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 athttp://www.standardmethods.org. 4 Available from ASTM International, 100 Barr Harbor Drive, West Conshohocken, PA 19428-2859, or http://astm.org. 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. NR 809.563(4)(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. NR 809.563(4)(a)(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. NR 809.563(4)(b)(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. NR 809.563(4)(c)(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. NR 809.563(4)(e)(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
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.
NR 809.563(5)(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. NR 809.563(6)(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: NR 809.563(6)(b)(b) Bromide. For measuring bromide use EPA Method 300.0 or EPA Method 300.1. NR 809.563(6)(c)(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). NR 809.563(6)(c)2.2. 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. NR 809.563(6)(d)(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. NR 809.563(6)(d)1.1. In order to determine SUVA, it is necessary to separately measure UV254 and DOC. NR 809.563(6)(d)2.2. 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. NR 809.563(6)(d)3.3. DOC and UV254 samples used to determine a SUVA value shall be taken at the same time and at the same location. NR 809.563(6)(e)(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. NR 809.563(6)(f)(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. NR 809.563 HistoryHistory: CR 09-073: cr. Register November 2010 No. 659, eff. 12-1-10; CR 15-049: am. (1), (2), r. and recr. (2) Table R, (3) Table S, am. (4) (a), (b), r. (4) (d), am. (4) (e), Table U, (5), (6) (intro.), cr. (6) (h) Register March 2016 No. 723, eff. 4-1-16. NR 809.565NR 809.565 Monitoring requirements for disinfection byproducts and disinfection residuals Stage 1 DBP. NR 809.565(1)(1) General requirements. General requirements under this subchapter for analytical requirements, determining maximum contaminant levels, conducting monitoring and control of disinfection byproducts are as follows: NR 809.565(1)(a)(a) Water suppliers shall take all samples during normal operating conditions. NR 809.565(1)(b)(b) Water suppliers may consider multiple wells drawing water from a single aquifer as one treatment plant for determining the minimum number of TTHM and HAA5 samples required, on a case-by-case basis with department approval. NR 809.565(1)(c)(c) Failure to monitor in accordance with the monitoring plan required under sub. (6) is a monitoring violation. NR 809.565(1)(d)(d) Failure to monitor shall be treated as a violation for the entire period covered by the annual average where compliance is based on a running annual average of monthly or quarterly samples or averages and the water supplier’s failure to monitor makes it impossible to determine compliance with MCLs or MRDLs. NR 809.565(1)(e)(e) Water suppliers may use only data collected under the provisions of this subchapter NR 809.565(2)(2) Monitoring frequency and location for TTHMs and HAA5s. Water suppliers shall monitor at the following frequency and locations for TTHMs and HAA5 disinfection byproducts: NR 809.565(2)(a)1.1. Water suppliers for public water systems serving at least 10,000 persons which are supplied by a surface water source or by a groundwater source under the direct influence of surface water shall collect and have analyzed 4 water samples per quarter per treatment plant. NR 809.565(2)(a)1.a.a. At least 25% of all samples collected each quarter at each treatment plant shall be at locations representing the maximum residence time in the public water system. NR 809.565(2)(a)1.b.b. The remaining samples shall be taken in the distribution system at locations representing at least average residence time in the public water system and representative of the entire distribution system, taking into account the number of people served, different sources of water and different treatment methods. NR 809.565(2)(a)2.2. Water suppliers for public water systems serving from 500 to 9,999 persons which are supplied by a surface water source or by a groundwater source under the direct influence of surface water shall collect and have analyzed one water sample per quarter per treatment plant. The samples shall be collected at locations representing the maximum residence time of water in the public water system. NR 809.565(2)(a)3.3. Water suppliers for public water systems serving fewer than 500 people which are supplied by a surface water source or by a groundwater source under the direct influence of surface water shall collect one sample per treatment plant annually. The samples shall be collected during the month with the warmest water temperature at locations representing the maximum residence time in the public water system. NR 809.565(2)(a)4.4. Water suppliers for public water systems using chemical disinfection, using only groundwater not under the direct influence of surface water, and serving at least 10,000 people shall collect one sample per treatment plant per quarter. The sample or samples shall be collected at the location representing the maximum residence time in the public water system. NR 809.565(2)(a)5.5. Water suppliers for public water systems using chemical disinfection, using only groundwater not under the direct influence of surface water, and serving fewer than 10,000 people shall collect one sample per treatment plant annually. The sample shall be collected during the month with the warmest water temperature, at locations representing the maximum residence time, in the public water system. NR 809.565(2)(b)(b) Monitoring after exceeding an MCL. If a sample or the average of samples, if more than one sample is taken, exceeds the MCL for TTHMs or HAA5 disinfection byproducts, the water supplier shall collect quarterly samples until the public water system meets the