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(a) General. (1) Systems must use only the analytical methods specified in this section, or their equivalent as approved by EPA, to demonstrate compliance with the requirements of this subpart and with the requirements of subparts U and V of this part. These methods are effective for compliance monitoring February 16, 1999, unless a different effective date is specified in this section or by the State.
(2) 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 CFR 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. 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). 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). 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). 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). 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, 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, 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. 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 http://www.epa.gov/nerlcwww/ordmeth.htm. 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. 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. 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-ClO2 E-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. 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 International, 1996 or any ASTM edition containing the IBR-approved version of the method may be used. 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. 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 International, 100 Barr Harbor Drive, West Conshohocken, PA 19428-2959.
(b) Disinfection byproducts. (1) Systems must measure disinfection byproducts by the methods (as modified by the footnotes) listed in the following table or one of the alternative methods listed in Appendix A to subpart C of this part:
| Contaminant and methodology1 | EPA method | Standard method2 | SM online9 | ASTM method3 |
| TTHM | ||||
| P&T/GC/EICD & PID | 502.24 | |||
| P&T/GC/MS | 524.2 | |||
| LLE/GC/ECD | 551.1 | |||
| HAA5 | ||||
| LLE (diazomethane) /GC/ECD | 6251 B 5 | 6251 B-94 | ||
| SPE (acidic methanol)/GC/ECD | 552.15 | |||
| 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. 2.06, 326.06 | |||
| IC/ICP-MS | 321.8 6 7 | |||
| Chlorite | ||||
| Amperometric titration | 4500-ClO2 E8 | 4500-ClO2 E-008 | ||
| Spectrophotometry | 327.0 Rev 1.18 | |||
| Ion chromatography | 300.0, 300.1, 317.0 Rev 2.0, 326.0 | D 6581-00 |
1 P&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 Annual Book of ASTM Standards, 2001 or any year containing the cited version of the method, Vol 11.01.
4 If TTHMs are the only analytes being measured in the sample, then a PID is not required.
5 The samples must be extracted within 14 days of sample collection.
6 Ion chromatography & 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).
7 Samples must be preserved at the time of sampling with 50 mg ethylenediamine (EDA)/L of sample and must be analyzed within 28 days.
8 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).
9 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.
(2) Analyses under this section for disinfection byproducts must be conducted by laboratories that have received certification by EPA or the State, except as specified under paragraph (b )(3) of this section. To receive certification to conduct analyses for the DBP contaminants in §§141.64, 141.135, and subparts U and V of this part, the laboratory must:
(b)(2)( i) Analyze Performance Evaluation (PE) samples that are acceptable to EPA or the State at least once during each consecutive 12 month period by each method for which the laboratory desires certification.
(ii) Until March 31, 2007, in these analyses of PE samples, the laboratory must achieve quantitative 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 between a maximum and minimum acceptance limit of 50% and 15% of the study mean.
(iii) 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 | ||
| Chloroform | ±20 | Laboratory must meet all 4 individual THM acceptance limits in order to successfully pass a PE sample for TTHM |
| Bromodichloromethane | ±20 | |
| Dibromochloromethane | ±20 | |
| Bromoform | ±20 | |
| HAA5 | ||
| Monochloroacetic Acid | ±40 | Laboratory must meet the acceptance limits for 4 out of 5 of the HAA5 compounds in order to successfully pass a PE sample for HAA5 |
| Dichloroacetic Acid | ±40 | |
| Trichloroacetic Acid | ±40 | |
| Monobromoacetic Acid | ±40 | |
| Dibromoacetic Acid | ±40 | |
| Chlorite | ±30 | |
| Bromate | ±30 |
(iv) 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 §§141.64, 141.135, and subparts U and V of this part:
| DBP | Minimum reporting level (mg/L)1 | Comments |
| TTHM2 | ||
| Chloroform | 0.0010 | |
| Bromodichloromethane | 0.0010 | |
| Dibromochloromethane | 0.0010 | |
| Bromoform | 0.0010 | |
| HAA52 | ||
| 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 0.0010 | Laboratories that use EPA Methods 317.0 Revision 2.0, 326.0 or 321.8 must meet a 0.0010 mg/L MRL for bromate. |
1 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.
2 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 State.
(3) A party approved by EPA or the State must measure daily chlorite samples at the entrance to the distribution system.
(c) Disinfectant residuals.
(1) Systems must measure residual disinfectant concentration for free chlorine, combined chlorine (chloramines), and chlorine dioxide by the methods listed in the following table or one of the alternative methods listed in Appendix A to subpart C of this part:
| Methodology | SM (19th or 20th ed) | SM Online2 | ASTM method | EPA method | Residual measured1 | |||
| 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 Titration | 4500-Cl E | 4500-Cl E-00 | X | |||||
| 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-Cl O2 E-00 | X | |||||
| Lissamine Green Spectrophotometric | 327.0 Rev 1.1 | X | ||||||
1 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.
2 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.
(2) If approved by the State, systems may also measure residual disinfectant concentrations for chlorine, chloramines, and chlorine dioxide by using DPD colorimetric test kits.
(3) A party approved by EPA or the State must measure residual disinfectant concentration.
(d) Additional analytical methods. Systems required to analyze parameters not included in paragraphs (b) and (c) of this section must use the following methods or one of the alternative methods listed in Appendix A to subpart C of this part. A party approved by EPA or the State must measure these parameters.
(1) Alkalinity. All methods allowed in §141.89(a) for measuring alkalinity.
(2) Bromide. EPA Methods 300.0, 300.1, 317.0 Revision 2.0, 326.0, or ASTM D 6581-00.
(3) 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 with minimal addition of the acid specified in the method or by the instrument manufacturer. Acidified TOC samples must be analyzed within 28 days.
(4) Specific Ultraviolet Absorbance (SUVA). SUVA is equal to the UV absorption at 254nm (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 paragraph (d)(4)(i) of this section to measure DOC and the method stipulated in paragraph (d)(4)(ii) of this section 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.
(i) 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 the 0.45 µm 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.
(ii) Ultraviolet Absorption at 254 nm (UV254). Standard 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 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 48 hours.
(5) pH. All methods allowed in §141.23(k)(1) for measuring pH.
(6) Magnesium. All methods allowed in §141.23(k)(1) for measuring magnesium.
[63 FR 69466 Dec. 16, 1998; 65 FR 20310 Apr. 14, 2000 (Withdrawn June 13, 2000); 66 FR 3776 Jan. 16, 2001; 71 FR 479 Jan. 4, 2006; 71 FR 37168 June 29, 2006; 74 FR 30958 June 29, 2009]