Statutes, codes, and regulations
Rhode Island Administrative Code
Title 216 - Department of healthChapter 50 - Environmental healthSubchapter 05 - Water Quality
Part 1 - Public Drinking Water
Section 216-RICR-50-05-1.21 - Appendix 1

216 R.I. Code R. 216-RICR-50-05-1.21

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Section 216-RICR-50-05-1.21 - Appendix 1
A. MICROBIOLOGY
1. Microbiological Testing - Analytical Methodology. Reference for § 1.6 of this Part - Surface Water and Groundwater Under the Influence of Surface Water and §§ 1.16.4 and 1.17 of this Part - Distribution Samples including Storage Facilities and Groundwater Sources Regulation.
a. The standard sample volume required for total coliform analysis, regardless of analytical method used, is 100 ml.
b. PWS need only determine the presence or absence of total coliforms; a determination of total coliform density is not required.
c. PWS must conduct total coliform analyses in accordance with one of the analytical methods in the following table.

Organism

Methodology1

Citation2

TCR3

SWTR3

Total Coliforms: 4 Enzyme Substrate Method

Chromogenic Substrate Coliform Test ONPG-MUG Test.5

SM 9223

X

X

Colisure Test.6

SM 9223

X

Colilert®, Colilert-18®

SM 9223

X

X

E*Colite® Test.7

X

Colitag® Test.8

X

Readycult® Coliforms 100 Presence/Absence

Test.9

X

Total Coliforms: 4 Membrane Filter Method

Total Coliforms10

EPA 1604; SM 9222 A, B, C

X

X

m-ColiBlue24® Test.11

X

Chromocult® Test.12

X

Coliscan® Test.13

X

X

The procedures shall be done in accordance with the documents listed below [DOUBLE DAGGER]:

[DOUBLE DAGGER] 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. Documents may be inspected at EPA's Drinking Water Docket, EPA West, 1301 Constitution Avenue, NW., EPA West, Room B102, Washington DC 20460 [Telephone: (202) 566-2426]; or at the National Archives and Records Administration (NARA). For information on the availability of this material at NARA, call (202) 741-6030, or go to: http://www.archives.gov/federal_register/code_of_federal_regulations/ibr_locations.html

1 The Director strongly recommends that laboratories evaluate the false-positive and negative rates for the method(s) they use for monitoring total coliforms. The Director also encourages laboratories to establish false- positive and false-negative rates within their own laboratory and sample matrix (drinking water or source water) with the intent that if the method they choose has an unacceptable false-positive or negative rate, another method can be used. The Director suggests that laboratories perform these studies on a minimum of 5% of all total coliform-positive samples, except for those methods where verification/ confirmation is already required, e.g., the M-Endo and LES Endo Membrane Filter Tests, Standard Total Coliform Fermentation Technique, and Presence-Absence Coliform Test. Methods for establishing false-positive and negative-rates may be based on lactose fermentation, the rapid test for [BETA]-galactosidase and cytochrome oxidase, multi-test identification systems, or equivalent confirmation tests. False-positive and false-negative information is often available in published studies and/or from the manufacturer(s).

2 Standard Methods for the Examination of Water and Wastewater, 18th edition (1992), 19th edition (1995), or 20th edition (1998). American Public Health Association, 1015 Fifteenth Street, NW., Washington, DC 20005.

3 TCR = Total Coliform Rule; SWTR = Surface Water Treatment Rule

4 The time from sample collection to initiation of analysis may not exceed 30 hours. Systems are encouraged but not required to hold samples below 10 ºC during transit.

5 The ONPG-MUG Test is also known as the Autoanalysis Collect System.

6 A description of the Colisure Test, Feb 28, 1994, may be obtained from IDEXX Laboratories, Inc., One IDEXX Drive, Westbrook, Maine 04092. The Colisure Test may be read after an incubation time of 24 hours.

7 A description of the E*Colite®Test, "Presence/Absence for Coliforms and E. Coli in Water," Dec 21, 1997, is available from Charm Sciences, Inc., 36 Franklin Street, Malden, MA 02148-4120.

8 Colitag®product for the determination of the presence/absence of total coliforms and E. coli is described in "Colitag® Product as a Test for Detection and Identification of Coliforms and E. coli Bacteria in Drinking Water and Source Water as Required in National Primary Drinking Water Regulations," August 2001, available from CPI International, Inc., 5580 Skylane Blvd., Santa Rosa, CA, 95403, telephone (800) 878-7654, Fax (707) 545-7901

9 The Readycult® Coliforms 100 Presence/Absence Test is described in the document, "Readycult®Coliforms 100 Presence/Absence Test for Detection and Identification of Coliform Bacteria and Escherichla coli in Finished Waters", November 2000, Version 1.0, available from EM Science (an affiliate of Merck KGgA, Darmstadt Germany), 480 S. Democrat Road, Gibbstown, NJ 08027-1297. Telephone: (800) 222-0342

10 Method 1604: Total Coliforms and Escherichia coli in Water by Memberane Filtration Using a Simultaneous Detection Technique (MU Medium) (September 1992). MI agar also may be used. Preparation and use of MI agar is set forth in the article, "New medium for the simultaneous detection of total coliform and Escherichia coli in water" by Brenner, K.P., et. al., 1993, Appl. Environ. Microbiol. 59:3534-3544. Also available from the Office of Water Resource Center (RC-4100T), 1200 Pennsylvania Avenue, NW., Washington, DC 20460, EPA/600/J-99/225. Verification of colonies is not required.

11 A description of the m-ColiBlue24® Test, Aug 17, 1999, is available from the Hach Company, 100 Dayton Avenue, Ames, IA 50010.

12 Membrane Filter Technique using Chromocult® Coliform Agar is described in the document, "Chromocult® Coliform Agar Presence/Absence Membrane Filter Test Method for Detection and Identification of Coliform Bacteria and Escherichla coli in Finished Waters", November 2000, Version 1.0, available from EM Science (an affiliate of Merck KGgA, Darmstadt Germany), 480 S. Democrat Road, Gibbstown, NJ 08027-1297. Telephone: (800) 222-0342

13 A description of the Coliscan® test, August 10, 2000, can be obtained from Micrology Laboratories, LLC P.O.Box 340, Goshen, IN 46527-0340

d. PWS must conduct analysis of Escherichia coli in accordance with one of the following analytical methods:
(1) 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 hours (but not to exceed 28 hours total), and again test the medium for fluorescence. The MMO-MUG Test with hepes buffer in lieu of phosphate buffer is the only approved formulation for the detection of E. coli.
(2) 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.
(3) The membrane filter method with MI agar, a description of which is cited in footnote 6 to the table in § 1.21(A)(1)(c) of this Part.
(4) E*Colite® Test, a description of which is cited in footnote 10 to the table in § 1.21(A)(1)(c) of this Part.
(5) m-ColiBlue24®Test, a description of which is cited in footnote 11 to the table in § 1.21(A)(1)(c) of this Part.
(6) Readycult® Coliforms 100 Presence/Absence Test, a description of which is cited in footnote 13 to the table in § 1.21(A)(1)(c) of this Part.
(7) Membrane Filter Technique using Chromocult® Coliform Agar, a description of which is cited in footnote 14 to the table in § 1.21(A)(1)(c) of this Part.
(8) Colitag®, a description of which is cited in footnote 15 to the table in § 1.21(A)(1)(c) of this Part.
e. The following materials are incorporated by reference in § 1.21 of this Part with the approval of the Director of the Federal Register in accordance with 5 U.S.C. § 552(a) and 1 C.F.R. Part 51 . Copies of the analytical methods cited in Standard Methods for the Examination of Water and Wastewater (18th, 19th, and 20th editions) may be obtained from the American Public Health Association et al.; 1015 Fifteenth Street, NW., Washington, DC 20005-2605. Copies of the MMO-MUG Test, as set forth in the article "National Field Evaluation of a Defined Substrate Method for the Simultaneous Enumeration of Total Coliforms and Escherichia coli from Drinking Water: Comparison with the Standard Multiple Tube Fermentation Method" (Edberg et al.) may be obtained from the American Water Works Association Research Foundation, 6666 West Quincy Avenue, Denver, CO 80235. A description of the Colisure Test may be obtained from the Millipore Corp., Technical Services Department, 80 Ashby Road, Bedford, MA 01730. Copies may be inspected at EPA's Drinking Water Docket; 401 M St., SW.; Washington, DC 20460, or at the National Archives and Records Administration (NARA). For information on the availability of this material at NARA, call (202) 741-6030, or go to: http://www.archives.gov/federal_register/code_of_federal_regulations/ibr_locations.html.
2. Invalidation of Samples
a. A total coliform sample invalidated under this Paragraph does not count towards meeting the minimum monitoring requirements of this Part.
b. The Director will invalidate a total coliform-positive sample and document same in writing only if:
(1) The laboratory establishes that improper sample analysis caused the total coliform-positive result;
(2) The Director determines that the total coliform-positive sample resulted from a domestic or other non-distribution system plumbing problem; or
(3) The Director has substantial grounds to believe that a total coliform-positive result is due to a circumstance or condition which does not reflect water quality in the distribution system. (In this case, the PWS must still collect all repeat samples required.)
c. A total coliform-positive sample will not be invalidated solely on the grounds that all repeat samples are total coliform negative.
d. A laboratory must invalidate a total coliform sample, unless total coliforms are detected, if
(1) The sample produces a turbid culture in the absence of gas production using the method cited in § 1.16.4(A)(5) of this Part;
(2) The sample produces a turbid culture in the absence of an acid reaction; using the method cited in § 1.16.4(A)(5) of this Part; or
(3) It exhibits confluent growth, or produces colonies too numerous to count, using the method cited in § 1.16.4(A)(5) of this Part.
e. If a laboratory invalidates a sample for the above reasons, the PWS must collect another sample from the same location as the original sample within twenty-four (24) hours of being notified of the result. The PWS must continue to re-sample within twenty-four (24) hours and have the samples analyzed until it obtains a valid result. The Director may extend the twenty-four (24)-hour limit on a case-by-case basis if the PWS has a logistical problem in collecting the repeat samples within twenty-four (24) hours that is beyond its control. In the case of a extension, the Director will specify how much time the PWS has to collect the repeat samples.
3. Analytical Methods for Source Water Monitoring

Fecal Indicator1

Methodology

Method Citation

E. coli

Colilert3

9223B2

Colisure

9223B2

Membrane Filter Method with MI

EPA Method 16044

Agar

m-ColiBlue24 Test5

E*Colite Test6

EC-MUG7

9221F2

NA-MUG7

9222G2

Enterococci

Multiple-Tube Technique

9230B2

Membrane Filter Technique

9230C2

Membrane Filter Technique

EPA Method 16008

Enterolert9

Coliphage

Two-Step Enrichment Presence-Absence

EPA Method 160110

Procedure

Single Agar Layer Procedure

EPA Method 160211

1 The time from sample collection to initiation of analysis may not exceed 30 hours. The ground water system is encouraged but is not required to hold samples below 10 °C during transit.