requirements of reduced monitoring in par. (c). NR 809.565(2)(c)(c) Reduced monitoring. Water suppliers may reduce monitoring for TTHMs and HAA5s as follows: NR 809.565(2)(c)1.1. Water suppliers for surface water systems or groundwater systems under the direct influence of surface water with an annual average of TTHM of < 0.040 mg/L and HAA5 =0.030 mg/L with an annual average TOC concentration of < 4.0 mg/L, before any treatment may reduce monitoring to the following: NR 809.565(2)(c)1.a.a. Water suppliers for a public water system serving at least 10,000 people may reduce monitoring to one sample per quarter per treatment plant so long as the sample is taken at a location representing maximum residence time in the public water system. NR 809.565(2)(c)1.b.b. Water suppliers for a public water system serving from 500 to 9,999 people may reduce monitoring to one sample per year per treatment plant so long as the sample is taken at a location representing maximum residence time in the public water system during the month of warmest water temperature. NR 809.565(2)(c)1.c.c. A water supplier for a public water system serving less than 500 people may not reduce monitoring to less than one sample during the month of warmest water temperature per treatment plant per year. NR 809.565(2)(c)2.2. A water supplier for a public water system using only groundwater not under the direct influence of surface water using chemical disinfection with an annual average of TTHM of < 0.040 mg/L and HAA5 < 0.030 mg/L may reduce sampling to the following: NR 809.565(2)(c)2.a.a. A water supplier for a public water system serving at least 10,000 people may reduce monitoring to one sample per year per treatment plant during the month of warmest water temperature at a location representing maximum residence time in the public water system. NR 809.565(2)(c)2.b.b. A water supplier for a public water system serving fewer than 10,000 people may reduce monitoring to one sample per treatment plant per 3 year monitoring cycle during the month of warmest water temperature at a location representing maximum residence time in the public water system. The reduced monitoring will begin on January 1 following the quarter in which the public water system first qualifies for reduced monitoring. NR 809.565(2)(c)2m.2m. To qualify for reduced monitoring for TTHM and HAA5 under this paragraph, water suppliers for surface water systems or groundwater systems under the direct influence of surface water not monitoring under the provisions of sub. (5) shall take monthly TOC samples every 30 days at a location prior to any treatment, beginning April 1, 2008, or earlier, if specified by the department. In addition to meeting other criteria for reduced monitoring in this paragraph, the source water TOC running annual average shall be =4.0 mg/L, based on the most recent four quarters of monitoring, on a continuing basis at each treatment plant to reduce or remain on reduced monitoring for TTHM and HAA5. Once qualified for reduced monitoring for TTHM and HAA5 under this paragraph, a system may reduce source water TOC monitoring to quarterly TOC samples taken every 90 days at a location prior to any treatment. NR 809.565(2)(c)3.3. Public water systems on a reduced monitoring schedule may remain on that reduced schedule as long as the average of all samples taken in the year, for public water systems which shall monitor quarterly, or the result of the sample, for public water systems which shall monitor no more frequently than annually, is no more than 0.060 mg/L and 0.045 mg/L for TTHMs and HAA5, respectively. A water supplier for a public water systems that do not meet these levels shall resume monitoring at the frequency identified in par. (a) in the quarter immediately following the quarter in which the public water system exceeds 0.060 mg/L and 0.045 mg/L for TTHMs and HAA5, respectively. NR 809.565(2)(d)(d) Return to routine monitoring. The department may return a public water system to routine monitoring at the department’s discretion. NR 809.565(3)(3) Monitoring frequency and location for chlorite and bromate. Water suppliers for public water systems shall monitor at the following frequency and locations for chlorite and bromate disinfection byproducts: NR 809.565(3)(a)(a) Chlorite. Water supplier for community and nontransient noncommunity water systems using chlorine dioxide, for disinfection or oxidation, shall conduct monitoring for chlorite as follows: NR 809.565(3)(a)1.1. ‘Routine daily monitoring.’ A water supplier for a public water system shall take daily samples at the entrance to the distribution system. For any daily sample that exceeds the chlorite MCL, the water supplier shall take additional samples in the distribution system the following day at the locations required by subd. 3. in addition to the sample required at the entrance to the distribution system. NR 809.565(3)(a)2.2. ‘Routine monthly monitoring.’ A water supplier shall take a 3-sample set each month in the distribution system. The water supplier shall take one sample at each of the following locations: near the first customer, at a location representative of average residence time, and at a location reflecting maximum residence time in the distribution system. Any additional routine sampling shall be conducted in the same manner, as 3-sample sets, at the specified locations. The water supplier may use the results of additional monitoring conducted under subd. 3. to meet the requirement for monitoring in this subdivision. NR 809.565(3)(a)3.3. ‘Additional monitoring.’ On each day following a routine sample monitoring result that exceeds the chlorite MCL at the entrance to the distribution system, the water supplier shall take 3 chlorite distribution system samples at the following locations: as close to the first customer as possible, in a location representative of average residence time, and as close to the end of the distribution system as possible, reflecting maximum residence time in the distribution system. NR 809.565(3)(a)4.4. ‘Reduced monitoring.’ Chlorite monitoring at the entrance to the distribution system required under subd. 1. may not be reduced. Chlorite monitoring in the distribution system required under subd. 2 may be reduced to one 3-sample set per quarter after one year of monitoring where no individual chlorite sample taken in the distribution system under subd. 2. has exceeded the chlorite MCL and the public water system has not been required to conduct monitoring under subd. 3. The public water system may remain on the reduced monitoring schedule until either any of the 3 individual chlorite samples taken quarterly in the distribution system under subd. 2. exceeds the chlorite MCL or the water supplier is required to conduct monitoring under subd. 3., at which time the public water system shall revert to routine monitoring. NR 809.565(3)(b)1.1. ‘Routine monitoring.’ Water suppliers for community and nontransient noncommunity systems using ozone, for disinfection or oxidation, shall take one sample per month for each treatment plant in the public water system using ozone. Water suppliers shall take samples monthly at the entrance to the distribution system while the ozonation treatment system is operating under normal conditions. NR 809.565(3)(b)2.2. ‘Reduced monitoring.’ Water suppliers for public water systems may reduce monitoring for bromate from monthly to once per quarter, if the water supplier demonstrates that the public water system’s running annual average concentration for bromate is =0.0025 mg/L based on monthly bromate measurements under par. (b) for the most recent four quarters. Samples shall be analyzed using Method 317.0 Revision 2.0, 326.0 or 321.8. If the running annual average bromate concentration is >0.0025 mg/L, the system must resume routine monitoring required by par. (b). NR 809.565(4)(4) Monitoring frequency and location for disinfectant residuals. Water suppliers for systems shall monitor at the following frequency and locations for disinfectant residuals: NR 809.565(4)(a)(a) Chlorine and chloramines. Water suppliers for public water systems shall perform routine monitoring by measuring the residual disinfectant level at the same points in the distribution system and at the same time as total coliforms are sampled, as specified in s. NR 809.31. The department may allow suppliers for surface water systems to take disinfectant residual samples at points other than the total coliform sampling points if the department determines that such points are more representative of disinfected water quality within the distribution system. Water suppliers for surface water systems may use the results of residual disinfectant concentration sampling conducted under s. NR 810.38 (1) (h) for unfiltered systems or s. NR 810.38 (2) (d) for public water systems that filter, in lieu of taking separate samples. Monitoring may not be reduced. NR 809.565(4)(b)1.1. ‘Routine monitoring.’ Water suppliers for community, nontransient noncommunity, and transient noncommunity water systems that use chlorine dioxide for disinfection or oxidation shall take daily samples at the entrance to the distribution system. For any daily sample that exceeds the MRDL, the water supplier shall take samples in the distribution system the following day at the locations required by subd. 2., in addition to the sample required at the entrance to the distribution system. NR 809.565(4)(b)2.2. ‘Additional monitoring.’ On each day following a routine sample monitoring result that exceeds the MRDL, the water supplier shall take 3 chlorine dioxide distribution system samples. If chlorine dioxide or chloramines are used to maintain a disinfectant residual in the distribution system, or if chlorine is used to maintain a disinfectant residual in the distribution system and there are no disinfection addition points after the entrance to the distribution system, i.e., no booster chlorination, the water supplier shall take 3 samples as close to the first customer as possible, at intervals of at least 6 hours. If chlorine is used to maintain a disinfectant residual in the distribution system and there are one or more disinfection addition points after the entrance to the distribution system, i.e., booster chlorination, the water supplier shall take one sample at each of the following locations: as close to the first customer as possible, in a location representative of average residence time, and as close to the end of the distribution system as possible, reflecting maximum residence time in the distribution system. NR 809.565(4)(b)3.3. ‘Reduced monitoring.’ Chlorine dioxide monitoring may not be reduced. NR 809.565(5)(5) Monitoring frequency and location for disinfectant byproduct precursors. Water suppliers for public water systems shall monitor at the following frequency and locations for disinfection byproduct precursors (DBPP): NR 809.565(5)(a)1.1. Water suppliers for public water systems which use conventional filtration treatment and are supplied by a surface water source or by a groundwater source under the direct influence of surface water shall monitor each treatment plant monthly for TOC no later than the point of combined filter effluent turbidity monitoring and representative of the treated water. NR 809.565(5)(a)2.2. All water suppliers for public water systems required to monitor under subd. 1. shall also monitor for TOC in the source water prior to any treatment at the same time as monitoring for TOC in the treated water. NR 809.565 NoteNote: These samples, source water and treated water, are referred to as paired samples.
NR 809.565(5)(a)3.3. At the same time as the source water sample is taken, all water suppliers shall monitor for alkalinity in the source water prior to any treatment. Water suppliers shall take one paired sample and one source water alkalinity sample per month per plant at a time representative of normal operating conditions and influent water quality.
