PURPOSE: This rule lists manuals containing acceptable analysis procedures for determination of contaminant levels.

PUBLISHER’S NOTE: The secretary of state has determined that the publication of the entire text of the material which is incorporated by reference as a portion of this rule would be unduly cumbersome or expensive. Therefore, the material which is so incorporated is on file with the agency who filed this rule, and with the Office of the Secretary of State. Any interested person may view this material at either agency’s headquarters or the same will be made available at the Office of the Secretary of State at a cost not to exceed actual cost of copy reproduction. The entire text of the rule is printed here. This note refers only to the incorporated by reference material.

1. (1) Inorganic and Radiological Contaminants. Unless substitute methods are approved by the department, analysis shall be conducted in accordance with the methods listed in the following table. All analytical methods listed in this rule are incorporated by reference. Criteria for analyzing arsenic, barium, beryllium, cadmium, calcium, chromium, copper, lead, nickel, selenium, sodium, and thallium with digestion or directly without digestion, and other analytical test procedures are contained in “Technical Notes on Drinking Water Methods,” EPA-600/R-94-173, October 1994. This document also contains approved analytical test methods which remain available for compliance monitoring until July 1, 1996. These methods will not be available for use after July 1, 1996. This document is available from the National Technical Information Service, NTIS PB95- 104766, U.S. Department of Commerce, 5285 Port Royal Road, Springfield, VA 22161. The toll-free number is 800-553- 6847. Contaminant

Aluminum

Antimony

Arsenic

Asbestos

Barium

Beryllium

Bromate

Bromide

Cadmium

Chloride

Chlorite

Chromium

Color Methodology Method (if appropriate) (if appropriate)

Inductively Coupled Plasma—Emission Spectroscopy

Inductively Coupled Plasma—Mass Spectrometry Atomic Absorption—Platform Technique

Atomic Absorption—Gaseous Hydride Atomic Absorption—Graphite Furnace Inductively Coupled Plasma—Mass Spectrometry Atomic Absorption—Platform Technique

Atomic Absorption—Graphite Furnace

Atomic Absorption—Gaseous Hydride

Atomic Absorption—Platform Inductively Coupled Plasma—Emission Spectroscopy

Inductively Coupled Plasma—Mass Spectrometry

Transmission Electron Microscopy

Inductively Coupled Plasma—Mass Spectrometry Atomic Absorption—Graphite Furnace Atomic Absorption—Direct Aspiration Inductively Coupled Plasma—Emission Spectroscopy

Atomic Absorption—Graphite Furnace

Atomic Absorption—Platform Inductively Coupled Plasma—Emission Spectroscopy

Inductively Coupled Plasma—Mass Spectrometry

Ion Chromatography

Ion Chromatography

Atomic Absorption—Graphite Furnace Atomic Absorption—Platform Inductively Coupled Plasma—Emission Spectroscopy Inductively Coupled Plasma—Mass Spectrometry

Ion Chromatography

Atomic Absorption—Furnace Technique Atomic Absorption—Platform Inductively Coupled Plasma—Emission Spectroscopy

Inductively Coupled Plasma—Mass Spectrometry Reference

200.7 3120 B 200.8 200.9 3113 B 3111 D

D3697-92 3113 B 200.8 200.9

D2972-93C 3113 B D2972-93B 3114 B 200.9 200.7 3120 B 200.8

100.1 100.2

200.8 3113 B 3111 D 200.7 3120 B

D3645-93B 3113 B 200.9 3120 B 200.7 200.8

300.1

300.0 300.1

3113 B 200.9 200.7 200.8

300.0 D4327-91 4500-Cl- D

300.0 300.1

3113 B 200.9 200.7 3120 B 200.8

2120 B Contaminant

Copper

Cyanide

Dissolved Organic Carbon (DOC)

Fluoride

Foaming Agents

Iron

Lead

Manganese

Mercury Methodology Method (if appropriate) (if appropriate)

Atomic Absorption—Furnace Technique

Atomic Absorption—Platform Atomic Absorption—Direct Aspiration

Inductively Coupled Plasma

Inductively Coupled Plasma—Mass Spectrometry

Manual distillation followed by— 1. Amenable Spectrophotometric

1. 2. Spectrophotometric—Manual
2. 3. Spectrophotometric— Manual—Semiautomated
3. 4. Selective Electrode

High-Temperature Combustion Persulfate-Ultraviolet or Heated-Persulfate Oxidation Wet-Oxidation

Colorimetric SPADNS, with distillation Ion Chromatography

Manual Electrode

Automated Alizarin Fluoride Blue, with distillation (complexone)

Automated Ion Selective Electrode

Atomic Absorption—Furnace Technique

Inductively Coupled Plasma—Mass Spectrometry Atomic Absorption—Platform Furnace

Manual cold vapor technique 10 CSR 60-5

Reference

D1688-90C 3113 B 200.9 D1688-90A 3111 B 200.7 3120 B 200.8

4500-CN- C D2036-91B 4500-CN- G D2036-91A 4500-CN- E 1-3300-85

335.4 4500-CN- F

5310 B 5310 C 5310 D

4500-F B&D 300.0 D4327-91 4110B D1179-93B 4500-F- C

4500-F E 129-71W 380-75WE

5540 C

200.7 200.9 3120 B 3111 B 3113 B

D3559-90D 3113 B 200.8 200.9

200.7 200.8 200.9 3120 B 3111 B 3113 B

245.1 D3223-91 3112 B Contaminant

Mercury (cont.)

