, 508, 508.1 or 525.2 as specified in Table C CM and must achieve the required detection limits in this subsection. SECTION 32.
NR 809.203 (4) (intro) is amended to read:
