LABORATORY REPORTING INSTRUCTIONS for

Transcription

1 LABORATORY REPORTING INSTRUCTIONS for RADIOLOGICAL CONTAMINANTS in DRINKING WATER SYSTEMS GROSS ALPHA PARTICLE RADIOACTIVITY RADIUM 226 RADIUM 228 URANIUM GROSS BETA PHOTON RADIOACTIVITY Technical Guidance Number For more information, visit keyword: Drinking Water.

2 DEPARTMENT OF ENVIRONMENTAL PROTECTION Bureau of Water Standards and Facility Regulation DOCUMENT NUMBER: TITLE: EFFECTIVE DATE: AUTHORITY: POLICY: PURPOSE: APPLICABILITY: DISCLAIMER: Laboratory Reporting Instructions for Radiological Contaminants in Drinking Water Systems Upon notice of final publication in the PA Bulletin. Pennsylvania s Safe Drinking Water Act (35 P.S. &721.1 et seq.) and regulations at 25 Pa. Code Chapter 109. It is the policy of the Department of Environmental Protection (DEP) to provide certified laboratory directors and public water suppliers with the information necessary to properly report radiological analytical compliance monitoring data under the safe drinking water program. The purpose of this document is to establish uniform instructions and protocol for implementing the drinking water reporting requirements for radiological analytical data. This guidance will apply to all certified laboratories and public water systems submitting drinking water radiological analytical data to DEP. The policies and procedures outlined in this guidance are intended to supplement existing requirements. thing in the policies or procedures shall affect regulatory requirements. The policies and procedures herein are not an adjudication or a regulation. There is no intent on the part of DEP to give the rules in these policies that weight or deference. This document establishes the framework within which DEP will exercise its administrative discretion in the future. DEP reserves the discretion to deviate from this policy statement if circumstances warrant. PAGE LENGTH: LOCATION: 51 Pages Volume 19, Tab 02B DEFINITIONS: See 25 Pa. Code Chapter / December 20, 2008 / Page i

3 TABLE OF CONTENTS Section 1: Section 2: Section 3: Introduction...1 Responsibilities of the Laboratory...3 Reporting Requirements for Natural Radiologicals...5 Section 4: Summary of Codes for Reporting Monitoring Results for Natural Radiologicals...11 Section 5: Section 6: Section 7: Section 8: Summary of Monitoring Requirements for Natural Radiologicals...18 Reporting Requirements for Man-Made Radiologicals...25 Summary of Codes for Reporting Monitoring Results for Man-Made Radiologicals...31 Summary of Monitoring Requirements for Man-Made Radiologicals...36 Section 9: Distribution of Completed Forms...40 Section 10: DEP Assistance Tools...41 Section 11: Case Studies...42 Appendices: Appendix 1: Appendix I DEP and CHD Offices Contact List...46 Appendix 2: Appendix II List of Regional DEP Field Offices / December 20, 2008 / Page ii

4 SECTION 1: INTRODUCTION This manual provides instructions for the reporting of monitoring results for radiological contaminants in public water supply systems. These requirements apply to all community water systems (CWSs). The previous Radionuclide Rule, promulgated in 1976, established regulations for gross alpha particle radioactivity, radium-226, radium-228, and beta particle and photon radioactivity. The Department s Radionuclide Rule, which was adopted by the Environmental Quality Board and published in the Pennsylvania Bulletin on April 3, 2004, establishes several amendments to the previous rule. The amendments include requirements for uranium, which was not previously regulated, and revisions to the monitoring requirements for combined radium-226 and radium-228, gross alpha particle radioactivity, and beta particle and photon radioactivity. The Department s Radionuclide Rule requires monitoring at each entry point to the distribution system. This will ensure that every Pennsylvania customer s water meets the MCLs for radionuclides. The previous rule required the collection of samples from a free flowing tap. This manual is separated into reporting requirements for the natural radiological contaminants (gross alpha, radium 226, radium 228, uranium) and the man-made radiological contaminants (gross beta, strontium-90, tritium, iodine-131, major radioactive beta particle constituents). The revised rule sets the following provisions for the natural radiological contaminants: Gross Alpha MCL = 15 pci/l, Combined Radium MCL = 5 pci/l, Uranium MCL = 30 ug/l, Monitoring must be conducted for each parameter at each entry point, Initial monitoring consists of four consecutive quarterly samples at each entry point, Repeat monitoring occurs every 3, 6, or 9 years. The revised rule sets the following provisions for the man-made radiological contaminants: Gross Beta screening level = 50 pci/l for systems determined to be vulnerable Gross Beta screening level = 15 pci/l for systems determined to be using source waters contaminated by effluent from a nuclear facility, Beta Particle and Photon Radioactivity MCL = 4 mrem/yr, Monitoring must be conducted at each entry point determined to be vulnerable or as using source waters contaminated by effluent from a nuclear facility, Routine monitoring for systems determined to be vulnerable consists of four consecutive quarterly samples for Gross Beta and annual samples for Strontium-90 and Tritium at each entry point, / December 20, 2008 / Page 1

5 Routine monitoring for systems determined to be using source waters contaminated by effluent from a nuclear facility consists of 12 monthly samples Gross Beta, quarterly samples for Strontium-90 and Tritium, and a composite analysis of 5 consecutive daily samples once each quarter for Iodine-131, Reduced monitoring occurs every 3 years. Analytical results must be reported to DEP on an SDWA-4 form. The SDWA-4 form has been modified to allow the reporting of the lower limit of detection and the counting error. The drinking water analysis results are entered into the Pennsylvania Drinking Water Information System (PADWIS), the computerized data management system used by DEP to track drinking water monitoring results. An effective surveillance program requires prompt follow-up to MCL, MRDL, treatment technique and monitoring violations for the protection of public health. Your assistance is critical in regard to accurate and prompt data reporting. Please read these instructions thoroughly. Failure to monitor, analyze and report analytical results correctly may result in the water supplier incurring a violation of the Safe Drinking Water Regulations / December 20, 2008 / Page 2

6 SECTION 2: RESPONSIBILITIES OF THE LABORATORY Under the provisions of Chapter 109, Safe Drinking Water Regulations, under the authority of the PA Safe Drinking Water Act, it is the responsibility of the certified laboratory to: 1. Submit to DEP, on forms, or in electronic format acceptable to DEP, the results of analyses performed by the laboratory under the Safe Drinking Water Regulations. 2. Report the results within either the first 10 days following the month in which the result is determined or the first 10 days following the end of the required monitoring period as stipulated by DEP, whichever is shorter. 3. Obtain and maintain DEP s current after-hours emergency response telephone numbers for each applicable regional office. 4. Establish and maintain a standard operating procedure to provide the information needed to report a violation listed below to DEP. This procedure should be verified at least annually. 5. Whenever an MCL, MRDL, action level or a treatment technique performance requirement is exceeded, or a sample result requires the collection of check or confirmation samples the laboratory must: a) tify the public water supplier by telephone within 1 hour of the laboratory s determination. If the supplier cannot be reached within that time, notify DEP by telephone within 2 hours of the determination with the information listed above. If it is necessary for the laboratory to contact DEP after DEP s routine business hours, the laboratory shall contact the appropriate DEP regional office s after-hours emergency response telephone number and provide information regarding the occurrence, the name of a contact person and the telephone number where that individual may be reached in the event further information is needed. If DEP s appropriate emergency number cannot be reached, the laboratory shall notify the appropriate DEP regional office by telephone within 1 hour of the beginning of the next business day. The information regarding the PWS shall include, but is not limited to, the PWSID number of the system, the system s name, the contaminant involved in the occurrence, the level of the contaminant found, where the sample was collected, the dates and times that the sample was collected and analyzed, / December 20, 2008 / Page 3

7 the name and identification number of the certified laboratory, the name and telephone number of a contact person at the laboratory, what steps the laboratory took to contact the PWS before calling DEP. b) tify the appropriate DEP district office in writing within 24 hours of the determination. For the purpose of determining compliance with this requirement, the postmark, if the notice is mailed, or the date the notice is received by DEP, whichever is earlier, will be used. Upon approval by DEP, the notice may be made electronically to DEP as long as the information is received within the 24-hour deadline. 6. tify DEP within 48 hours of termination of the laboratory certification from the Environmental Protection Agency (EPA) or another agency with primary enforcement responsibility. 7. tify each public water supplier served by the laboratory within 48 hours of a: (a) (b) Failure to renew or DEP denial of renewal of existing certification for a category of certification. Revocation of certification by DEP under the Safe Drinking Water Regulations. NOTES: Proper reporting and notification of analytical results to DEP is a condition of your certification. Failure to properly report results may lead to revocation of your certification. Report any unadjusted gross alpha result > 15 pci/l as an MCL exceedance. Report any gross beta result > screening level (15 or 50 pci/l) as an MCL exceedance / December 20, 2008 / Page 4

