Section 327IAC8-2.5-5. Analytical requirements; disinfectant residuals, disinfection byproducts, and disinfection byproducts precursors

   (a) Systems shall use only one (1) or more of the analytical methods specified in this subsection or an EPA-approved equivalent method to demonstrate compliance with this rule. These methods are incorporated by reference and may be obtained as follows:

(1) EPA Method 552.1 is in Methods for the Determination of Organic Compounds in Drinking Water-Supplement II, U.S. EPA, 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, U.S. EPA, August 1995, EPA/600/R-95/131 (available through NTIS, PB95-261616).

(3) EPA Methods 300.0 and 150.1 are in Methods for the Determination of Inorganic Substances in Environmental Samples, U.S. EPA, 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, U.S. EPA, 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", U.S. EPA, July 2001, EPA 815-B-01-001 may be accessed and downloaded directly online at http://www.epa.gov/safewater/methods/sourcalt.html.

(6) EPA Method 326.0, Revision 1.0, "Determination of Oxyhalide Disinfection By-Products in Drinking Water Using Ion Chromatography Incorporating the Addition of a Suppressor Acidified Postcolumn Reagent for Trace Bromate Analysis", U.S. EPA, June 2002, EPA 815-R-03-007 may be accessed and downloaded directly online at http://www.epa.gov/safewater/methods/sourcalt.html.

(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", U.S. EPA, May 2005, EPA 815-R-05-008 may be accessed and downloaded directly online at http://www.epa.gov/safewater/methods/sourcalt.html.

(8) EPA Method 552.3, Revision 1.0. "Determination of Haloacetic Acids and Dalapon in Drinking Water by Liquid-liquid Microextraction, Derivitization, and Gas Chromatography with Electron Capture Detection", U.S. EPA, July 2003, EPA 815-B-03-002 may be accessed and downloaded directly online at http://www.epa.gov/safewater/methods/sourcalt.html.

(9) 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", U.S. EPA, February 2005, EPA/600-R-05/055 may be accessed and downloaded directly online at http://www.epa.gov/nerlcwww/ordmeth.html.

(10) EPA Method 200.7 is found in "Methods for the Determination of Metals in Environmental Samples - Supplement I", U.S. EPA, May 1994, EPA 600-R-94-111(available through NTIS PB95-125472).

(11) Standard Methods 3111 B and 3500-Mg E must be followed in accordance with Standard Methods for the Examination of Water and Wastewater, 18th Edition or 19th Edition, American Public Health Association, 1992 and 1995, respectively. The cited method published in either edition may be used. Copies may be obtained from the American Public Health Association, 1015 Fifteenth Street NW, Washington, D.C. 20005.

(12) Standard Method 3120 B must be followed in accordance with the Standard Methods for the Examination of Water and Wastewater, 18th Edition, 19th Edition, or 20th Edition, American Public Health Association, 1992, 1995, and 1998 respectively. The cited method published in any of these three (3) editions may be used. Copies may be obtained from the American Public Health Association, 1015 Fifteenth Street NW, Washington, D.C. 20005.

(13) 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, 4500-H⁺ B, 6251 B, and 5910 B shall be followed in accordance with Standard Methods for the Examination of Water and Wastewater, 19th Edition or 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, D.C. 20005.

(14) Standard Method 3500-Mg B must be followed in accordance with Standard Methods for the Examination of Water and Wastewater, 20th Edition, American Public Health Association, 1998. Copies may be obtained from the American Public Health Association, 1015 Fifteenth Street NW, Washington, D.C. 20005.

(15) 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, American Public Health Association, 1996 or the Standard Methods for the Examination of Water and Wastewater, 20th Edition, 1998. 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, D.C. 20005.

(16) 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 at 1301 Constitution Avenue NW, EPA West, Room B, Washington, D.C. 20460. The year in which each method was approved by the Standard Methods Committee is designated by the last two (2) digits in the method number. The methods listed are the only online versions that are IBR-approved.

(17) 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. Copies may be obtained from the American Society for Testing and Materials, 100 Barr Harbor Drive, West Conshohocken, Pennsylvania 19428.