Nickel

Nitrate

Nitrite

Odor

Operational Monitoring— Disinfection Byproducts— Chlorite

Operational Monitoring— General

Operational Monitoring— Lead and Copper Regulation Methodology Method (if appropriate) (if appropriate)

Automated cold vapor technique Inductively Coupled Plasma—Mass Spectrometry

Atomic Absorption—Direct Aspiration Atomic Absorption—Platform Technique Inductively Coupled Plasma—Emission Spectroscopy

Inductively Coupled Plasma—Mass Spectrometry Atomic Absorption—Graphite Furnace

Manual Cadmium Reduction

Automated Cadmium Reduction

Ion Selective Electrode

Ion Chromatography

Spectrophotometric Automated Cadmium Reduction

Manual Cadmium Reduction

Ion Chromatography

Amperometric Titration

pH Electrometric

Conductivity

Calcium (EDTA Titrimetric)

(Inductively Coupled Plasma)

(Atomic Absorption—Direct Aspiration)

Alkalinity (Titrimetic)

(Electrometric Titration) Reference

245.2 200.8

3111 B 200.9 200.7 3120 B 200.8 3113 B

D3867-90B - E 4500-NO3 353.2 D3867-90A - F 4500-NO3 - D 4500-NO3

300.0 B1011 4110 B D4327-91

- B

4500-NO3 353.2 D3867-90A - F 4500-NO3 D3867-90B - E 4500-NO3 300.0 B1011 D4327-91 4110 B

2150 B

4500-CIO2E

150.1 150.2 D1293-84 4500-H+-B D1125-91A 2510 B D511-93A 3500-Ca-D 200.7 3120 B D511-93B 3111 B D1067-92B 2320 B I-1030-85 Contaminant

Operational Monitoring— Lead and Copper Regulation (cont.)

Operational Monitoring— pH

Operational Monitoring— Residual Disinfectant Monitoring— Chlorine Dioxide

Combined Chlorine

Free Chlorine

Ozone Total Chlorine

Operational Monitoring— Temperature Radionuclides Methodology (if appropriate)

Orthophosphate (unfiltered, no digestion or hydroloysis) (Colorimetric, automated ascorbic acid)

(Colorimetric, ascorbic acid single reagent)

(Colorimetric, phosphomolybdate, automated-segmented flow, automated discrete) (Ion Chromatography)

Silica (Cholorimetric, molybdate blue, automated-segmented flow)

(Colorimetric) (Molybdosilicate) (Heteropoly blue) (Automated method for molybdate-reatine silica) (Inductively Coupled Plasma)

pH Value

Amperometric Method II DPD Method Amperometric Titration

DPD Ferrous Titrimetric DPD Colorimetric Amperometric Titration

DPD Ferrous Titrimetric DPD Colorimetric Syringaldazine (FACTS)

Indigo Amperometric Titration

Low Level Amperometric Titration DPD Ferrous Titrimetric DPD Colorimetric Iodometric Electrode

Thermometric

Examination of Water & Wastewater for Radioactivity Gamma Spectrometry in Water 10 CSR 60-5

Method (if appropriate)

365.1 4500-P-F D515-88A 4500-P-E I-1601-85 I-2601-90 I-2598-85 300.0 D4327-91

I-1700-85 I-2700-85 D859-88 4500-Si-D 4500-Si-E 4500-Si-F 200.7 3120 B

150.1 150.2 D1293-84 4500-H+ B

4500-ClO2 E 4500-ClO2 D 4500-Cl D D 1253-86 4500-Cl F 4500-Cl G 4500-Cl D D 1253-86 4500-Cl F 4500-Cl G 4500-Cl H D 1253-86 4500-O B 4500-Cl D D 1253-86 4500-Cl E 4500-Cl F 4500-Cl G 4500-Cl I

2550 B

D2459 Reference Contaminant

Radionuclides (cont.)

Secondary Contaminants

Selenium

Silver

Sulfate

Thallium

Total Dissolved Solids

Total Organic Carbon (TOC)

Turbidity

Sodium

Ultraviolet Absorption at 254 nm (UV254)

Zinc

Footnotes 1) If approved by the department, systems may also measure residual disinfectant concentrations for chlorine, chloramines, and chlorine dioxide by using DPD colorimetric test kits. 2) A party approved by the department must measure residual disinfectant concentration. 3) Amperometric titration may be used for routine daily monitoring of chlorite at the entrance to the distribution system. Ion chromatography must be used for routine monthly monitoring of chlorite and additional monitoring of chlorite in the distribution system. Methodology Method (if appropriate) (if appropriate)

Microquantities of Uranium in Water by Fluorometry

Atomic Absorption—Hydride Generation

Atomic Absorption—Graphite Furnace

Atomic Absorption—Platform Inductively Coupled Plasma—Mass Spectrometry

Atomic Absorption—Graphite Furnace Inductively Coupled Plasma—Emission Spectroscopy Inductively Coupled Plasma—Mass Spectrometry Atomic Absorption—Platform Technique

Colorimetric—Methylthymol blue Gravimetric Turbidimetric Ion Chromatography

Atomic Absorption—Platform Technique Inductively Coupled Plasma—Mass Spectrometry

High-Temperature Combustion Persulfate-Ultraviolet or Heated-Persulfate Oxidation Wet-Oxidation