2 Methods are described in Standard Methods for the Examination of Water and Wastewater 20th edition (1998) and copies may be obtained from the American Public Health Association, 1015 Fifteenth Street, NW., Washington, DC 20005-2605.

3 Medium is available through IDEXX Laboratories, Inc., One IDEXX Drive, Westbrook, Maine 04092.

4 EPA Method 1604: Total Coliforms and Escherichia coli in Water by Membrane Filtration Using a Simultaneous Detection Technique (MI Medium); September 2002, EPA 821-R-02-024. Method is available at http://www.epa.gov/nerlcwww/1604sp02.pdf or from EPA's Water Resource Center (RC-4100T), 1200 Pennsylvania Avenue, NW., Washington, DC 20460.

5 A description of the m-ColiBlue24 Test, "Total Coliforms and E. coli Membrane Filtration Method with m- ColiBlue24® Broth," Method No. 10029 Revision 2, August 17, 1999, is available from Hach Company, 100 Dayton Ave., Ames, IA 50010 or from EPA's Water Resource Center (RC- 4100T), 1200 Pennsylvania Avenue, NW., Washington, DC 20460.

6 A description of the E*Colite Test, "Charm E*Colite Presence/Absence Test for Detection and Identification of Coliform Bacteria and Escherichia coli in Drinking Water, January 9, 1998, is available from Charm Sciences, Inc., 659 Andover St., Lawrence, MA 01843-1032 or from EPA's Water Resource Center (RC-4100T), 1200 Pennsylvania Avenue, NW., Washington, DC 20460.

7 EC-MUG (Method 9221F) or NA-MUG (Method 9222G) can be used for E. coli testing step as described in Appendix I - Section 1 A.(6) after use of Standard Methods 9221 B, 9221 D, 9222 B, or 9222 C.

8 EPA Method 1600: Enterococci in Water by Membrane Filtration Using membrane-Enterococcus Indoxyl-[BETA]-D- Glucoside Agar (mEI) EPA 821-R-02-022 (September 2002) is an approved variation of Standard Method 9230C. The method is available at http://www.epa.gov/nerlcwww/1600sp02.pdf or from EPA's Water Resource Center (RC-4100T), 1200 Pennsylvania Avenue, NW., Washington, DC 20460. The holding time and temperature for ground water samples are specified in footnote 1 above, rather than as specified in Section 8 of EPA Method 1600.

9 Medium is available through IDEXX Laboratories, Inc., One IDEXX Drive, Westbrook, Maine 04092. Preparation and use of the medium is set forth in the article "Evaluation of Enterolert for Enumeration of Enterococci in Recreational Waters," by Budnick, G.E., Howard, R.T., and Mayo, D.R., 1996, Applied and Environmental Microbiology, 62:3881-3884

10 EPA Method 1601: Male-specific (F+) and Somatic Coliphage in Water by Two-step Enrichment Procedure; April 2001, EPA 821-R-01-030. Method is available at http://www.epa.gov/nerlcwww/1601ap01.pdf or from EPA's Water Resource Center (RC-4100T), 1200 Pennsylvania Avenue, NW., Washington, DC 20460.

11 EPA Method 1602: Male-specific (F+) and Somatic Coliphage in Water by Single Agar Layer (SAL) Procedure; April 2001, EPA 821-R-01-029. Method is available at http://www.epa.gov/nerlcwww/1602ap01.pdf or from EPA's Water Resource Center (RC-4100T), 1200 Pennsylvania Avenue, NW., Washington, DC 20460.

4. Cyanobacteria Identification and Counting (Screening) and Algal Toxin Monitoring
a. Cyanobacteria identification and enumeration shall be conducted using compound microscopy.
b. Algal toxin monitoring shall be performed using enzyme-linked immunosorbent assay (ELISA) or Liquid Chromatography-Tandem Mass Spectrometry (LC-MS/MS) for microcystin and saxitoxin analyses if the required reporting limits for drinking water (or in this Part) can be achieved.
c. If algal toxin monitoring performed using ELISA determines the concentration of microcystin to be above the safe drinking water health criteria the samples must be reanalyzed using by LC-MS/MS to confirm the microcystin concentration in the sample.
d. Algal toxin monitoring shall be done using LC-MS/MS or ELISA for anatoxin and cylindrospermopsin.
e. If no Rhode Island-certified laboratory is available to perform algal toxin testing, then an EPA-certified laboratory may be used. The R.I.DOH State Health Laboratories may also be used for algal toxin monitoring.
B. CHEMISTRY
1. Inorganic Chemistry References for §§ 1.6, 1.7, 1.16.1 and 1.17.2 of this Part.
a. Surface Water Treatment Rule and Ground Water Rule Monitoring
(1) PWSs which must conduct analyses to meet the requirements of §§ 1.6 and 1.13.4 of this Part for turbidity, temperature and measure residual disinfectant concentrations must use the methods contained in the following table. Residual disinfectant concentrations for free chlorine and combined chorine also may be measured by using DPD colorimetric test kits. ITS free chlorine test strip may also be used for the determination of free chlorine. Use of the test strips is described in Method D99-003, Free Chlorine Species (HOCl- and OCl-) by Test Strip, Revision 3.0, November 21, 2003, available from Industrial Test Systems, Inc., 1875 Langston St., Rock Hill, SC 29730. Free and total chlorine residuals may be measured continuously by adapting a specified chlorine residual method for use with a continuous monitoring instrument provided the chemistry, accuracy and precision remain same. Instruments used for continuous monitoring must be calibrated with a grab sample measurement at least every five (5) days with Method 334.0 at least seven (7) days, or with a protocol approved by the Director.
b. Residual Disinfectant Concentration

Residual

Methodology

SM1

SM

Online2

Other

Free Chlorine

Amperometric Titration

4500-Cl D

4500-Cl D

D1253-863

DPD Ferrous Titrimetric

4500-Cl F

4500-Cl F

DPD Colorimetric

4500-Cl G

4500-Cl G

Syringaldazine (FACTS)

4500-Cl H

4500-Cl H

On-line Chlorine Analyzer

EPA 334.05

Total Chlorine

Amperometric Titration

4500-Cl D

4500-Cl D

D1253-863

Amperometric Titration (low level measurement)

4500-Cl E

4500-Cl E

DPD Ferrous Titrimetric

4500-Cl F

4500-Cl F

DPD Colorimetric

4500-Cl G

4500-Cl G

Iodometric Electrode

4500-Cl I

4500-Cl I

On-line Chlorine Analyzer

EPA 334.05

Combined Chlorine (Chloramines)

Amperometric Titration

4500-Cl D

Chlorine Dioxide

Amperometric Titration

4500-ClO2 C

4500-ClO2 C

DPD Method

4500-ClO2 D

Amperometric Titration

4500-ClO2 E

4500-ClO2 E

Ozone

Indigo Method

4500-O3 B

4500-O3 B

1 All the listed methods are contained in the 18th, 19th, and 20th editions of Standard Methods for the Examination of Water and Wastewater, 1992, 1995, and 1998; the cited methods published in any of these three editions may be used.

2 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.

3 Annual Book of ASTM Standards, Vol. 11.01, 2004; ASTM International; any year containing the cited version of the method may be used. Copies of this method may be obtained from ASTM International, 100 Barr Harbor Drive, P.O. Box C700 West Conshohocken, PA 19428-2959.

4 EPA Method 327.0, Revision 1.1, "Determination of Chlorine Dioxide and Chlorite Ion in Drinking Water Using Lissamine Green B and Horseradish Peroxidase with Detection by Visible Spectrophotometry," USEPA, May 2005, EPA 815-R-05-008. Available online at http://www.epa.gov/safewater/methods/sourcalt.html.

5 EPA Method 334.0. "Determination of Residual Chlorine in Drinking Water Using an On-line Chlorine Analyzer." August 2009. EPA 815-B-09-013. Available at http://epa.gov/safewater/methods/analyticalmethods_ogwdw.html.

c. Turbidity:

Parameter

Methodology

Citation1

Turbidity2

Nephelometric Method

2130B

Nephelometric Method

180.13

Great Lakes Instruments

Method 24

Hach FilterTrak

101335

Footnotes:

The procedures shall be done in accordance with the documents listed below:

1 Except where noted, all methods refer to Standard Methods for the Examination of Water and Wastewater, 18th edition (1992), 19th edition (1995), or 20th edition (1998), American Public Health Association, 1015 Fifteenth Street, NW., Washington, DC 20005. The cited methods published in any of these three editions may be used. In addition, the following online versions may also be used: 2130 B-01. 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.

