Wisconsin Administrative Code › Department of Natural Resources › NR 800 - Environmental Protection - Water Supply › Chapter NR 809 - Safe Drinking Water › Subchapter III - Maximum Contaminant Levels, Maximum Residual Disinfectant Levels, Monitoring, Analytical Requirements and Control of Disinfection Byproducts, Disinfection Residuals and Stage 1 and Stage 2 DBP › Section NR 809.563 - Analytical requirements for disinfection byproducts and disinfection residuals Stage 1 DBP and Stage 2 DBP

Current through June 24, 2024
(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
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.