Nephelometric

Great Lakes Instruments

Inductively Coupled Plasma Atomic Absorption—Direct Aspiration

Ultraviolet Absorption Reference

D2907

D3859-93A 3114 B D3859-93 3113 B 200.9 200.8

I-3720-85 200.7 200.8 200.9 3120 B 3111 B 3113 B

375.2 2- C, D 4500-SO4 2- F 4500-SO4 300.0

D4327-91

200.9 200.8

2540 C

5310 B 5310 C 5310 D

2130 B 180.1 Method 2

200.7 3111 B

5910 B

200.8 3111 B 4) TOC samples may not be filtered prior to analysis. TOC samples must either be analyzed or must be acidified to achieve pH less than 2.0 by minimal addition of phosphoric or sulfuric acid as soon as practical after sampling, not to exceed twenty-four (24) hours. Acidified TOC samples must be analyzed within twenty-eight (28) days. 5) UV absorption must be measured at 253.7 nm (may be rounded off to 254 nm). Prior to analysis, UV254 samples must be filtered through a 0.45 µm pore-diameter filter. The pH of UV254 samples may not be adjusted. Samples must be analyzed as soon as practical after sampling, not to exceed forty-eight (48) hours. 6) Specific Ultraviolet Absorbance (SUVA). SUVA is equal to the UV absorption at 254 nm (UV254) (measured in m-1) divided by the dissolved organic carbon (DOC) concentration (measured as mg/l)). In order to determine SUVA, it is necessary to separately measure UV254 and DOC. When determining SUVA, systems must use the methods stipulated in subparagraph (7)(D)4.A. of this rule to measure DOC and the method stipulated in subparagraph (7)(D)4.B. of this rule to measure UV254. SUVA must be determined on water prior to the addition of disinfectants/oxidants by the system. DOC and UV254 samples used to determine a SUVA value must be taken at the same time and at the same location. 7) Prior to analysis, DOC samples must be filtered through a 0.45 µm pore-diameter filter. Water passed through the filter prior to filtration of the sample must serve as the filtered blank. This filtered blank must be analyzed using procedures identical to those used for analysis of the samples and must meet the following criteria: DOC < 0.5 mg/L. DOC samples must be filtered through the 0.45 µm pore-diameter filter prior to acidification. DOC samples must either be analyzed or must be acidified to achieve pH less than 2.0 by minimal addition of phosphoric or sulfuric acid as soon as practical after sampling, not to exceed forty-eight (48) hours. Acidified DOC samples must be analyzed within twenty-eight (28) days. (A) References for analytical methods incorporated by reference in 10 CSR 60-5.010(1).

1. 1. “Methods of Chemical Analysis of

Water and Wastes,” EPA Environmental Monitoring and Support Laboratory, Cincinnati, OH 45268 (EPA-600/4-79-020), March 1983. Available from National Technical Information Service, PB84-128677. Methods 150.1, 150.2 and 246.2 are also available from U.S. EPA, EMSL, Cincinnati, OH 45268.

1. 2. Annual Book of ASTM Standards,

Vols. 11.01 and 11.02, 1991, American Society for Testing and Materials, 1916 Race Street, Philadelphia, PA 19103.

1. 3. Standard Methods for the

Examination of Water and Wastewater, 16th edition, American Public Health Association, American Water Works Association, Water Pollution Control Federation, 1985.

1. 4. “Methods for Determination of

Inorganic Substances in Water and Fluvial Sediments,” Techniques of Water-Resources Investigations of the U.S. Geological Survey Books, Book 5, Chapter A1, Third Edition, 1989. Available at Superintendent of Documents, U.S. Government Printing Office, Washington, DC 20402.

1. 5. “Orion Guide to Water and Waste-

water Analysis.” Form WeWWG/5880, p. 5, 1985. Orion Research, Inc., Cambridge, MA 02139.

1. 6. 200.7A “Inductively Coupled Plasma

Atomic Emission Analysis of Drinking Water,” Appendix to Method 200.7, March 1987, U.S. EPA, Environmental Monitoring and Support Laboratory, Cincinnati, OH 45268.

1. 7. “Analytical Method for Determina-

tion of Asbestos Fibers in Water,” Method 100.1, EPA-600/4-83-043, September 1983. Available from National Technical Information Service, PB83-260471.

1. 8. “Waters Test Method for the Deter-

mination of Nitrite/Nitrate in Water Using Single Column Ion Chromatography,” Method B-1011, Millipore Corporation, Waters Chromatography Division, 34 Maple Street, Milford, MA 01757.

1. 9. “Fluoride in Water and Wastewater,”

Industrial Method 129-71W, Technicon Industrial Systems, Tarrytown, NY 10591, December 1972.

1. 10. “Fluoride in Water and Wastewater,”

Industrial Method No. 380-75WE, Technicon Industrial Systems, Tarrytown, NY 10591, February 1976.

1. 11. “Radiochemical Methodology for

Drinking Water,” Environmental Monitoring Support Laboratory, EPA-600/4-75-008, U.S. EPA, Cincinnati, OH 45268.

1. 12. “Procedures for Radiochemical

Analysis of Nuclear Reactor Aqueous Solutions,” H.L. Krieger and S. Gold, EPA-R4- 730014, U.S. EPA, Cincinnati, OH, May 1973.

1. 13. HASL Procedure Manual, edited by

John H. Harley, HASL 300, ERDA Health and Safety Laboratory, New York, NY, 1973.

1. 14. “Determination of and Trace Ele-

ments in Water and Wastes by Inductively Coupled Plasma-Mass Spectrometry,” Method 200.8, version 4.3, August 1990, EPA, Environmental Monitoring and Systems Laboratory, Cincinnati, OH 45268. Available from ORD Publication, CERI, EPA, Cincinnati, OH 45268.

1. 15. “Determination of Metals and Trace

Elements by Stabilized Temperature Graphite Furnace Atomic Absorption Spectrometry,” Method 200.9, version 1.1, August 1990, EPA, Environmental Monitoring and Systems Laboratory, Cincinnati, OH 45268.

1. 16. “Determination of Ozone in Water

by the Indigo Method; A Submitted Standard Method,” Ozone Science and Engineering, Volume 4, pages 169–176, Pergamon Press Ltd., 1982. 10 CSR 60-5

1. 17. Standard Methods for the Examin-

ation of Water and Wastewater, 18th edition, American Public Health Association, American Water Works Association, Water Pollution Control Federation, 1992.

1. 18. “Turbidity,” GLI Method 2, Nov-

ember 2, 1992, Great Lakes Instruments, Inc., 8855 North 55 Street, Milwaukee, WI 53223.

1. 19. Annual Book of ASTM Standards,

Vols. 11.01 and 11.02, 1994, American Society for Testing and Materials, 1916 Race Street, Philadelphia, PA 19103.

1. 20. “Determination of Metals and Trace

Elements in Water and Wastes by Inductively Coupled Plasma-Mass Spectrometry” Method 200.8, August 1990, Revision 3.2 EPA EMSL. Available from U.S. EPA, EMSL Cincinnati, OH 45268.

1. 21. “Determination of Inorganic Ions in

Water by Ion Chromatography” Method 300.8, December 1989, U.S. EPA EMSL. Available from U.S. EPA, EMSL, Cincinnati, OH 45268.