2 Styrene divinyl benzene beads (e.g., AMCO-AEPA-1 or equivalent) and stabilized formazin (e.g., Hach StablCalTM or equivalent) are acceptable substitutes for formazin.

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

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

5 A description of the Hach FilterTrak Method 10133, Determination of Turbidity by Laser Nephelometry, January 2000, Revision 2.0, can be obtained from; Hach Co., P.O. Box 389, Loveland, CO 80539-0389, telephone: 800-227-4224.

d. Regulated Inorganic Chemical Monitoring
(1) Methodology
(AA) PWSs conducting analyses of inorganic chemicals as required in §§ 1.7, 1.16.0 and 1.17.0 of this Part, shall conduct these analyses in accordance with one of the following analytical methods or their equivalent as determined by EPA. Criteria for analyzing arsenic, barium, beryllium, cadmium, 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, Virginia 22161. The toll-free number is 800-553-6847.

Contaminant

Methodology1

EPA

ASTM2

Standard methods3 (18th, 19th, Ed.)

Standard methods3 (20th Ed.)

Standard methods online4

Other

1. Alkalinity

Titrimetric

D1067-92, 02B

2320 B

2320 B

2320 B-97

Electrometric titration

I-1030-855

2. Antimony

Inductively

Coupled Plasma (ICP)-Mass

Spectrometry

200.86

Hydride-Atomic Absorption

D3697-92, 02.

Atomic

Absorption;

Platform

200.96

Atomic

Absorption;

Furnace

3113 B

3113 B-99

3. Arsenic7

Inductively

Coupled

Plasma8

200.76

3120 B

3120 B

3120 B-99

ICP-Mass

Spectrometry

200.86

Atomic

Absorption;

Platform

200.96

Atomic

Absorption;

Furnace

D2972-97, 03C

3113 B

3113 B-99

Hydride Atomic Absorption

D2972-97, 03B

3114 B

3114 B-97

4. Asbestos

Transmission Electron

Microscopy

100.19

Transmission Electron

Microscopy

100.210

5. Barium

Inductively Coupled Plasma

200.76

3120 B

3120 B

3120 B-99

ICP-Mass

Spectrometry

200.86

Atomic Absorption; Direct

3111 D

3111 D-99

Atomic

Absorption;

Furnace

3113 B

3113 B-99

6. Beryllium

Inductively Coupled Plasma

200.76

3120 B

3120 B

3120 B-99

ICP-Mass

Spectrometry

200.86

Atomic

Absorption;

Platform

200.96

Atomic

Absorption;

Furnace

D3645-97, 03B

3113 B

3113 B-99

7. Cadmium

Inductively Coupled Plasma

200.76

ICP-Mass

Spectrometry

200.86

Atomic

Absorption;

Platform

200.96

Atomic

Absorption;

Furnace

3113 B

3113 B-99

8. Calcium

EDTA titrimetric

D511-93, 03B

3500-Ca D

3500-Ca B

3500-Ca B-97

Atomic Absorption; Direct Aspiration.

D511-93, 03A

3111 B

3111 B-99

Inductively Coupled Plasma

200.76

3120 B

3120 B

3120 B-99

Ion

Chromatogra phy

D6919-03

9.

Chromium

Inductively Coupled Plasma

200.76

3120 B

3120 B

3120 B-99

ICP-Mass

Spectrometry

200.86

Atomic

Absorption;

Platform

200.96

Atomic

Absorption;

Furnace

3113 B

3113 B-99

10. Copper

Atomic

Absorption;

Furnace

D1688-95, 02C

3113 B

3113 B-99

Atomic Absorption; Direct Aspiration

D1688-95, 02A

3111 B

3111 B-99

Inductively Coupled Plasma

200.76

3120 B

3120 B

3120 B-99

ICP-Mass

Spectrometry

200.86

Atomic

Absorption;

Platform

200.96

11.

Conductivity

Conductance

D1125-95 (Reapproved 1999) A

2510 B

2510 B

2510 B-97

12. Cyanide

Manual Distillation followed by:

D2036-98 A

4500-CN-C

4500-CN-C

Spectrophoto metric, Amenable

D2036-98 B

4500-CN-G

4500-CN-G

4500-CN-G-99

Spectrophoto metric Manual

4500-CN-E

4500-CN-E

4500-CN-E-99

I-3300-855

Spectro-photometric Semi-automated

335.411

Selective

Electrode

4500-CN-F

4500-CN-F

4500-CN-F-99

UV, Distillation, Spectrophoto metric

Micro Distillation, Flow Injection, Spectro- photometric.

Ligand Exchange and Amperometry1 4

D6888-04

Kelad a-0112

Quik Che m 10- 204- 00-1- X13

OIA- 1677, DW15

13. Fluoride

Ion

Chromatogra phy

300.011

, 300.116

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-97

Manual

Electrode

D1179-93, 99B

4500-F-C

4500-F-C

4500-F-C-97

Automated Electrode

380-75W E17

Automated Alizarin

4500-F-E

4500-F-E

4500-F-E-97

129-71W17

Capillary Ion Electrophoresis

D650 8, Rev. 218

14. Lead

Atomic

Absorption;

Furnace

D3559-96, 03

D

3113 B

3113 B-99

ICP-Mass spectrometry

200.86

Atomic

Absorption;

Platform.

200.96

Differential Pulse Anodic Stripping Voltametry

Method 10011 9

15.

Magnesium

Atomic

Absorption

D511-93, 03

B

3111 B

3111 B-99

ICP

200.76

3120 B

3120 B

3120 B-99

Complexation Titrimetric Methods

D511-93, 03

A

Ion

Chromatogra phy

D6919-03

3500-Mg E

3500-Mg B

3500-Mg B-97

16. Mercury

Manual, Cold

Vapor

245.16

D3223-95, 02

3112 B

3112 B-99

Automated, Cold Vapor

245.220

ICP-Mass

Spectrometry

200.86

17. Nickel

Inductively Coupled Plasma

200.76

3120 B

3120 B

3120 B-99

ICP-Mass

Spectrometry

200.86

Atomic

Absorption;

Platform

200.96

Atomic

Absorption; Direct

3111 B

3111 B-99

Atomic

Absorption;

Furnace

3113 B

3113 B-99

18. Nitrate

Ion

Chromatography

300.011

300.116

D4327-97, 03

4110 B

4110 B

4110 B-00

B-10112 1

Automated Cadmium Reduction

353.211

D3867-90 A

4500-

NO3 -F

4500-NO3

-F

4500-NO3

-F-00

Ion Selective Electrode

4500-

NO3 -D

4500-NO3

-D

4500-NO3

-D-00

60122

Manual Cadmium Reduction

D3867-90 B

4500-

NO3 -E

4500-NO3

-E

4500-NO3

-E-00

Capillary Ion Electrophoresis

D650 8, Rev. 218

19. Nitrite

Ion

Chromatography

300.011

300.116

D4327-97, 03

4110 B

4110 B

4110 B-00

B- 10112 1

Automated Cadmium Reduction

353.211

D3867-90 A

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-00

Spectrophoto metric

4500-

NO2 -B

4500- NO2-B

4500-NO2

-B-00

Capillary Ion Electrophoresis

D650 8, Rev. 218

20. Ortho- phosphate23

Colorimetric, Automated, Ascorbic Acid

365.111

4500-P F

4500-P F

Colorimetric, ascorbic acid, single reagent

D515-88 A

4500-P E

4500-P E

Colorimetric Phosphomoly bdate

I-1601-855

Automated-segmented flow

I-2601-905

Automated Discrete

I-2598-855

Ion

Chromatography

300.011

300.116

D4327-97, 03

4110 B

4110 B

4110 B-00

Capillary Ion Electrophoresis

D650 8, Rev. 218

21. pH

Electrometric

150.1, 150.220

D1293-95, 99

4500-H+ B

4500-H+ B

4500-H+ B-00

22. Selenium

Hydride-Atomic Absorption

D3859-98, 03 A

3114 B

3114 B-97

ICP-Mass

Spectrometry

200.86

Atomic

Absorption;

Platform

200.96

Atomic

Absorption;

Furnace

D3859-98, 03 A

3113 B

3113 B-99

23. Silica

Colorimetric, Molybdate Blue

I-1700-855

Automated-segmented Flow

I-2700-855

Colorimetric

D859-94, 00

Molybdosilicate

4500-

SiO2 D

4500-SiO2 C

4500-SiO2 C-97

Heteropoly blue

4500-

SiO2 E

4500-SiO2 D

4500-SiO2 D-97

Automated for Molybdate-reactive Silica

4500-

SiO2 F

4500-SiO2 E

4500-SiO2 E-97

Inductively Coupled Plasma

200.76

3120 B

3120 B

3120 B-99

24. Sodium

Inductively Coupled Plasma

200.76

Atomic Absorption; Direct Aspiration

3111 B

3111 B-99

Ion

Chromatography

D6919-03

25. Temperature

Thermometric

2550

2550

2550-00

26. Thallium

ICP-Mass

Spectrometry

200.86

The procedures shall be done in accordance with the documents listed below. The incorporation by reference of the following documents listed in footnotes 2-6, 9-13, and 15-22 was approved by the Director of the Federal Register in accordance with 5 U.S.C. 552(a) and 1 CFR Part 51 . 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. Documents may be inspected at EPA's Drinking Water Docket, EPA West, 1301 Constitution Avenue, NW., Room 3334, Washington, DC 20460 (Telephone: 202-566-2426); or at the National Archives and Records Administration (NARA). For information on the availability of this material at NARA, call 202-741-6030, or go to:

http://www.archives.gov/federal_register/code_of_federal_regulations/ibr_locations.html.

1 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.

2 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.

3 Standard Methods for the Examination of Water and Wastewater, 18th edition (1992), 19th edition (1995), or 20th edition (1998). 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.