(18) ASTM Methods D 511-93A and D 511-93B shall be followed in accordance with the Annual Book of ASTM Standards, Volumes 11.01 and 11.02, American Society for Testing and Materials, 1994, 1996, 1999, 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 Conshohocken, Pennsylvania 19428.

(19) ASTM Method D 1253-03 shall be followed in accordance with the Annual Book of ASTM Standards, Volume 11.01, American Society for Testing and Materials, 2004 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 Conshohocken, Pennsylvania 19428.

(20) 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, 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 Conshohocken, Pennsylvania 19428.

These methods are also available for copying at the Indiana Department of Environmental Management, Office of Water Quality, 100 North Senate Avenue, Room N1255, Indianapolis, Indiana 46204.

  (b) Analytical requirements for disinfection byproducts are as follows:

(1) Systems shall measure disinfection byproducts by the methods, as modified by the footnotes, listed in the following tables or with the alternative methods listed in Appendix A to Subpart C of 40 CFR 141:

APPROVED METHODS FOR DISINFECTION BYPRODUCT COMPLIANCE MONITORING
Methodology1	EPA Method	Standard Method	SM Online8	ASTM Method3
P&T/GC/E1CD & PID	502.24
P&T/GC/MS	524.2
LLE/GC/ECD	551.1
LLE (diazomethane)		6251 B5	6251B-94
SPE (acidic methanol)/ GC/ECD	552.15
LLE (acidic methanol)/ GC/ECD	552.2, 552.3
IC and post column reaction	317.0, Rev 2.06, 326.06
IC/ICP-MS	321.86,7
Spectrophotometry	327.0, Rev 1.18
Amperometric titration		4500-ClO2 E8	4500-ClO2 E - 008
IC	300.1, 317.0, Rev 2.0, 326.0
IC	300.1			D6581-00
1P&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 extractor; IC = ion chromatography.
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.
3Annual Book of ASTM Standards, 2001 or any year containing the cited version of the method, Vol 11.01.
4If TTHMs are the only analytes being measured in the sample, then a PID is not required.
5The samples must be extracted within fourteen (14) days of sample collection.
6Ion chromatography and 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 section 6(b)(3)(B) of this rule.
7Samples must be preserved at the time of sampling with fifty (50) mg ethylenediamine (EDA)/L of sample and must be analyzed within twenty-eight (28) days.
8The Standard Methods Online version that is approved is indicated by the last two (2) digits in the method number, which is the year of approval by the Standard Methods Committee. Standard Methods Online are available at http://www.standardmethods.org.

METHODOLOGY APPROVED FOR EACH BYPRODUCT MEASURED1
Methodology1	TTHM	HAA5	Chlorite2	Bromate
P&T/GC/E1CD& PID	X
P&T/GC/MS	X
LLE/GC/ECD	X
LLE (diazomethane)		X
SPE (acidic methanol)/GC/ ECD		X
LLE (acidic methanol)/GC/ ECD		X
IC and post column reaction			X
IC/ICP-MS				X
Spectrophotometry				X
Amperometric titration			X
IC			X
IC			X	X
1X indicates method is approved for measuring specified disinfection byproduct.
2Amperometric titration may be used for routine daily monitoring of chlorite at the entrance to the distribution system, as prescribed in section 6(b)(2)(A)(i) of this rule. Ion chromatography must be used for routine monthly monitoring of chlorite and additional monitoring of chlorite in the distribution system, as prescribed in section 6(b)(2)(A)(ii) and 6(b)(2)(B) of this rule.

(2) Analysis under this subsection for disinfection byproducts must be conducted by laboratories that have received certification by EPA or the commissioner, except as specified under subdivision (3). To receive certification to conduct analyses for the DBP contaminants in sections 2(a) and 9 through 20 of this rule, the laboratory must do the following:

(A) Analyze performance evaluation (PE) samples approved by EPA or the commissioner at least once during each consecutive twelve (12) month period by each method for which the laboratory desires certification.