1. 22. “Methods for the Determination of

Metals in Environmental Samples—Supplement I, EPA-600/R-94-111, May 1994.” Available from National Technical Information Service (NTIS) NTIS PB 94-184942, U.S. Department of Commerce, 5285 Port Royal Road, Springfield, VA 22161. The toll free number is (800) 553-6847.

1. 23. “Method 300. Determination of In-

organic Anions in Water by Ion Chromatography.” Inorganic Chemistry Branch, Environmental Monitoring Systems Laboratory, August 1991.

1. 24. Available from the Books and Open-

File Reports Section, United States Geological Survey, Federal Center, Box 25425, Denver, CO 80225-0425.

1. 25. “Methods for the Determination of

Inorganic Substances in Environmental Samples,” EPA-600/R-93-100, August 1993. Available from National Technical Information Service, PB94-121811.

1. 26. 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. Available from ATI, Orion, 529 Main Street, Boston, MA 02129.

1. 27. “Determination of Asbestos Struc-

ture over 10-Fm in Length in Drinking Water,” Method 100.2, EPA-600/R-94-134, June 1994. Available from NTIS, PB94- 201902.

1. 28. Standard Methods for the Examina-

tion of Water and Wastewater, 19th edition, American Public Health Association, 1995. Copies may be obtained from the American Public Health Association, 1015 Fifteenth Street, NW, Washington, DC 20005.

1. 29. Supplement to the 19th Edition of

Standard Methods for the Examination of Water and Wastewater, American Public Health Association, 1996. Copies may be obtained from the American Public Health Association, 1015 Fifteenth Street, NW, Washington, DC 20005.

1. 30. Annual Book of ASTM Standards,

Volume 11.01, American Society for Testing and Materials, 1996 edition. Copies may be obtained from American Society for Testing and Materials, 100 Barr Harbor Drive, West Conshohoken, PA 19428.

1. 31. EPA Method 300.1 is titled “USEPA

Method 300.1, Determination of Inorganic Anions in Drinking Water by Ion Chromatography, Revision 1.0,” U.S. EPA, 1997, EPA/600/R-98/118 (available through NTIS, PB98-169196); also available from: Chemical Exposure Research Branch, Microbiological & Chemical Exposure Assessment Research Division, National Exposure Research Laboratory, U.S. Environmental Protection Agency, Cincinnati, OH 45268, fax number: 513-569-7757, phone number: 513-569- 7586.

1. (2) Organic Contaminants. Unless substitute methods are approved, the following table includes acceptable analysis procedures incorporated by reference for organic contaminants:

Contaminant Method

2,3,7,8-TCDD (Dioxin) 1613 2,4-D 515.1 515.2

2,4,5-TP (Silvex) 515.1 515.2

3-Hydrodroxycarbofuran 531.1 Contaminant

Alachlor

Aldicarb

Aldicarb sulfoxide

Aldicarb sulfone

Aldrin

Atrazine

Benzo(a)pyrene

Butachlor

Carbaryl

Carbofuran

Chlordane

Dalapon

Di(2-ethylhexyl)adipate

Di(2-ethylhexyl)phthalate

Dibromochloropropane (DBCP)

Dicamba

Dieldrin

Dinoseb

Diquat Endothall Endrin

Ethylene dibromide (EDB)

Glyphosate Method Contaminant

Haloacetic Acids (HAA5)

525.2 508.1 Heptachlor 531.1

531.1 Heptachlor epoxide 531.1

Hexachlorobenzene

525.2 508.1

Hexachlorocyclopentadiene

525.2 508.1 525.2 Lindane 550.1

525.2 531.1 Methomyl 531.1 Methoxychlor

Metolachlor

525.2 508.1 515.1 Metribuzin 552.1

525.2 Oxamyl (vydate) 525.2 Pentachlorophenol 504.1

515.1 515.2 Picloram

508.1 Polychlorinated biphenyls 525.2 Aroclors) 515.1 515.2

Aroclors)

549.1 508A (as deca- 548.1 chlorobiphenyl) Propachlor 525.2 508.1 Simazine 504.1 Method

552.1 552.2 6251 B

525.2 508.1

525.2 508.1

525.2 508.1

525.2

508.1

525.2 508.1 531.1

525.2 508.1

508.1 525.2

508.1 525.2 531.1

515.1 515.2 525.2

515.1 515.2

(as

(as

508.1 525.2

508.1 525.2 Contaminant Method

Toxaphene 505

525.2

Total Trihalomethanes (TTHM) 502.2 524.2 551.1 Volatile Organic Chemicals (regulated and unregulated) 502.2 524.2

Footnotes 1) A nitrogen-phosphorous detector should be substituted for the electron capture detector in Method 505 (or another approved method should be used) to determine alachlor, atrazine and simazine, if lower detection limits are required. 2) PCBs are qualitatively identified as Aroclors and measured for compliance purposes as decachlorobiphenyl. Each system which monitors for PCBs shall analyze each sample using either Method 505 or Method 508. 3) Analyses of total trihalomethanes shall be conducted in accordance with these methods and “Technical Notes on Drinking Water Methods,” EPA-600/R94-173, October 1994, which is available at NTIS, PB95-104766. 4) In addition to Methods 502.2 and 524.2, analysis for bromodichloromethane, bromoform, chlorodibromomethane, chloroform, carbon tetrachloride, tetrachlorethylene, 1,1,1-trichloroethane, and trichloroethylene may also be conducted by EPA Method 551. Analysis for 1,2,3-trichloropropane may be conducted by Methods 502.1, 524.2 and 504.1. 5) For method 502.2, if TTHMs are the only analytes being measured, then a photoionization detector is not required.