4 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.

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 Metals in Environmental Samples--Supplement I," EPA/600/R-94/111, May 1994. Available at NTIS, PB95-125472.

7 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 µL 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.

8 Starting January 23, 2006, analytical methods using the ICP-AES technology may not be used because the detection limits for these methods are 0.008 mg/L or higher. This restriction means that the two ICP-AES methods (EPA Method 200.7 and SM 3120 B) approved for use for the MCL of 0.05 mg/L may not be used for compliance determinations for the revised MCL of 0.010 mg/L. However, prior to January 23, 2006, systems may have compliance samples analyzed with these less sensitive methods.

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-µm In Length In Drinking Water," EPA/600/R-94/134, June 1994. Available at NTIS, PB94- 201902.

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

12 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 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.

13 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.

14 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.

15 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.

16 "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.

17 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 amp; Luebbe, 1025 Busch Parkway, Buffalo Grove, IL 60089.

18 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.

19 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.

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

21 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.

22 The procedure shall be done in accordance with the Technical Bulletin 601 "Standard Method of Test for Nitrate in Drinking Water," July 1994, PN221890-001, Analytical Technology, Inc. Copies may be obtained from ATI Orion, 529 Main Street, Boston, MA 02129.

23 Unfiltered, no digestion or hydrolysis.

(2) Sampling Protocol
(AA) Sample collection for antimony, arsenic, asbestos, barium, beryllium, cadmium, chromium, cyanide, fluoride, mercury, nickel, nitrate, nitrite, selenium, and thallium under this Section shall be conducted using the sample preservation containers and maximum holding time procedures specified in the table below:

Contaminant

Preservative1

Container2

Time3

Antimony

HNO3

P or G

6 months

Arsenic

Conc HNO3 to pH <2

P or G

6 months

Asbestos

4° C

P or G

48 hours4

Barium

HNO3

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

Cyanide

4° C, NaOH

P or G

14 days

Fluoride

None

P or G

1 month

Mercury

HNO3

P or G

28 days

Nickel

HNO3

P or G

6 months

Nitrate

4° C

P or G

48 hours5

Nitrate-Nitrite6

H2SO4

P or G

28 days

Nitrite

4° C

P or G

48 hours

Selenium

HNO3

P or G

6 months

Thallium

HNO3

P or G

6 months

1 For cyanide determinations samples must be adjusted with sodium hydroxide to pH 12 at the time off 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 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. Follow additional (if any) information on preservation, containers or holding times that is specified in method.

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 100.1.

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) Acceptance Criteria. Analysis under this Section shall only be conducted by laboratories that have been certified by EPA or the Director. To receive certification to conduct analyses for antimony, arsenic, asbestos, barium, beryllium, cadmium, chromium, cyanide, fluoride, mercury, nickel, nitrate, nitrite and selenium and thallium, the laboratory must:
(AA) Analyze Performance Evaluation (PE) samples provided by EPA, the Director or by a third party (with the approval of the Director or EPA) at least once a year.
(BB) Acceptance Limits. For each contaminant that has been included in the PE sample and for each method for which the laboratory desires certification achieves quantitative results on the analyses that are within the following acceptance limits:

Contaminant

Acceptance Limit

Antimony

±30 at [GREATER THAN OR EQUAL TO]0.006 mg/1

Arsenic1

±30 at [GREATER THAN OR EQUAL TO]0.003 mg/L

Asbestos

2 standard deviations based on study statistics.

Barium

±15% at [GREATER THAN OR EQUAL TO]0.15 mg/1

Beryllium

±15% at [GREATER THAN OR EQUAL TO]0.001 mg/1

Cadmium

±20% at [GREATER THAN OR EQUAL TO]0.002 mg/1

Chromium

±15% at [GREATER THAN OR EQUAL TO]0.01 mg/1

Cyanide

±25% at [GREATER THAN OR EQUAL TO]0.1 mg/1

Fluoride

±10% at [GREATER THAN OR EQUAL TO]1 to 10 mg/1

Mercury

±30% at [GREATER THAN OR EQUAL TO]0.0005 mg/1

Nickel

±15% at [GREATER THAN OR EQUAL TO]0.01 mg/1

Nitrate

±10% at [GREATER THAN OR EQUAL TO]0.4 mg/1

Nitrite

±15% at [GREATER THAN OR EQUAL TO]0.4 mg/1

Selenium

±20% at [GREATER THAN OR EQUAL TO]0.01 mg/1

Thallium

±30% at [GREATER THAN OR EQUAL TO]0.002 mg/1

1 The arsenic acceptance limit criteria became effective January 23, 2006

(CC) For samples which include lead and copper and for each method for which the laboratory desires certification achieve quantitative results on the analyses that are within the following acceptance limits:
(i) Lead: ±30 percent of the actual amount in the Performance Evaluation sample when the actual amount is greater than or equal to 0.005 mg/L. The Practical Quantitation Level, or PQL for lead is 0.005 mg/L.
(ii) Copper: ±10 percent of the actual amount in the Performance Evaluation sample when the actual amount is greater than or equal to 0.050 mg/L. The Practical Quantitation Level, or PQL for copper is 0.050 mg/L.
(iii) Achieve method detection limits as follows for lead and copper: Lead: 0.001 mg/L must be achieved (only if source water compositing is done under § 1.7.9 of this Part). Copper: 0.001 mg/L or 0.020 mg/L when atomic absorption direct aspiration is used (only if source water compositing is done under § 1.7.9 of this Part).
(DD) The Director has the authority to allow the use of previously collected monitoring data for purposes of monitoring, if the data were collected and analyzed in accordance with the requirements in § 1.7.10 of this Part.
(EE) All lead levels measured between the PQL and MDL must be either reported as measured or they can be reported as one-half the PQL (0.0025mg/L). All levels below the lead MDL must be reported as zero.
(FF) All copper levels measured between the PQL and MDL must be either reported as measured or they can be reported as one-half the PQL (0.025 mg/L). All levels below the copper MDL must be reported as zero.
2. Volatile Organic Chemistry (VOCs). References for §§ 1.16.2, 1.17.3 and 1.17.5 of this Part.
a. Regulated Volatile Organic Chemicals
(1) Methodology
(AA) PWSs conducting analyses of inorganic chemicals as listed below and as required in §§ 1.16 and 1.17 of this Part shall conduct these analyses in accordance with one (1) of the following analytical methods or their equivalent as determined by EPA:

Contaminant

Method1

Benzene

502.2; 524.2

Carbon tetrachloride

502.2; 524.2; 551.1

Chlorobenzene

502.2; 524.2

1,2-Dichlorobenzene

502.2; 524.2

1,4-Dichlorobenzene

502.2; 524.2

1,2-Dichloroethane

502.2; 524.2

Cis-Dichloroethylene

502.2; 524.2

Trans-dichloroethylene

502.2; 524.2

Dichloromethane

502.2; 524.2

1,2-Dichloropropane

502.2; 524.2

Ethylbenzene

502.2; 524.2

Styrene

502.2; 524.2

Tetrachloroethylene

502.2; 524.2; 551.1

1,1,1-Trichloroethane

502.2; 524.2; 551.1

Trichloroethylene

502.2; 524.2; 551.1

Toluene

502.2; 524.2

1,2,4-Trichlorobenzene

502.2; 524.2

1,1-Dichloroethylene

502.2; 524.2

1,1,2-Trichloroethane

502.2; 524.2; 551.1

Vinyl chloride

502.2; 524.2

Xylenes (total)

502.2; 524.2

1 Methods 502.2, 524.2 and 551.1 are in Methods for the Determination of Organic Compounds in Drinking Water--Supplement III, EPA/600/R-95-131, August 1995

