Wisconsin Administrative Code, Subchapter III, Section NR 809.563 - Analytical requirements for disinfection byproducts and disinfection residuals Stage 1 DBP and Stage 2 DBP | Wisconsin Administrative Code

(1) GENERAL. Water suppliers shall use only the analytical methods specified in this section, or otherwise approved by EPA for monitoring under this subchapter, to demonstrate compliance with the requirements of this subchapter.

(2) APPROVED ANALYTICAL METHODS FOR DISINFECTANT RESIDUALS. Water suppliers shall measure residual disinfectant concentrations for total chlorine, free chlorine, combined chlorine chloramines, and chlorine dioxide by the methods listed in Table R. Water suppliers may also measure residual disinfectant concentrations for chlorine, chloramines and chlorine dioxide by using N, N-diethly-p-phenylenediamine (DPD) colorimetric using a colorimeter as prescribed in the approved methods.

(3) APPROVED ANALYTICAL METHODS FOR DISINFECTANT BYPRODUCTS. Water suppliers shall measure disinfection byproducts by the methods, as modified by the footnotes, prescribed in Table S. Samples for TTHM shall be dechlorinated upon collection to prevent further production of trihalomethanes, according to the procedures described in the methods, except acidification is not required if only THMs or TTHMs are to be determined. Samples for maximum TTHM potential shall not be dechlorinated or acidified, and shall be held for 7 days at 25° C or above prior to analysis. Samples for bromate analyzed using EPA method 321.8 samples must be preserved at the time of sampling with 50 mg ethylenediamine (EDA)/L of sample and must be analyzed within 28 days. Samples for TTHM and HAA5 shall be collected using the containers, preservative and holding times specified in s. NR 809.203(4) Table D. In all cases, samples should be analyzed as soon after collection as possible.

Table R

Approved Methodology for Disinfectant Residuals

Methodology	SM (19th, 20th, 21st, and 22nd ed)2	SM Online3	ASTM4 method	EPA method	Residual measured1
Methodology	SM (19th, 20th, 21st, and 22nd ed)2	SM Online3	ASTM4 method	EPA method	FreeCl2	Combined Cl2	Total Cl2	ClO2
Amperometric Titration	4500-Cl D	4500-Cl D-00	D 1253-86 (96), 03, D1253-08		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-ClO2 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 Standard Methods for the Examination of Water and Wastewater, 19th edition (1995), 20th edition (1998), 21st edition (2005), 22nd edition (2012). Available from American Public Health Association, 800 I Street, NW., Washington, DC, 20001-3710.

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 Available from ASTM International, 100 Barr Harbor Drive, West Conshohocken, PA 19428-2859, or http://astm.org.

Table S Approved Methods for Disinfectant Byproduct Compliance Monitoring
Contaminant and methodology1	EPA method10	Standard Methods2	SM online9	ASTM method3
TTHM
P&T/GC/ELCD & PID	502.24
P&T/GC/MS	524.2
LLE/GC/ECD	551.1
HAA5
LLE (diazomethane) GC/ELCD		6251 B5 6610 (20th Edition)	6251 B-94
SPE (acidic methanol) GC/ECD	552.15
LLE (acidic methanol) GC/ECD	552.2, 552.3
Ion chromatography electrospray ion-ization tandem mass spectrometry (IC-ESI-MS/MS)	557
Bromate
Ion chromatography	300.1			D 6581-00 D6581-08 A D6581-08 B
Ion chromatography and post-column reaction	317.0 Rev 2.06, 326.06
IC/ICP-MS	321.86, 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 D 6581-08 A D 6581-08 B

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 Standard Methods for the Examination of Water and Wastewater, 19th edition (1995), 20th edition (1998), 21st edition (2005), 22nd edition (2012). Available from American Public Health Association, 800 I Street, NW., Washington, DC, 20001-3710.

3 Available from ASTM International, 100 Barr Harbor Drive, West Conshohocken, PA 19428-2859, or http://astm.org.,

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 and post column reaction or IC/ICP-MS must be used for monitoring of bromate for purposes of demonstrating eligibility of reduced monitoring.

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 NR 809.565(3)(a)1. Ion chromatography must be used for routine monthly monitoring of chlorite and additional monitoring of chlorite in the distribution system, as prescribed in NR 809.565 (30(a) 2. and. NR 809.565(3) (a)3.