References for analytical methods incorporated by reference in 10 CSR 60-5.010(2): Methods 505, 507, 508, 508A, 515.1 and 531.1 are in “Methods for the Determination of Organic Compounds in Drinking Water,” EPA-600/4-88-039, December 1988, revised July 1991. Methods 506, 547, 550, 550.1 and 551 are in “Methods for the Determintion of Organic Compounds in Drinking Water—Supplement I,” EPA-600-4-90-020, July 1990. Methods 515.2, 548.1, 549.1, 552.1 and 555 are in “Methods for the Determination of Organic Compounds in Drinking Water—Supplement II,” EPA- 600/R-92-129, August 1992. EPA Method 502.2, 524.2, 551.1, and 552.2 are in “Methods for the Determination of Organic Compounds in Drinking Water—Supplement III,” U.S. EPA, August 1995, EPA/600/R- 95/131. Method 1613 is titled “Tetra-through Octa-Chlorinated Dioxins and Furans by Isotope-Dilution HRGC/HRMS,” EPA-821- B-94-005, October 1994. These documents are available from National Technical Information Service (NTIS) NTIS PB91- 231480, PB91-146027, PB92-207703, PB95- 261616, and PB95-104774, U.S. Department of Commerce, 5285 Port Royal Road, Springfield, VA 22161. The toll free number is (800) 553-6847. Method 6651 shall be followed in accordance with the 18th edition of “Standard Methods for the Examination of Water and Wastewater,” 1992. Available from the American Public Health Association, 1015 Fifteenth Street NW, Washington, DC 20005. 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. Available from the American Public Health Association, 1015 Fifteenth Street NW, Washington, DC 20005. Method 6251 B shall be followed in accordance with the 19th edition of “Standard Methods for the Examination of Water and Wastewater,” 1995. Available from the American Public Health Association, 1015 Fifteenth Street, NW, Washington, DC 20005. EPA Methods 504.1, 508.1 and 525.2 are available from U.S. EPA EMSL, Cincinnati, OH 45268. The phone number is (513) 569-7586. Other analytical test procedures are contained in Technical Notes on Drinking Water Methods, EPA-600/R-94-173, October 1994, NTIS PB95-104766.

502.1 Volatile halogenated organic chemicals in water by purge and trap gas chromatography 502.2 Volatile organic compounds in water by purge and trap capillary column gas chromatography with photoionization and electrolytic conductivity detectors in series 503.1 Volatile aromatic and unsaturated organic compounds in water by purge and trap gas chromatography 504.1 1,2-Dibromoethane (EDB), 1,2- Dibromo-3-chloropropane (DBCP), a n d 1 , 2 , 3 - Tr i c h l o r o p r o p a n e (123TCP) in Water by Microextraction and Gas Chromatography 505 Analysis of organohalide pesticides and commercial polychlorinated biphenyl products (Aroclors) in water by microextraction and gas chromatography 506 Determination of phthalate and adipate esters in drinking water by liquid-liquid extraction or liquid-solid 10 CSR 60-5

extraction and gas chromatography with photoionization detection

507 Determination of nitrogenand phosphorus-containing pesticides in groundwater by gas chromatography with a nitrogen-phosphorus detector 508 Determination of chlorinated pesticides in water by gas chromatography with an electron capture detector 508.1 Determination of chlorinated pesticides, herbicides, and organohalides by liquid-solid extraction and electron capture gas chromatography 508A Screening for polychlorinated biphenyls by perchlorination and gas chromatography (for quantification if detected with Method 505 or 508) 515.1 Determination of chlorinated acids in water by gas chromatography with an electron capture detector, revision 5.0, May 1991 524.1 Measurement of purgeable organic compounds in water by purged column gas chromatography/mass spectrophotometry 524.2 Volatile organic chemicals in water by purge and trap capillary column gas chromatography/mass spectrophotometry 525.2 Determination of organic compounds in drinking water by liquidsolid extraction in capillary column gas chromatography/mass spectrometry 531.1 Measurement of N-methyl carbamoyloximes and N-methyl carbamates in water by direct aqueous injection HPLC with post-column derivatization 547 Analysis of glyphosate in drinking water by direct-aqueous-injection HPLC, with post-column derivatization 548 Determination of endothall in aqueous samples 549.1 Determination of diquat and paraquat in drinking water by liquid-solid extraction and high performance liquid chromatography with ultraviolet detection 550 Determination of polycyclic aromatic hydrocarbons in drinking water by liquid-liquid extraction and HPLC with coupled ultraviolet and fluorescence detection 550.1 Determination of polycyclic aromatic hydrocarbons in drinking water by liquid-solid extraction and HPLC with coupled ultraviolet and fluorescence detection 551 Determination of chlorination disinfection byproducts and chlorinated solvents in drinking water by liquidliquid extraction and gas chromatography with electron-capture detection 551.1 Determination of chlorination disinfection byproducts, chlorinated solvents, and halogenated pesticides/herbicides in drinking water by liquid-liquid extraction and gas chromatography with electron capture detection, Revision 1.0 552.1 Determination of haloacetic acids and dalapon in drinking water by ion exchange liquid-liquid extraction and gas chromatography with an electron capture detector, Revision 1.0 552.2 Determination of haloacetic acids and dalapon in drinking water by liquid-liquid extraction, derivatization and gas chromatography with electron capture detection, Revision 1.0 555 Determination of chlorinated acids in water by high performance liquid chromatography with a photodiode array ultraviolet detector 1613 “Tetra-through Octa-Chlorinated Dioxins and Furans by Isotope Dilution.” This method is available from U.S. EPA-OST, Sample Control Center, P.O. Box 1407, Alexandria, VA 22313. 6251 B Micro Liquid-Liquid Extration Gas Chromatographic Method 6610 Carbamate pesticides 6651 Glyphosate herbicide

1. (3) Microbiological Contaminants. Unless substitute methods are approved, this section
2. (3) lists acceptable analysis procedures for microbiological contaminants. Contaminant Approved Manual or Procedure

3. (A) Escherichia coli. Public water systems must conduct analysis of Escherichia coli in accordance with one (1) of the (E. coli) following analytical methods:

   1. 1. EC medium supplemented with fifty (50) F/ml of 4-methylumbelliferyl-beta-D-glucuronide