b. Certification Criteria. To receive certification to conduct analyses for the contaminants listed in § 1.21 of this Part above the laboratory must:
(1) Analyze Performance Evaluation (PE) samples provided by EPA, the Director, or by a third party (with the approval of the Director or EPA) at least once a year by each method for which the laboratory desires certification.
(2) Achieve the quantitative acceptance limits under §§ 1.21(B)(2)(b) ((3)) and ((4)) of this Part for at least 80 percent of the regulated organic chemicals included in the PE sample.
(3) Achieve quantitative results on the analyses performed under § 1.21(B)(2)(b) ((1)) of this Part that are within ±20% of the actual amount of the substances in the Performance Evaluation sample when the actual amount is greater than or equal to 0.010 mg/1.
(4) Achieve quantitative results on the analyses performed under § 1.21(B)(2)(b) ((1)) of this Part that are within ±40 percent of the actual amount of the substances in the Performance Evaluation sample when the actual amount is less than 0.010 mg/1.
(5) Achieve a method detection limit of 0.0005 mg/1.
(6) To receive certification for vinyl chloride, the laboratory must:
(AA) Analyze Performance Evaluation (PE) samples w provided by EPA, the Director, or by a third party (with the approval of the Director or EPA) at least once a year by each method for which the laboratory desires certification.
(BB) Achieve quantitative results on the analyses performed under Paragraph ref of this Section that are within ±40 percent of the actual amount of vinyl chloride in the Performance Evaluation sample.
(CC) Achieve a method detection limit of 0.0005 mg/1.
(DD) Obtain certification for the contaminants listed in § 1.21 of this Part.
c. Total Trihalomethane Chemistry
(1) Methodology
(AA) Sampling and analyses made pursuant to § 1.16 of this Part, shall be conducted by the total trihalomethane methods [502.2, 524.2 or 551.1] as listed in Methods for the Determination of Organic Compounds in Drinking Water--Supplement III, EPA/600/R- 95-131, August 1995.
d. Unregulated Contaminants and Special Monitoring
(1) Unregulated Volatile Organic Contaminants Methodology
(AA) Analysis for the unregulated contaminants listed in 40 C.F.R. § 141.40 shall be conducted using PA Methods 502.2 or 524.2, or their equivalent as determined by EPA, except analysis for romodichloromethane, bromoform, chlorodibromomethane and chloroform may be conducted by EPA Method 551.1, and analysis for 1,2,3- trichloropropane also may be conducted by EPA Method 504.1. Methods 502.2, 524.2, 504.1 and 551.1 are in Methods for the Determination of Organic Compounds in Drinking Water--Supplement III, EPA/600/R-95-131, August 1995.
e. Compositing of Samples: All samples must be composited in the laboratory and analyzed within fourteen (14) days of sample collection.
(1) The following procedure must be followed for the compositing samples prior to GC analysis.
(AA) Add 5 ml or equal larger amounts of each sample (up to 5 samples are allowed) to a 25-ml glass syringe. Special precautions must be made to maintain zero headspace in the syringe.
(BB) The samples must be cooled at 4 degrees C during this step to minimize volatilization losses.
(CC) Mix well and draw out a 5-ml aliquot for analysis.
(DD) Follow sample introduction, purging and desorption steps described in the method.
(EE) If less than five (5) samples are used for compositing, a proportionately small syringe may be used.
(2) The following procedure must be followed for the compositing samples prior to GC/MS analysis.
(AA) Inject 5-ml or equal larger amounts of each aqueous sample (up to 5 samples are allowed) into a 25-ml purging device using the sample introduction technique described in the method.
(BB) The total volume of the sample in the purging device must be 25 ml.
(CC) Purge and desorb as described in the method.
3. Synthetic Organic Chemistry (SOCs) References for §§ 1.16.2, 1.17.3 and 1.17.5 of this Part.
a. Regulated Synthetic Organic Chemicals
(1) Methodology
(AA) PWSs conducting analyses of the inorganic chemicals listed below as required in §§ 1.16 and 1.17 of this Part shall conduct these analyses in accordance with one (1) of the following analytical methods or their equivalent as determined by EPA.
(BB) Methods 508A and 515.1 are in Methods for the Determination of Organic Compounds in Drinking Water, EPA-600/4-88-039, December 1988, Revised, July 1991. Methods 502.2, 504.1, 505, 506, 507, 508, 508.1, 515.2, 524.2 525.2, 531.1, 551.1 and 552.2 are in Methods for the Determination of Organic Compounds in Drinking Water- Supplement III, EPA/600/R-95-131, August 1995.
(CC) Methods 547, 550 and 550.1 are in Methods for the Determination of Organic Compounds in Drinking Water-Supplement I, EPA-600-4-90-020, July 1990.
(DD) Methods 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.
(EE) Method 1613 is titled Tetra-through Octa-Chlorinated Dioxins and Furans by Isotope- Dilution HRGC/HRMS, EPA-821-B-94-005, October 1994. The documents referenced in items ii to v above are available from the National Technical Information Service, NTIS PB91-231480, PB91-146027, PB92-207703, PB95-261616 and PB95-104774, U.S. Department of Commerce, 5285 Port Royal Road, Springfield, Virginia 22161. The toll-free number is: 800-553-6847.
(FF) EPA Methods 515.3 and 549.2 are available from U.S. Environmental Protection Agency, National Exposure Research Laboratory (NERL)-Cincinnati, 26 West Martin Luther King Drive, Cincinnati, OH 45268.
(GG) Methods 6651 and 6610 shall be followed in accordance with Standard Methods for the Examination of Water and Wastewater, 18th edition (1992), 19th edition (1995), or 20th edition (1998), American Public Health Association (APHA); any of these three editions may be used. Copies may be obtained from the American Public Health Association, 1015 Fifteenth Street NW., Washington DC 20005. Other required analytical test procedures germane to the conduct of these analyses are contained in Technical Notes on Drinking Water Methods, EPA-600/R-94-173, October 1994, NTIS PB95-104766. This document also contains approved analytical methods which will not be acceptable after July 1, 1996.
(HH) ASTM Method D 5317-93, 98 (Reapproved 2003) is available in the Annual Book of ASTM Standards, (1999), Vol. 11.02, ASTM International, 100 Barr Harbor Drive, West Conshohocken, PA 19428, any edition containing the cited version of the method may be used.
(II) EPA Method 515.4, Determination of Chlorinated Acids in Drinking Water by Liquid- Liquid Microextraction, Derivatization and Fast Gas Chromatography with Electron Capture Detection, Revision 1.0, April 2000, EPA/815/B-00/001 and EPA Method 552.3, Determination of Haloacetic Acids and Dalapon in Drinking Water by Liquid- Liquid Microextraction, Derivatization, and Gas Chromatography with Electron Capture Detection, Revision 1.0, July 2003, EPA 815-B-03-002, can be accessed and downloaded directly online at http://www.epa.gov/safewater/methods/sourcalt.html.
(JJ) Syngenta Method AG-625, Atrazine in Drinking Water by Immunoassay, February 2001, is available from Syngenta Crop Protection, Inc., 410 Swing Road, P.O. Box 18300, Greensboro, NC 27419. Telephone: 336-632-6000.
(KK) Method 531.2 Measurement of N-methylcarbamoyloximes and N-methylcarbamates in Water by Direct Aqueous Injection HPLC with Postcolumn Derivatization, Revision 1.0, September 2001, EPA 815-B-01-002, can be accessed and downloaded directly online at http://www.epa.gov/safewater/methods/sourcalt.html.

Synthetic Organic Chemicals

Contaminant

EPA Method

Standard Methods

ASTM

Other

2,3,7,8-TCDD (dioxin)

1613

2,4-D3(as acids, salts, and esters)

515.2, 555, 515.1, 515.3, 515.4

D5317-93, 98 (Reapproved 2003)

2,4,5-TP3 (Silvex)

515.2, 555, 515.1, 515.3, 515.4

D5317-93, 98 (Reapproved 2003)

Alachlor1

505, 507, 525.2, 508.1, 551.1

Atrazine1

505, 507, 525.2, 508.1, 551.1

Syngenta 4AG-625

Benzo(a)pyr ene

525.2, 550, 550.1

Carbofuran

531.1, 531.2

6610

Chlordane

505, 508, 525.2, 508.1

Dalapon

552.1, 515.1, 552.2, 515.3, 515.4, 552.3

Di(2-ethylhexyl) adipate

506, 525.2

Di(2-ethylhexyl) phthalate

506, 525.2

Dibromochlo ropropane (DBCP)

504.1, 551.1

Dinoseb3

515.2, 555, 515.1

Diquat

549.2

Endothall

548.1

Endrin

505, 508, 525.2, 508.1, 551.1

Ethylene dibromide (EDB)

504.1, 551.1

Glyphosate

547

6651

Heptachlor

505, 508, 525.2, 508.1, 551.1

Heptachlor Epoxide

505, 508, 525.2, 508.1, 551.1

Hexachlorobenzene

505, 508, 525.2, 508.1, 551.1

Hexachlorocyclopentadiene

505, 525.2, 508, 508.1, 551.1

Lindane

505, 508, 525.2, 508.1, 551.1

Methoxychlor

505, 508, 525.2, 508.1, 551.1

Oxamyl

531.1, 531.2

6610

PCBs2 (as decachlorobi phenyl)

508A

PCBs2 (as Aroclors)

505, 508, 508.1, 525.2

Perfluorodec onoic Acid (PFDA)

533, 537.1

Perfluorohep tanoic Acid (PFHpA)

533, 537.1

Perfluorohex ane sulfonate (PFHxS)

533, 537.1

Perfluoronon oic Acid (PFNA)

533, 537.1

Perfluorooct ane sulfonate (PFOS)

533, 537.1

Perfluorooct anoic Acid (PFOA)

533, 537.1

Pentachloro phenol

515.2, 525.2, 555, 515.1, 515.3, 515.4

D5317-93, 98 (Reapprove d 2003)

Picloram3

515.2, 555, 515.1, 515.3, 515.4

D5317-93, 98 (Reapprove d 2003)

Simazine1

505, 507, 525.2, 508.1, 551.1

Toxaphene

505, 508, 508.1, 525.2

Total Trihalometh anes

502.2, 524.2, 551.1

1 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 phosphorous detector may be used provided all regulatory requirements and quality control criteria are met.

2 PCBs are qualitatively identified as Aroclors and measured for compliance purposes as decachlorobiphenyl. Users of Method 505 may have more difficulty in achieving the required detection limits than users of Methods 508.1, 525.2 or 508

3 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 D5317-93.

4This 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 for atrazine generated by Method AG-625 that is greater than one-half the maximum contaminant level (MCL) (in other words, greater than 0.0015mg/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.

(LL) Polychlorinated biphenyls (PCBs) (as decachlorobiphenyl)
(i) Analysis for PCBs shall be conducted as follows using either Method 505, or Method 508, 508.1or 525.2. Users of Method 505 may have more difficulty in achieving the required Aroclor detection limits than users of Methods 508.1, 525.2 or 508.
(ii) If PCBs (as one (1) of seven (7) Aroclors) are detected (as designated in this Paragraph) in any sample analyzed using Method505 or 508, the PWS shall reanalyze the sample using Method 508A to quantitate PCBs (as decachlorobiphenyl).