(B) Until March 31, 2007, in these analyses of PE samples, the laboratory must achieve quantitative results within the acceptance limit on a minimum of eighty percent (80%) of the analytes included in each PE sample. The acceptance limit is defined as the ninety-five percent (95%) confidence interval calculated around the mean of the PE study data between a maximum and minimum acceptance limit of plus or minus fifty percent (50%) and plus or minus fifteen percent (15%) of the study mean.

(C) Beginning April 1, 2007, the laboratory must achieve quantitative results on the PE sample analyses that are within the acceptance limits shown in the following table:

DBP Group	DBP	Acceptance Limits (percent of true value)	Comments
TTHM	Chloroform	+ 20	Laboratory shall meet all four (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 shall meet the acceptance limit for four (4) out of five (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

(D) Beginning April 1, 2007, the laboratory must 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 sections 9 through 20 of this rule:

DBP Group	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 327 IAC 8-2.5-6(b)(2)(A)(ii) and 327 IAC 8-2.5-6(b)(2)(B)
	Bromate	0.0050 or 0.0010	Laboratories that use EPA Methods 317.0, Revision 2.0, 326.0 or 321.8 shall meet 0.010 mg/L MRL for bromate.
1The calibration curve must encompass the regulatory minimum reporting level (MRL) concentration. Data can be reported by 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 shall 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 one hundred ten percent (110%) of the MRL with each batch of samples. The measured concentration of the MRL check standard must be plus or minus fifty percent (+ 50%) of the expected value if any field sample in the batch has a concentration less than five (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.
2When adding the individual THM or haloacetic acid concentrations to calculate the TTHM or HAA5 concentrations, respectively, a zero (0) is used for any analytical result that is less than the MRL for that DBP, unless otherwise specified by the commissioner.

(3) A certified operator or other party as approved by the commissioner shall measure daily chlorite samples at the entrance to the distribution system.

  (c) Analytical requirements for disinfectant residuals are as follows:

(1) A system shall measure residual disinfectant concentrations for free chlorine, combined chlorine (chloramines), and chlorine dioxide by the methods listed in the following tables or with the alternative methods listed in Appendix A to Subpart C of 40 CFR 141:

APPROVED METHODS FOR DISINFECTANT RESIDUAL COMPLIANCE MONITORING
Methodology	Standard Method (19th or 20th Edition)	SM Online1	ASTM Method	EPA Method
Amperometric titration	4500-Cl D	4500-Cl D-00	D 1253-86 (96), 03
Low level amperometric titration	4500-Cl E	4500-Cl E-00
DPD2 ferrous titrimetric	4500-Cl F	4500-Cl F-00
DPD2 colorimetric	4500-Cl G	4500-Cl G-00
Syringaldazine (FACTS)	4500-Cl H	4500-Cl H-00
Iodometric electrode	4500-Cl I	4500-Cl I-00
DPD2	4500-ClO2 D
Amperometric method II	4500-ClO2 E	4500-ClO2 E-00
Lissamine green spectrophotometric				327.0, Rev 1.1
1The Standard Methods Online version that is approved is indicated by the last two (2) digits in the method number, which is the year of approval by the Standard Methods Committee. Standard Methods Online are available at http://www.standardmethods.org.
2DPD means N,N-diethyl-4-phenylene diamine.
METHODOLOGY APPROVED FOR EACH DISINFECTANT RESIDUAL MEASURED1
Methodology	Free Chlorine	Combined Chlorine	Total Chlorine	Chlorine Dioxide
Amperometric titration	X	X	X
Low level amperometric titration			X
DPD2 ferrous titrimetric	X	X	X
DPD2 colorimetric	X	X	X
Syringaldazine (FACT)	X
Iodometric electrode			X
DPD2				X
Amperometric method ii				X
Lissamine green spectrophotometric				X
1X indicates method is approved for measuring specified disinfectant residual.
2DPD means N,N-diethyl-4-phenylene diamine.

(2) If approved by the commissioner, a system may also measure residual disinfectant concentrations for chlorine, chloramines, and chlorine dioxide by using DPD colorimetric test kits.

(3) Residual disinfectant concentration may be measured only by a certified operator or a party approved by the commissioner.