4. (MUG) (final concentration). EC medium is described in Standard Methods for the Examination of Water and Wastewater, 1992, American Public Health Association, 18th edition, Method 9221E, p. 9–52, paragraph 1a. MUG may be added to EC medium before autoclaving. EC medium supplemented with fifty (50) F/ml of MUG is commercially available. At least ten (10) ml of EC medium supplemented with MUG must be used. The inner inverted fermentation tube may be omitted. The procedure for transferring a total coliform-positive culture to EC medium supplemented with MUG shall be as specified in 10 CSR 60-5.010(1)(B)2. for transferring a total coliform-positive culture to EC medium. Observe fluorescence with an ultraviolet light (366 nm) in the dark after incubating tube at 44.5 ± 0.2 degrees Celsius for 24 ± 2 hours;

   1. 2. Nutrient agar supplemented with 100 F/ml MUG (final concentration). Nutrient agar is described in Standard Methods for the Examination of Water and Wastewater, 1992, American Public Health Association, 18th edition, p. 9-47 to 9-48. This test is used to determine if a total coliform-positive sample, as determined by the membrane filter technique (MFT) or any other method in which a membrane filter is used, contains E. coli. Transfer the membrane filter containing a total coliform colony(ies) to nutrient agar supplemented with 100 F/ml (final concentration) MUG. After incubating the agar plate at thirty-five degrees Celsius (35°C) for four (4) hours, observe the colony(ies) under ultraviolet light (366 nm) in the dark for fluorescence. If fluorescence is visible, E. coli are present;
   2. 3. Minimal Medium ONPG-MUG (MMO-MUG) Test, as set forth in the article “National Field Evaluation of a Defined Substrate Method for the Simultaneous Detection of Total Coliforms and Escherichia coli from Drinking Water: Comparison with Presence-Absence Techniques” (Edberg et al.), Applied and Environmental Microbiology, Volume 55, pp. 1003–1008, April 1989. (Note: The Autoanalysis Colilert System is an MMO-MUG test.) If the MMO-MUG test is total coliform-positive after a 24-hour incubation, test the medium for fluorescence with a 366-nm ultraviolet light (preferably with a 6-watt lamp) in the dark. If fluorescence is observed, the sample is E. coli-positive. If fluorescence is questionable (cannot be definitively read) after 24 hours incubation, incubate the culture for an additional four (4) hours (but not to exceed 28 hours total). And again test the medium for flouresecence. The MMO-MUG Test with hepes buffer in lieu of phosphate buffer is the only approved formulation for the detection of E. coli;
   3. 4. As an option to paragraph (3)(A)3. of this rule, a system with a total coliform-positive, MUG- negative, MMO-MUG test may further analyze the culture for the presence of E. coli by transferring a 0.1 ml 28-hour MMO-MUG culture to EC Medium + MUG. Observation of the results are described in 40 CFR 141.21(f)(6)(i); or
   4. 5. The Colisure test. A description of the Colisure test may be obtained from the Millipore Corporation, Technical Services Department, 80 Ashby Road, Bedford, MA 01730.

5. (B) Fecal Coliform. 1. Public water systems must conduct fecal coliform analysis in accordance with the following procedure: When the multiple-tube fermentation (MTF) technique or presence-absence (P-A) coliform test is used to test for total coliform, shake the lactose-positive presumptive tube or P-A vigorously and transfer the growth with a sterile three millimeter (3 mm) loop or sterile applicator stick into brilliant green lactose bile broth and EC medium to determine the presence of total and fecal coliforms, respectively. For EPA-approved analytical methods which use a membrane filter, transfer the total coliformpositive culture by one (1) of the following methods: Remove the membrane containing the total coliform colonies from the substrate with a sterile forceps and carefully curl and insert the membrane into a tube of EC medium (the laboratory may first remove a small portion of selected colonies for verification), swab the entire membrane filter surface with a sterile cotton swab and transfer the inoculum to EC medium (do not leave the cotton swab in the EC medium), or inoculate individual total coliformpositive colonies into EC medium. Gently shake the inoculated tubes of EC medium to insure adequate mixing and incubate in a waterbath at 44.5 ± 0.2 degrees Celsius for 24 ± 2 hours. Gas production of any amount in the inner fermentation tube of the EC medium indicates a positive fecal coliform test. The preparation of EC medium is described in Standard Methods for the Examination of Water and Wastewater, 1992, American Public Health Association, 18th edition, Method 9221E, p. 9-2, paragraph 1a. Public water systems need only determine the presence or absence of fecal coliforms; a determination of fecal coliform density is not required. Only this method for fecal coliform is allowed for compliance with 10 CSR 60-4.020(5); or

   1. 2. Standard Methods for the Examination of Water and Wastewater, 1992, American Public Health Association, 18th edition.

      1. A. Fecal coliform most probable number (MPN) procedures, method 9221E, pages 9-52 to 9-53

(Note: A-1 Broth may be held up to three (3) months in a tightly closed screwcap tube at four degrees Celsius (4°C));

1. B. Fecal coliform membrane filter procedure, method 9222D, pages 9-60 to 9-61.

Contaminant (C) Heterotrophic Bacteria.

1. (D) Total Coliform.
2. (4) Sample collection for the contaminants listed in this rule must be conducted using the sample preservation, container and maximum holding time procedures specified in the following table. All other samples for contaminates in 10 CSR 60-5.010 shall be collected in accordance with procedures contained in the appropriate analytical method.

Contaminant Antimony Asbestos Barium Beryllium Cadmium Chromium Copper Preserved Unpreserved Cyanide Fluoride Lead Preserved Unpreserved Mercury Approved Manual or Procedure Standard Methods for the Examination of Water and Wastewater, 1992, American Public Health Association, 18th edition, pour plate method, method 9215B. The time from sample collection to initiation of analysis may not exceed twenty-four (24) hours.

1. 1. The standard sample volume required for total coliform analysis, regardless of analytical method used, is one hundred milliliters (100 ml). The time from sample collection to initiation of analysis may not exceed thirty (30) hours.