Aroclor

Detection limit (mg/L)

1016

0.00008

1221

0.02

1232

0.0005

1242

0.0003

1248

0.0001

1254

0.0001

1260

0.0002

(iii) Compliance with the PCB MCL shall be determined based upon the quantitative results of analysis using Method 508A.
(MM) Per- and Polyfluoroalkyl Substances (PFAS)
(i) Analysis for PFAS shall be conducted using the following methods or their equivalent as approved by the EPA: Method 533 Determination of Per- and Polyfluoroalkyl Substances in Drinking Water by Isotope Dilution Anion Exchange Solid Phase Extraction and Liquid Chromatography/Tandem Mass Spectrometry, November 2019 or Method 537.1 Determination of Selected Per-and Polyfluorinated Alkyl Substances in Drinking Water by Solid Phase Extraction and Liquid Chromatography/Tandem Mass Spectrometry (LC/MS/MS), November 2018.
(2) Laboratory Criteria
(AA) Analysis under this Section shall only be conducted by laboratories that have received certification by EPA or the State and have met the following conditions. To receive certification to conduct analyses for the contaminants in § 1.21 of this Part (SOC's) above the laboratory must:
(i) Analyze Performance Evaluation (PE) samples provided by the State provided by EPA, the Director, or by a third party (with the approval of the Director or EPA) at least once a year by each method for which the laboratory desires certification.
(ii) Achieve quantitative results on the analyses that are within the following acceptance limits:

Contaminant

Acceptance Limits (percent)

Alachlor

±45

Aldicarb

2 standard deviations

Aldicarb sulfoxide

2 standard deviations

Aldicarb sulfone

2 standard deviations

Atrazine

+45

Benzo(a)pyrene

2 standard deviations

Carbofuran

+45

Chlordane

+45

Dalapon

2 standard deviations

Di(2-ethylhexyl)adipate

2 standard deviations

Dibromochloropropane (DBCP)

+40

2,3,7,8-TCDD (Dioxin)

2 standard deviations

2,4-D

±50

2,4,5-TP (Silvex)

±50

Di(2-ethylhexyl) phthalate

2 standard deviations

Dinoseb

2 standard deviations

Diquat

2 standard deviations

Endothall

2 standard deviations

Endrin

±30

Ethylene dibromide (EDB)

±40

Glyphosate

2 standard deviations

Heptachlor

±45

Heptachlor epoxide

±45

Hexachlorobenzene

2 standard deviations

Hexachloro-cyclopentadiene

2 standard deviations

Lindane

±45

Methoxychlor

±45

Oxamyl

2 standard deviations

PCBs (as Decachlorobiphenyl)

0-200

Picloram

2 standard deviations

Pentachlorophenol

±50

Simazine

2 standard deviations

Toxaphene

±45

(iii) Detection shall be defined as greater than or equal to the following concentrations for each contaminant:

Contaminant

Detection Limit (mg/L)

Alachlor

0.0002

Aldicarb

0.0005

Aldicarb sulfoxide

0.0005

Aldicarb sulfone

0.0008

Atrazine

0.0001

Benzo(a)pyrene

0.00002

Carbofuran

0.0009

Chlordane

0.0002

Dalapon

0.001

1,2-Dibromo-3-chloropropane (DBCP)

0.00002

Di(2- ethylhexyl)adipate

0.0006

Di(2-ethylhexyl)phthalate

0.0006

2,4-D

0.0001

Dinoseb

0.0002

Diquat

0.0004

Endothall

0.009

Endrin

0.00001

Ethylene dibromide (EDB)

0.00001

Glyphosate

0.006

Heptachlor

0.00004

Heptachlor epoxide

0.00002

Hexachlorobenzene

0.0001

Hexachloro-cyclopentadiene

0.0001

Lindane

0.00002

Methoxychlor

0.0001

Oxamyl

0.002

PCBs (as

Decachlorobiphenyl)

0.0001

Perfluorodeconoic

Acid (PFDA)

0.000002

Perfluoroheptanoic

Acid (PFHpA)

0.000002

Perfluorohexane sulfonate (PFHxS)

0.000002

Perfluorononoic

Acid (PFNA)

0.000002

Perfluorooctane sulfonate (PFOS)

0.000002

Perfluorooctanoic

Acid (PFOA)

0.000002

Picloram

0.0001

Pentachlorophenol

0.00004

Simazine

0.00007

Toxaphene

0.001

2,3,7,8-TCDD (Dioxin)

0.000000005

2,4,5-TP (Silvex)

0.0002

4. Radiological Chemistry Reference for § 1.16.5 of this Part.
a. Analysis for the contaminants in Table A shall be conducted to determine compliance with § 1.16.5 of this Part in accordance with the methods in Table A, or their equivalent as approved by the Director, with prior approval by EPA.

Contaminant

Methodology

TABLE A: Reference (Method of Page Number)

EPA1

EPA2

EPA3

EPA4

SM5

ASTM6

USGS7

DOE8

Other

Naturally Occurring:

Gross alpha9 and beta

Evaporation

900.0

p. 1

00-01

p. 1

302, 7110 B, 7110 B-00

R-1120-76

Gross alpha9

Coprecipitation

00-02

7110 C, 7110 C-00

Radium 226

Radon emanation

903.1

p. 16

Ra-04

p. 19

305, 7500-Ra C, 7500- Ra C-01

D3454-97

R-1141-76

Ra-04

NY10

Radiochemical

903.0

p. 13

Ra-03

304, 7500-Ra

B, 7500-Ra B-01

D2460-97

R-1140-76

GA12

Radium 228

Radiochemical

904.0

p. 24

Ra-05

p. 19

7500-Ra D, 7500-Ra D-01

R-1142-76

NY10, NJ11, GA12

Uranium13

Radiochemical

908.0

7500-U B,

7500-U B-00

Fluorometric

908.1

7500-U C (17thEd.).

D2907-97

R-1180-76, R-1181-76

U-04

ICP-MS

200.814

3125

D5673-03

Alpha Spectrometry

00-07

p. 33

7500-U C (18th, 19th, or 20th Ed.), 7500-U C-00

D3972-97, 02.

R-1182-76

U-02

Laser

Phosphorimetry

D5174-97, 02

Man-Made:

Radioactive Cesium

Radiochemical

901.0

p. 4

7500-Cs B,

7500-Cs B-00

D2459-72

R-1111-76

Gamma Ray Spectrometry

901.1

p. 92

7120, 7120-97.

D3649- 91, 98a

R-1110-76

4.5.2.3

Radioactive Iodine

Radiochemical

902.0

p. 6

7500-I B, 7500-I B-00

p. 9

7500-I C, 7500-I C-00

7500-I D, 7500-I D-00

D3649- 91, 98a

Gamma Ray Spectrometry

901.1

p. 92

7120, 7120-97

D4785-93, 00a

4.5.2.3

Radioactive Strontium 89, 90

Radiochemical

905.0

p. 29

Sr-04

p. 65

303, 7500-Sr B, 7500-SrB-01

R-1160-76

Sr- 01,Sr-02

Tritium

Liquid Scintillation

906.0

p. 34

H-02

p. 87

306, 7500-3 H B, 7500-3H

B-00

D4107-91, 98 (Re-approve d 2002)

R-1171-76

Gamma Emitters

Gamma Ray Spectrometry

901.1

p. 92

7120, 7120-97.

D3649-91, 98a

R-1110-76

Ga-01-R

902.0

7500Cs B, 7500Cs B-00

D4785-93, 00a

901.0

7500-I B, 7500-I B-00

The procedures shall be done in accordance with the documents listed below.

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. Documents may be inspected at EPA's Drinking Water Docket, EPA West, 1301 Constitution Avenue, NW., Room 3334, Washington, DC 20460 (Telephone: 202-566-2426); or at the National Archives and Records Administration (NARA). For information on the availability of this material at NARA, call 202-741-6030, or go to: http://www.archives.gov/federal_register/code_of_federal_regulations/ibr_locations.html.

1 "Prescribed Procedures for the Measurement of Radioactivity in Drinking Water," EPA 600/4-80-032, August 1980. Available at the U.S. Department of Commerce, National Technical Information Service (NTIS), 5285 Port Royal Road, Springfield, VA 22161 (Telephone 800-553-6847), PB 80-224744.

2 "Interim Radiochemical Methodology for Drinking Water," EPA 600/4-75-008 (revised), March 1976. Available NTIS, ibid.

3 "Radiochemistry Procedures Manual," EPA 520/5-84-006, December 1987. Available NTIS, ibid.

4 "Radiochemical Analytical Procedures for Analysis of Environmental Samples," March 1979. Available at NTIS, ibid. EMSL LV 053917.

5 "Standard Methods for the Examination of Water and Wastewater," 13th, 17th, 18th, 19th or 20th edition, 1971, 1989, 1992, 1995, 1998. Available at American Public Health Association, 1015 Fifteenth Street, NW., Washington, DC 20005. Methods 302, 303, 304, 305 and 306 are only in the 13th edition. Methods 7110B, 7500-Ra B, 7500-Ra C, 7500-Ra D, 7500-U B, 7500-Cs B, 7500-I B, 7500-I C, 7500-I D, 7500-Sr B, and 7500-3H B are in the 17th, 18th, 19th and 20th editions. Method 7110 C is in the 18th, 19th and 20th editions. Method 7500-U C Fluorometric Uranium is only in the 17th Edition, and 7500-U C Alpha spectrometry is only in the 18th, 19th and 20th editions. Method 7120 is only in the 19th and 20th editions. Method 3125 is only in the 20th edition. Methods 7110 B-00, 7110 C-00, 7500-Ra B-01, 7500- Ra C-01, 7500-Ra D-01, 7500-U B-00, 7500-U C-00, 7500-I B-00, 7500-I C-00, 7500-I D-00, 7120-97, 7500-Sr B-01, and 7500-3H B-00 are available online 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.

6 Annual Book of ASTM Standards, Vol. 11.01 and 11.02, 2002; ASTM International; any year containing the cited version of the method may be used. Copies of these two volumes and the 2003 version of D 5673-03 may be obtained from ASTM International, 100 Barr Harbor Drive, P.O. Box C700, West Conshohocken, PA 19428-2959.

7 "Methods for Determination of Radioactive Substances in Water and Fluvial Sediments," Chapter A5 in Book 5 of Techniques of Water-Resources Investigations of the United States Geological Survey, 1977. Available at U.S. Geological Survey (USGS) Information Services, Box 25286, Federal Center, Denver, CO 80225-0425.