  (d) Systems required to analyze parameters not included in subsections (b) and (c) shall use the following methods or with the alternative methods listed in Appendix A to Subpart C of 40 CFR 141:

(1) All methods allowed in 327 IAC 8-2-45 for measuring alkalinity and pH.

(2) A system shall use one (1) or more of the following methods for bromide:

(A) EPA Method 300.0.

(B) EPA Method 300.1.

(C) EPA Method 317.0, Revision 2.0.

(D) EPA Method 326.0, Revision 1.0.

(E) ASTM Method D 6581-00.

(3) A system shall use one (1) or more of the following methods for TOC:

(A) Standard Method 5310 B or 5310 B-00 (High-Temperature Combustion Method).

(B) Standard Method 5310 C or 5310 C-00 (Persulfate-Ultraviolet or Heated-Persulfate Oxidation Method).

(C) Standard Method 5310 D or 5310 D-00 (Wet-Oxidation Method).

(D) 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 two (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.

(4) SUVA means specific ultraviolet absorption at two hundred fifty-four (254) nanometers, an indicator of the humic content of water. It is a calculated parameter obtained by dividing a sample's ultraviolet absorption at a wavelength of two hundred fifty-four (254) nanometers (UV₂₅₄) (in m^-1) by its concentration of dissolved organic carbon (DOC) (in milligrams per liter). In order to determine SUVA, UV₂₅₄ and DOC must be measured separately. When determining SUVA, a system shall use the following methods:

(A) A system shall use one (1) or more of the following methods to measure DOC:

(i) Standard Method 5310 B or 5310 B-00 (High-Temperature Combustion Method).

(ii) Standard Method 5310 C or 5310 C-00 (Persulfate-Ultraviolet or Heated-Persulfate Oxidation Method).

(iii) Standard Method 5310 D or 5310 D-00 (Wet-Oxidation Method).

(iv) EPA Method 415.3, Revision 1.1.

(B) DOC samples must be filtered through a forty-five hundredths (0.45) micrometer pore-diameter filter as soon as practical after sampling, not to exceed forty-eight (48) hours. After filtration, DOC samples must be acidified to achieve pH less than or equal to two (2.0) with minimal addition of the acid specified in the method or by the instrument manufacturer. Acidified DOC samples must be analyzed within twenty-eight (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 DOC that is less than five-tenths (0.5) milligram per liter.

(C) The following apply to a system required to measure UV₂₅₄ under this subdivision:

(i) A system shall use Standard Method 5910 B or 5910 B-00 (Ultraviolet Absorption Method) or EPA Method 415.3, Revision 1.1 to measure ultraviolet absorption at two hundred fifty-four (254) nanometers (UV₂₅₄). UV absorption must be measured at two hundred fifty-three and seven-tenths (253.7) nanometers (may be rounded off to two hundred fifty-four (254) nanometers).

(ii) Prior to analysis, UV₂₅₄ samples must be filtered through a forty-five hundredths (0.45) micrometer pore-diameter filter.

(iii) The pH of UV₂₅₄ samples may not be adjusted.

(iv) Samples must be analyzed as soon as practical after sampling, not to exceed forty-eight (48) hours.

SUVA must be determined on water prior to the addition of disinfectants or oxidants, or both, 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.

(5) A system required to measure for magnesium under this subsection shall use one (1) of the following methods for magnesium:

(A) EPA Method 200.7.

(B) ASTM Method D 511-93 A or D 511-93 B.

(C) Standard Method 3111 B, 3120 B, 3500-Mg B, or 3500-Mg E.

  (e) Parameters measured under subsection (d) must be measured by a certified operator or a party approved by the commissioner. (Water Pollution Control Division; 327 IAC 8-2.5-5; filed May 1, 2003, 12:00 p.m.: 26 IR 2841; errata filed Feb 6, 2006, 11:15 a.m.: 29 IR 1937; filed May 7, 2010, 9:30 a.m.: 20100602-IR-327080198FRA; errata filed Jul 2, 2010, 1:12 p.m.: 20100714-IR-327100432ACA; filed Feb 25, 2013, 8:36 a.m.: 20130327-IR-327110667FRA)