2. 2. Standard Methods for the Examination of Water and Wastewater, 1992, American Public Health Association, 18th edition—

   1. A. Fermentation technique, method 9221A, B.

      1. (I) Lactose broth, as commercially available, may be used in lieu of lauryl tryptose broth, if

the system conducts at least twenty-five (25) parallel tests between this medium and lauryl tryptose broth using the water normally tested, and this comparison demonstrates that the false-positive rate for total coliforms, using lactose broth, is less than ten percent (10%).

1. (II) If inverted tubes are used to detect gas production, the media should cover these tubes at

least one-half (1/2) to two-thirds (2/3) after the sample is added.

1. (III) No requirement exists to run the completed phase on ten percent (10%) of all total col-

iform-positive confirmed tubes.

1. B. Membrane filter (MF) technique, method 9222A, B, C.

2. C. Presence-absence (P-A) coliform test, method 9221D.

   1. (I) Six-times formulation strength may be used if the medium is filter-sterilized rather than

autoclaved.

1. (II) No requirement exists to run the completed phase on ten percent (10%) of all total col-

iform-positive confirmed tubes.

1. D. ONPG-MUG Test (also known as the Autoanalysis Colilert System, method 9223).
2. E. Colisure test. The Colisure test must be incubated for twenty-eight (28) hours before exam-

ining the results. If an examination of the results at twenty-eight (28) hours is not convenient, then results may be examined at any time between twenty-eight (28) and forty-eight (48) hours. A description of the Colisure test may be obtained from the Millipore Corporation, Technical Service Department, 80 Ashby Road, Bedford, MA 01730.

Preservative Concentrated HNO3 to pH<2 Cool to 4°C Concentrated HNO3 to pH<2 Concentrated HNO3 to pH<2 Concentrated HNO3 to pH<2 Concentrated HNO3 to pH<2

Concentrated HNO3 to pH<2 NONE Cool to 4°C, NaOH to pH>12 NONE

Concentrated HNO3 to pH<2 NONE Concentrated HNO3 to pH<2

Container P or G P or G P or G P or G P or G P or G

P or G P or G P or G P or G

P or G P or G P or G Holding Time 6 months

6 months 6 months 6 months 6 months

6 months 14 days 14 days 1 month

6 months 14 days 28 days Contaminant Nickel Nitrate Chlorinated Nonchlorinated Nitrite Selenium Thallium

1. (A) If HNO3 cannot be used because of shipping restrictions, sample may be initially preserved by icing and immediately shipping to the laboratory. Upon receipt in the laboratory, the sample must be acidified with concentrated HNO3to pH<2 and held for sixteen

1. (16) hours before analysis. At time of analysis, sample container should be thoroughly rinsed with 1:1 HNO3; washings should be added to the sample.

   1. (B) P = Plastic, hard or soft.
   2. (C) G = Glass, hard or soft.
   3. (D) In all cases samples should be analyzed as soon after collection as possible.
   4. (E) For cyanide see method(s) for the information for preservation.
   5. (F) The system shall take each sample at the same sampling point unless conditions make another sampling point more representative of each source or treatment plant.
   6. (G) If a system draws water from more than one (1) source and the sources are combined before distribution, the system must sample at an entry point to the distribution system during periods of normal operating conditions (that is, when water is representative of all sources being used).

2. (5) The department may reduce the total number of samples a system must analyze by allowing the use of compositing. Composite samples from a maximum of five (5) sampling points are allowed provided that the detection limit of the method used for analysis is less than one-fifth (1/5) of the MCL. For a lower number of composited samples the allowable relationship between the detection limit and MCL will change proportionally. Compositing of samples must be done in the laboratory and the composite sample must be analyzed within fourteen (14) days of collection. If the population served by the system is greater than thirty-three hundred (>3,300) persons, then compositing is permitted only at sampling points within a single system. In systems serving less than or equal to thirty-three hundred (≤3,300) persons, the department may permit compositing among different systems provided the five (5)-sample limit is maintained.

   1. (A) Compositing of samples may be allowed for inorganic chemicals (IOCs) listed Preservative Container P or G Concentrated HNO3 to pH<2

Cool to 4°C P or G P or G Concentrated H2SO4 to pH<2 Cool to 4°C P or G P or G Concentrated HNO3 to pH<2 P or G Concentrated HNO3 to pH<2 in 10 CSR 60-4.030(1) and synthetic organic chemicals (SOCs) listed in 10 CSR 60-4.040 and volatile organic chemicals (VOCs) listed in 10 CSR 60-4.100(2) and unregulated organic and inorganic chemicals listed in 10 CSR 60-4.110(2).

1. (B) If the concentration in the composite sample is greater than or equal to 0.0005 mg/l for any organic contaminant listed in 10 CSR 60-4.100(2), then a follow-up sample must be taken within fourteen (14) days at each sampling point included in the composite. These samples must be analyzed for the contaminants which exceeded 0.0005 mg/l in the composite sample. Resampling is not required for unregulated organic and inorganic chemicals listed in 10 CSR 60-4.110(2).
2. (C) If the concentration in the composite sample detects one (1) or more synthetic organic contaminants listed in subsection (6)(B) of this rule, then a follow-up sample must be taken within fourteen (14) days at each sampling point included in the composite. The follow-up sample must be analyzed for the contaminant(s) detected.
3. (D) If duplicates of the original sample from each sampling point used in the composite are available, the system may use these duplicates instead of resampling. The duplicate must be analyzed and the results reported to the department within fourteen (14) days of collection.

4. (E) Compositing Samples Prior to Gas Chromatograph (GC) Analysis.

   1. 1. Add five milliliter (5 ml) or equal

larger amounts of each sample (up to five (5) samples are allowed) to a twenty-five milliliter (25 ml) glass syringe. Special precautions must be made to maintain zero headspace in the syringe.

1. 2. The samples must be cooled at four

degrees Centigrade (4°C) during this step to minimize volatilization losses.

1. 3. Mix well and draw out a five milliliter

(5 ml) aliquot for analysis.

1. 4. Follow sample introduction, purging

and desorption steps described in the method.

1. 5. If less than five (5) samples are used

for compositing, a proportionately small syringe may be used.