8 "EML Procedures Manual," 28th (1997) or 27th (1990) Editions, Volumes 1 and 2; either edition may be used. In the 27th Edition Method Ra-04 is listed as Ra-05 and Method Ga-01-R is listed as Sect. 4.5.2.3. Available at the Environmental Measurements Laboratory, U.S. Department of Energy (DOE), 376 Hudson Street, New York, NY 10014-3621.

9 Natural uranium and thorium-230 are approved as gross alpha calibration standards for gross alpha with co-precipitation and evaporation methods; americium-241 is approved with co-precipitation methods.

10 "Determination of Ra-226 and Ra-228 (Ra-02)," January 1980, Revised June 1982. Available at Radiological Sciences Institute for Laboratories and Research, New York State Department of Health, Empire State Plaza, Albany, NY 12201.

11 "Determination of Radium 228 in Drinking Water," August 1980. Available at State of New Jersey, Department of Environmental Protection, Division of Environmental Quality, Bureau of Radiation and Inorganic Analytical Services, 9 Ewing Street, Trenton, NJ 08625.

12 "The Determination of Radium-226 and Radium-228 in Drinking Water by Gamma-ray Spectrometry Using HPGE or Ge(Li) Detectors," Revision 1.2, December 2004. Available from the Environmental Resources Center, Georgia Institute of Technology, 620 Cherry Street, Atlanta, GA 30332-0335, USA, Telephone: 404- 894-3776. This method may be used to analyze for radium-226 and radium-228 in samples collected after January 1, 2005 to satisfy the radium-226 and radium-228 monitoring requirements specified at 40 CFR 141.26.

13 If uranium (U) is determined by mass, a 0.67 pCi/µg of uranium conversion factor must be used. This conversion factor is based on the 1:1 activity ratio of U-234 and U-238 that is characteristic of naturally occurring uranium.

14 "Determination of Trace Elements in Waters and Wastes by Inductively Coupled Plasma-Mass Spectrometry," Revision 5.4, which is published in ``Methods for the Determination of Metals in Environmental Samples--Supplement I," EPA 600-R-94-111, May 1994. Available at NTIS, PB 95-125472.

b. When the identification and measurement of radionuclides other than those listed in § 1.21(B)(4)(a) of this Part is required, the following references are to be used, except in cases where alternative methods have been approved by the Director.
(1) Procedures for Radiochemical Analysis of Nuclear Reactor Aqueous Solutions, H.L. Krieger and S. Gold, EPA-R4-73-014. USEPA, Cincinnati, Ohio, May 1973.
(2) HASL Procedure Manual, Edited by John H. Harley. HASL 300, ERDA Health and Safety Laboratory, New York, NY., 1973.
c. For the purpose of monitoring radioactivity concentrations in drinking water, the required sensitivity of the radio analysis is defined in terms of a detection limit. The detection limit shall be that concentration which can be counted with a precision of plus or minus 100 percent at the 95 percent confidence level (1.96 s where s is the standard deviation of the net counting rate of the sample).
(1) To determine compliance with §§ 1.16.5(B) and 1.16.5(C) of this Part, the detection limit shall not exceed the concentrations in Table B.

TABLE B Detection Limits for Gross Alpha Particle Activity, Radium 226, Radium 228, and Uranium

Contaminant

Detection Limit

Gross alpha particle activity

3 pCi/l

Radium-226

1 pCi/l

Radium-228

1 pCi/l

Uranium

1 µg/L

(2) To determine compliance with § 1.16.5(D) of this Part, Man-made Beta Particle and Photon Emitters, the detection limits shall not exceed the concentrations listed in Table C.

TABLE C Detection Limits for Man-made Beta Particle and Photon Emitters

Radionuclide

Detection Limit

Tritium

1,000 pCi/l

Strontium-89

10 pCi/l

Strontium-90

2 pCi/l

Iodine-131

1 pCi/l

Cesium-134

10 pCi/l

Gross beta

4 pCi/l

Other radionuclides

1/10 of the applicable limit

(3) To judge compliance with the maximum contaminant levels listed in §§ 1.16.5(B), (C) and (D) of this Part, averages of data shall be used and shall be rounded to the same number of significant figures as the maximum contaminant level for the substance in question.
5. Disinfectant Residuals, Disinfection Byproducts, and Disinfection Byproduct Precursors References for §§ 1.8.4(A) through (D) of this Part.
a. Incorporation by Reference: The following documents are incorporated by reference: The Director of the Federal Register approves this incorporation by reference in accordance with 5 U.S.C. § 552(a) and 1 C.F.R. Part 51 . Copies may be inspected at EPA's Drinking Water Docket, 1301 Constitution Avenue, NW., EPA West, Room B102, Washington, DC 20460, or at the National Archives and Records Administration (NARA). For information on the availability of this material at NARA, call 202-741-6030, or go to: http://www.archives.gov/federal_register/code_of_federal_regulations/ibr_locations.html
(1) EPA Method 552.1 is in Methods for the Determination of Organic Compounds in Drinking Water-Supplement II, USEPA, August 1992, EPA/600/R-92/129 (available through National Information Technical Service (NTIS), PB92-207703).
(2) EPA Methods 502.2, 524.2, 551.1, and 552.2 are in Methods for the Determination of Organic Compounds in Drinking Water-Supplement III, USEPA, August 1995, EPA/600/R-95/131. (available through NTIS, PB95-261616).
(3) EPA Method 300.0 is in Methods for the Determination of Inorganic Substances in Environmental Samples, USEPA, August 1993, EPA/600/R-93/100. (available through NTIS, PB94-121811).
(4) EPA Methods 300.1 and 321.8 are in Methods for the Determination of Organic and Inorganic Compounds in Drinking Water, Volume 1, USEPA, August 2000, EPA 815-R-00- 014 (available through NTIS, PB2000-106981).
(5) EPA Method 317.0, Revision 2.0, "Determination of Inorganic Oxyhalide Disinfection By- Products in Drinking Water Using Ion Chromatography with the Addition of a Postcolumn Reagent for Trace Bromate Analysis," USEPA, July 2001, EPA 815-B-01-001,
(6) EPA Method 326.0, Revision 1.0, "Determination of Inorganic Oxyhalide Disinfection By- Products in Drinking Water Using Ion Chromatography Incorporating the Addition of a Suppressor Acidified Postcolumn Reagent for Trace Bromate Analysis," USEPA, June 2002, EPA 815-R-03-007,
(7) EPA Method 327.0, Revision 1.1, "Determination of Chlorine Dioxide and Chlorite Ion in Drinking Water Using Lissamine Green B and Horseradish Peroxidase with Detection by Visible Spectrophotometry," USEPA, May 2005, EPA 815-R-05-008 and EPA Method 552.3, Revision 1.0, "Determination of Haloacetic Acids and Dalapon in Drinking Water by Liquid-liquid Microextraction, Derivatization, and Gas Chromatography with Electron Capture Detection," USEPA, July 2003, EPA-815-B-03-002 can be accessed and downloaded directly on-line at: http://www.epa.gov/safewater/methods/sourcalt.html.
(8) EPA Method 415.3, Revision 1.1, "Determination of Total Organic Carbon and Specific UV Absorbance at 254 nm in Source Water and Drinking Water," USEPA, February 2005, EPA/600/R-05/055 can be accessed and downloaded directly on-line at: www.epa.gov/nerlcwww/ordmeth.htm.
(9) Standard Methods 4500-Cl D, 4500-Cl E, 4500-Cl F, 4500-Cl G, 4500-Cl H, 4500-Cl I, 4500-ClO2 D, 4500-ClO2 E, 6251 B, and 5910 B shall be followed in accordance with Standard Methods for the Examination of Water and Wastewater, 19th or 20th Editions, American Public Health Association, 1995 and 1998, respectively. The cited methods published in either edition may be used.
(10) Standard Methods 5310 B, 5310 C and 5310 D shall be followed in accordance with the Supplement to the 19th Edition of Standard Methods for the Examination of Water and Wastewater, or the Standard Methods for the Examination of Water and Wastewater, 20th Edition, American Public Health Association, 1996 and 1998, respectively. The cited methods published in either edition may be used. Copies may be obtained from the American Public Health Association, 1015 Fifteenth Street, NW, Washington, DC 20005.
(11) Standard Methods 4500-Cl D-00, 4500-Cl E-00, 4500-Cl F-00, 4500-Cl G-00, 4500-Cl H-00, 4500-Cl I-00, 4500-ClO2E-00, 6251 B-94, 5310 B-00, 5310 C-00, 5310 D-00 and 5910 B-00 are available at http://www.standardmethods.org or at EPA's Water Docket. 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 are IBR-approved.
(12) ASTM Methods D 1253-86 and D 1253-86 (Reapproved 1996) shall be followed in accordance with the Annual Book of ASTM Standards, Volume 11.01, American Society for Testing and Materials, 1996 edition or any ASTM edition containing the IBR-approved version of the method may be used.
(13) ASTM Method D1253-03 shall be followed in accordance with the Annual Book of ASTM Standards, Volume 11.01, American Society for Testing and Materials International, 2004 or any ASTM edition containing the IBR-approved version of the method may be used.
(14) ASTM Method D 6581-00 shall be followed in accordance with the Annual Book of ASTM Standards, Volume 11.01, American Society for Testing and Materials International, 2001 or any ASTM edition containing the IBR-approved version of the method may be used; Copies may be obtained from the American Society for Testing and Materials, 100 Barr Harbor Drive, West Conshohoken, PA 19428-2959.
b. Disinfection Byproducts
(1) Approved Methods for Disinfection Byproduct Compliance Monitoring

Contaminant & Methodology1

EPA Method

Standard Method2

SM Online3

ASTM Method4

TTHM

P&T/GC/ElCD &PID

502.25

P&T/GC/MS

524.2

LLE/GC/ECD

551.1

HAA5

LLE

6251 B6

6251 B-94

(diazomethane)/GC/ECD

SPE (acidic methanol)/

552.16

GC/ECD

LLE (acidic methanol)/ GC/ECD

552.2, 552.3

Bromate

Ion chromatography

300.1

D 6581-00

Ion chromatography & post column reaction

317.0 Rev 2.07, 326.07

IC/ICP-MS

321.87,8

Chlorite

Amperometric titration

4500-ClO2 E9

4500-ClO2 E-009

Spectrophotometry

327.0 Rev 1.19

Ion chromatography

300.0, 300.1,

317.0

D 6581-00

Rev 2.0, 326.0

1 Pamp; T = purge and trap; GC = gas chromatography; ElCD = electrolytic conductivity detector; PID = photoionization detector; MS = mass spectrometer; LLE = liquid/liquid extraction; ECD = electron capture detector; SPE = solid phase extraction; IC = ion chromatography; ICP-MS = inductively coupled plasma/mass spectrometer.