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.

10 EPA methods are available at http://epa.gov/safewater/methods/analyticalmethods_ogwdw.html.

(4) LABORATORY CERTIFICATION FOR DISINFECTANT BYPRODUCTS. Laboratories that are certified by the department or EPA shall conduct the analysis under this section for disinfection byproducts.

(a) To receive certification to conduct analyses for the contaminants in this subchapter, a laboratory shall analyze performance evaluation samples approved by the department or EPA at least once during each consecutive 12-month period by each method for which a laboratory desires certification.

(b) When analyzing performance evaluation samples, the laboratory shall achieve quantitative results on the PE sample analyses that are within the acceptance limits in Table T.

(c) The acceptance limit shall be 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.

(e) Laboratories shall report quantitative data for concentrations as low as the ones listed in Table U for all DBP samples analyzed for compliance.

Table U

Minimum Reporting Levels for DBP Samples

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 s. NR 809.565(3) (a) 2. and 3.
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 detection limit 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 department.

(5) APPROVAL OF PERSONS MEASURING DISINFECTANT RESIDUAL CONCENTRATIONS AND CHLORITE. A person approved by the department or EPA shall measure residual disinfectant concentrations and daily chlorite samples at the entrance to the distribution system.

(6) ANALYTICAL METHODS FOR ADDITIONAL REQUIRED PARAMETERS. Water suppliers for public water systems required to analyze for additional parameters not included in sub. (3) shall have these parameters analyzed by a person approved by the department or EPA using the following methods:

(a) Alkalinity. For measuring alkalinity use the methods allowed in s. NR 809.113 Table A.

(b) Bromide. For measuring bromide use EPA Method 300.0 or EPA Method 300.1.

(c) Total organic carbon (TOC). For measuring total organic carbon, use Standard Method 5310 B (High-Temperature Combustion Method) or Standard Method 5310 C (Persulfate-Ultraviolet or Heated-Persulfate Oxidation Method) or Standard Method 5310 D (Wet-Oxidation Method).

1. TOC samples may not be filtered prior to analysis.

2. TOC samples shall either be analyzed or shall be acidified to achieve pH less than 2.0 by minimal addition of phosphoric or sulfuric acid as soon as practical after sampling, not to exceed 24 hours.

3. Acidified TOC samples shall be analyzed within 28 days.

(d) 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.

1. In order to determine SUVA, it is necessary to separately measure UV254 and DOC.

2. When determining SUVA, water suppliers shall use the methods stipulated in par. (e) to measure DOC and the method stipulated in par. (f) to measure UV254 SUVA shall be determined on water prior to the addition of disinfectants or oxidants, or both, by the water supplier.

3. DOC and UV254 samples used to determine a SUVA value shall be taken at the same time and at the same location.

(e) Dissolved organic carbon (DOC). For measuring dissolved organic carbon, use Standard Method 5310 B (High-Temperature Combustion Method) or Standard Method 5310 C (Persulfate-Ultraviolet or Heated-Persulfate Oxidation Method) or Standard Method 5310 D (Wet-Oxidation Method). Prior to analysis, DOC samples shall be filtered through a 0.45 mm pore-diameter filter. Water passed through the filter prior to filtration of the sample shall serve as the filtered blank. This filtered blank shall be analyzed using procedures identical to those used for analysis of the samples and shall meet the following criteria: DOC < 0.5 mg/L. DOC samples shall be filtered through the 0.45 mm pore-diameter filter prior to acidification. DOC samples shall either be analyzed or shall be acidified to achieve pH less than 2.0 by minimal addition of phosphoric or sulfuric acid as soon as practical after sampling, not to exceed 48 hours. Acidified DOC samples shall be analyzed within 28 days.

(f) Ultraviolet absorption at 254 nm (UV254). For measuring ultraviolet absorption at 254 nm, use Method 5910 B (Ultraviolet Absorption Method). UV absorption shall be measured at 253.7 nm (may be rounded off to 254 nm). Prior to analysis, UV254 samples shall be filtered through a 0.45 mm pore-diameter filter. The pH of UV254 samples may not be adjusted. Samples shall be analyzed as soon as practical after sampling, not to exceed 48 hours.

(g) pH. For measuring pH, use any method allowed in s. NR 809.113(1) Table A.

(h) Magnesium. All methods allowed in s. NR 809.113(1) Table A.