1. (F) Compositing Samples Prior to GC/Mass Spectrophotometer (MS) Analysis. 10 CSR 60-5

   Holding Time 6 months

   28 days 14 days 48 hours 6 months 6 months

   1. 1. Inject five milliliter (5 ml) or equal

larger amounts of each aqueous sample (up to five (5) samples are allowed) into a twentyfive milliliter (25 ml) purging device using the sample introduction technique described in the method.

1. 2. The total volume of the sample in the

purging device must be twenty-five milliliters (25 ml).

1. 3. Purge and desorb as described in the

method.

1. (G) For lead and copper monitoring, composite samples from a maximum of five (5) sampling points per composite sample are allowed with prior approval of the department. The reportable value, as required in 10 CSR 60-7.020, for each of the samples in the composite is the concentration detected multiplied by the number of samples composited. If the concentration in the composite sample is less than the detection limit, the reportable value for each of the samples in the composite is the detection limit multiplied by the number of samples composited. If the ninetieth percentile concentration, calculated in accordance with 10 CSR 60-15.010(3)(C), exceeds the lead and copper action level established in 10 CSR 60-15.010(3)(A) and (B), each of the samples from which the composite was derived must be analyzed individually and reported as required in 10 CSR 60- 7.020.

1. (6) Detection Limits.

   1. (A) Detection limits for inorganic chemical analytical methods are the following:

      Detection Limits for Inorganic Contaminants Detection

Contaminant Method Limit (mg/l) Antimony Atomic Absorption— Furnace Technique 0.003 Atomic Absorption— Platform 0.0008 Inductively Coupled Plasma—Mass Spectrometry 0.0004 Atomic Absorption— Gaseous Hydride 0.001 Asbestos Transmission Electron Microscopy 0.01 million fibers per liter Beryllium Atomic Absorption— Furnace Technique Atomic Absorption— Platform Inductively Coupled Plasma Inductively Coupled Plasma—Mass Spectrometry Cadmium Atomic Absorption— Furnace Technique Inductively Coupled Plasma Chromium Atomic Absorption— Furnace Technique Inductively Coupled Plasma Inductively Coupled Plasma (EPA Method 200.7A) Copper All Methods Except Atomic Absorption Atomic Absorption With Direct Aspiration Cyanide Distillation, Spectrophotometric (screen) Distillation, Automated Spectrophotometric (screen) Distillation, Selective Electrode (screen) Distillation, Amenable, Spectrophotometric (free) Lead All Methods Mercury Manual Cold Vapor Technique Automated Cold Vapor Technique Nickel Atomic Absorption— Furnace Technique Atomic Absorption— Platform Inductively Coupled Plasma Inductively Coupled Plasma—Mass Spectrometry Nitrate Manual Cadmium Reduction Automated Hydrazine Reduction Automated Cadmium Reduction Ion Selective Electrode Ion Chromatography Thallium Atomic Absorption— 0.0002 Furnace Technique Atomic Absorption— 0.00002 Platform Inductively Coupled 0.0003 Plasma—Mass Spectrometry 0.0003

1. (B) Detection limits for SOCs are the following:

0.0001 Contaminant Detection Limit 0.001 2,3,7,8-TCDD (Dioxin) 0.001 2,4-D 2,4,5-TP (Silvex) 0.007 Alachlor Aldicarb 0.001 Aldicarb sulfoxide Aldicarb sulfone 0.0002 Atrazine Benzo(a)pyrene 0.0002 Carbofuran Chlordane 0.02 Dalapon Dibromochloropropane (DBCP) 0.005 Di(2-ethylhexyl)adipate 0.02 Di(2-ethylhexyl)phthalate Dinoseb Diquat 0.02 Endothall 0.001 Endrin Ethylene dibromide (EDB) Glyphosate 0.0002 Heptachlor 0.0002 Heptachlor epoxide Hexachlorobenzene Hexachlorocyclopentadiene 0.001 Lindane 0.0006 Methoxychlor Oxamyl (Vydate) 0.005 Pentachlorophenol Picloram 0.0005 Polychlorinated biphenyls (PCBs) (as decachlorobiphenyl) Aroclor 1016 0.01 Aroclor 1221 0.01 Aroclor 1232 Aroclor 1242 0.05 Aroclor 1248 0.01 Aroclor 1254 0.001 0.0007

0.0003

(mg/l) 0.000000005 0.0001 0.0002 0.0002 0.0005 0.0005 0.0008 0.0001 0.00002 0.0009 0.0002 0.001

0.00002 0.0006 0.0006 0.0002 0.0004 0.009 0.00001 0.00001 0.006 0.00004 0.00002 0.0001 0.0001 0.00002 0.0001 0.002 0.00004 0.0001

0.0001 0.00008 0.02 0.0005 0.0003 0.0001 0.0001 Radium 226, 228 Gross Alpha Tritium Strontium-89 Strontium-90 Iodine-131 Cessium-134 Gross Beta Other radionuclides

AUTHORITY: sections 640.100 RSMo Supp. 2003 and 640.125.1, RSMo 2000.* Original rule filed May 4, 1979, effective Sept. 14, 1979. Amended: Filed April 14, 1981, effective Oct. 11, 1981. Amended: Filed June 2, 1988, effective Aug. 31, 1988. Rescinded and readopted: Filed Dec. 4, 1990, effective July 8, 1991. Rescinded and readopted: Filed March 31, 1992, effective Dec. 3, 1992. Amended: Filed Aug. 4, 1992, effective May 6, 1993. Amended: Filed May 4, 1993, effective Jan. 13, 1994. Amended: Filed Feb. 1, 1996, effective Oct. 30, 1996. Amended: Filed July 1, 1999, effective March 30, 2000. Amended: Filed Dec. 15, 1999, effective Sept. 30, 2000. Amended: Filed April 15, 2003, effective Jan. 30, 2004. *Original authority: 640.100, RSMo 1939, amended 1978, 1981, 1982, 1988, 1989, 1992, 1993, 1995, 1996, 1998, 1999, 2002; and 640.125, RSMo 1978, amended 1998.