2 19th and 20th editions of Standard Methods for the Examination of Water and Wastewater, 1995 and 1998, respectively, American Public Health Association; either of these editions may be used.

3 The Standard Methods Online version that is approved is indicated by the last two digits in the method number which is the year of approval by the Standard Method Committee. Standard Methods Online are available at: http://www.standardmethods.org.

4 Annual Book of ASTM Standards, 2001 or any year containing the cited version of the method, Vol 11.01.

5 If TTHMs are the only analytes being measured in the sample, then a PID is not required.

6 The samples must be extracted within 14 days of sample collection.

7 Ion chromatography amp; post column reaction or IC/ICP-MS must be used for monitoring of bromate for purposes of demonstrating eligibility of reduced monitoring, as prescribed in § 141.132(b)(3)(ii).

8 Samples must be preserved at the time of sampling with 50 mg ethylenediamine (EDA)/L of sample and must be analyzed within 28 days.

9 Amperometric titration or spectrophotometry may be used for routine daily monitoring of chlorite at the entrance to the distribution system, as prescribed in § 141.132(b)(2)(i)(A). Ion chromatography must be used for routine monthly monitoring of chlorite and additional monitoring of chlorite in the distribution system, as prescribed in § 141.132(b)(2)(i)(B) and (b)(2)(ii).

(2) Analysis under § 1.8.4 of this Part for disinfection byproducts must be conducted by laboratories that have received certification by EPA or the Director, except as specified under § 1.8.4(B)(3) of this Part. To receive certification to conduct analyses for the DBP contaminants in § 1.8.1(A) of this Part, the laboratory must:
(AA) Analyze Performance Evaluation (PE) samples that are acceptable to EPA or the Director at least once during each consecutive twelve (12) month period by each method for which the laboratory desires certification.
(BB) Until March 31, 2007, in these analyses of PE samples, the laboratory must achieve results within the acceptance limit on a minimum of 80% of the analytes included in each PE sample. The acceptance limit is defined as the 95% confidence interval calculated around the mean of the PE study data between a maximum and minimum acceptance limit of ±50% and ± 15% of the study mean.
(CC) Beginning April 1, 2007, the laboratory must achieve quantitative results on the PE sample analyses that are within the following acceptance limits:

DBP

Acceptance Limits (percent of true value)

Comments

TTHM

Laboratory must meet all 4

Chloroform

±20

individual THM acceptance limits

Bromodichloromethane

±20

in order to successfully pass a PE

Dibromochloromethane

±20

sample for TTHM

Bromoform

±20

HAA5

Laboratory must meet the

Monochloroacetic Acid

±40

acceptance limits for 4 out of 5 of the HAA5

Dichloroacetic Acid

±40

compounds in order to successfully pass a PE

Trichloroacetic Acid

±40

sample for HAA5

Monobromoacetic Acid

±40

Dibromoacetic Acid

±40

Chlorite

±30

Bromate

±30

(DD) Beginning April 1, 2007, report quantitative data for concentrations at least as low as the ones listed in the following table for all DBP samples analyzed for compliance with § 1.8.4 of this Part:

DBP

Minimum Reporting Level (mg/L)10

Comments

TTHM11

Chloroform

0.0010

Bromodichloromethane

0.0010

Dibromochloromethane

0.0010

Bromoform

0.0010

HAA511

Monochloroacetic Acid

0.0020

Dichloroacetic Acid

0.0010

Trichloroacetic Acid

0.0010

Monobromoacetic Acid

0.0010

Dibromoacetic Acid

0.0010

Chlorite

0.020

Applicable to monitoring as prescribed

in § 141.132 (b)(2)(1)(B) and (b)(2)(ii).

Bromate

0.0050 or

Laboratories that use EPA Methods

0.0010

317.0 Revision 2.0, 326.0 or 321.8

must meet a 0.0010 mg/L MRL for bromate.

10 The calibration curve must encompass the regulatory minimum reporting level (MRL) concentration. Data may be reported for concentrations lower than the regulatory MRL as long as the precision and accuracy criteria are met by analyzing an MRL check standard at the lowest reporting limit chosen by the laboratory. The laboratory must verify the accuracy of the calibration curve at the MRL concentration by analyzing an MRL check standard with a concentration less than or equal to 110% of the MRL with each batch of samples. The measured concentration for the MRL check standard must be ±50% of the expected value, if any field sample in the batch has a concentration less than 5 times the regulatory MRL. Method requirements to analyze higher concentration check standards and meet tighter acceptance criteria for them must be met in addition to the MRL check standard requirement.

11 When adding the individual trihalomethane or haloacetic acid concentrations to calculate the TTHM or HAA5 concentrations, respectively, a zero is used for any analytical result that is less than the MRL concentration for that DBP, unless otherwise specified by the Director.

c. Analy sis of Disinfec tant Residuals

Methodology

SM (19th or 20th ed)

SM

Online12

ASTM

Method

EPA

Method

Residual Measured13

Free Cl2

Combined Cl2

Total Cl2

ClO2

Amperometric Titration

4500-Cl D

4500-Cl D-00

D 1253-86 (96), 03

X

X

X

Low Level Amperometric

4500-Cl E

4500-Cl E-00

X

Titration

DPD Ferrous Titrimetric

4500-Cl F

4500-Cl F-00

X

X

X

DPD

Colorimetric

4500-Cl G

4500-Cl G-00

X

X

X

Syringaldazine (FACTS)

4500-Cl H

4500-Cl H-00

X

Iodometric Electrode

4500-Cl I

4500-Cl I-00

X

DPD

4500-

ClO2 D

X

Amperometric

Method II

4500-

ClO2 E

4500-ClO2

E-00

X

Lissamine Green Spectro-photometric

327.0

Rev 1.1

X

12 The Standard Methods Online version that is approved is indicated by the last two digits in the method number which is the year of approval by the Standard Method Committee. Standard Methods Online are available at http://www.standardmethods.org.

13 X indicates method is approved for measuring specified disinfectant residual. Free chlorine or total chlorine may be measured for demonstrating compliance with the chlorine MRDL and combined chlorine, or total chlorine may be measured for demonstrating compliance with the chloramine MRDL.

d. Additional Analytical Methods
(1) Bromide. EPA Methods 300.0, 300.1, 317.0 Revision 2.0, 326.0, or ASTM D 6581-00.
(2) Total Organic Carbon (TOC). Standard Method 5310 B or 5310 B-00 (High-Temperature Combustion Method) or Standard Method 5310 C or 5310 C-00 (Persulfate-Ultraviolet or Heated-Persulfate Oxidation Method) or Standard Method 5310 D or 5310 D-00 (Wet- Oxidation Method) or EPA Method 415.3 Revision 1.1. Inorganic carbon must be removed from the samples prior to analysis. TOC samples may not be filtered prior to analysis. TOC samples must be acidified at the time of sample collection to achieve pH less than or equal to 2.0 by minimal addition of the acid specified in the method or by the instrument manufacturer. Acidified TOC samples must be analyzed within twenty-eight (28) days.
(3) Specific Ultraviolet Absorbance (SUVA). In order to determine SUVA, it is necessary to separately measure UV254 and DOC. When determining SUVA, PWSs must use the methods stipulated in § 1.21(B)(5)(d) ((3))((AA)) of this Part to measure DOC and the method stipulated in § 1.21(B)(5)(d) ((3))((BB)) of this Part to measure UV254. SUVA must be determined on water prior to the addition of disinfectants/ oxidants by the PWS. DOC and UV254 samples used to determine a SUVA value must be taken at the same time and at the same location.
(AA) Dissolved Organic Carbon (DOC). Standard Method 5310 B or 5310 B-00 (High- Temperature Combustion Method) or Standard Method 5310 C or 5310 C- 00(Persulfate-Ultraviolet or Heated-Persulfate Oxidation Method) or Standard Method 5310 D or 5310 D-00 (Wet-Oxidation Method) or EPA Method 415.3 Revision 1.1. DOC samples must be filtered through a 0.45 m pore-diameter filter as soon as practical after sampling, not to exceed 48 hours. After filtration, DOC samples must be acidified to achieve pH less than or equal to 2 with minimal addition of the acid specified in the method or by the instrument manufacturer. Acidified DOC samples must be analyzed within 28 days of sample collection. Inorganic carbon must be removed from the samples prior to analysis. 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.
(BB) Ultraviolet Absorption at 254 nm (UV254). Method 5910 B or 5910 B-00 (Ultraviolet Absorption Method) or EPA Method 415.3 Revision 1.1. 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 m 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.

216 R.I. Code R. 216-RICR-50-05-1.21

Amended effective 9/18/2024