8 SECTION 3: REPORTING REQUIREMENTS FOR NATURAL RADIOLOGICALS Regulated Contaminants, Maximum Contaminant Levels (MCLs), and United States Environmental Protection Agency (EPA) Detection Limits: Contaminant MCL EPA Specified Detection Limit Gross Alpha particle 15 pci/l 3 pci/l Radium-226 Monitoring Summary: 1 pci/l Radium pci/l Combined radium 226/228 5 pci/l Uranium 30 μg/l 1 μg/l Initial monitoring consists of at least 4 consecutive quarterly samples. Repeat monitoring is conducted every 3, 6, or 9 years. The repeat monitoring frequency is based on the most recent sample results. Repeat monitoring is annual for entry points where treatment has been installed. Annual monitoring is required only for those contaminants for which the treatment was installed. Monitoring is specific for each contaminant at each entry point. Monitoring for Radium 226/Radium 228 is based on the combined radium value. For more information about gross alpha monitoring requirements, see Section 5. Reporting Summary and Important tes: 1. Report all results on an SDWA-4 form. Enter the result of each sample analyzed to at least 3 decimal places if the result is a valid detect. Do not round. 2. Report the results within either the first 10 days following the month in which the result is determined or the first 10 days following the end of the required monitoring period, whichever is shorter. 3. For gross alpha: Always report the unadjusted value. Do not subtract uranium. Report uranium separately. Always report the unadjusted value as contaminant code Always report the associated counting error on the SDWA-4 form. If the unadjusted result value is > 15 pci/l and uranium is not analyzed, report the result to the water supplier and the Department the same as any other MCL exceedance / December 20, 2008 / Page 5

9 4. Do not report substituted values. For further explanation of substitutions, see the Analysis Result instructions for the SDWA-4 form. 5. If gross alpha is greater than 5 pci/l (or gross alpha plus the counting error is greater than 5 pci/l), additional analysis of the same or equivalent sample will be needed for Ra 226 (if Ra 226 monitoring is required). The laboratory and water system should discuss plans for substituting gross alpha results for radium-226 and/or uranium before sample collection and analysis. 6. Report all results in pci/l, including uranium, even though the MCL is in μg/l. If your analysis produces a mass result (μg/l) for uranium, the value must be converted. This conversion process is described in the Analysis Result instruction for the SDWA-4 form. 7. Any result that is less than the EPA detection limit (shown above) is reported as zero (0). To be a valid detect, the value must be greater than the EPA detection limit and greater than or equal to the laboratory detection limit. Example: Gross alpha result = pci/l Laboratory detection limit = 3.0 pci/l This is a valid detect. 8. The Department s data system, PADWIS, will calculate adjusted gross alpha values, substitution values, and uranium mass values. 9. Composite Analysis Reporting: After the composite sample is analyzed at the end of four quarters, report the composite result on four separate SDWA-4 forms. Submit one form for each quarter used in the composite sample. Report the sample date on the form as the actual sample collection date for the quarterly sample. Report the sample period on the form for the quarter in which it was sampled. For data tracking purposes, DEP s data system needs four quarters of data, even though the result will be the same in each quarter. Example: Composite Result for Gross Alpha at EP 101: pci/l Report the composite result on four separate SDWA-4 forms: SDWA-4 Form 1: Result = pci/l; Sample Date 02/09/2005 SDWA-4 Form 2: Result = pci/l; Sample Date 05/17/2005 SDWA-4 Form 3: Result = pci/l; Sample Date 08/23/2005 SDWA-4 Form 4: Result = pci/l; Sample Date 10/15/ / December 20, 2008 / Page 6

10 3800-FM-WSFR0128 7/2005 COMMONWEALTH OF PENNSYLVANIA DEPARTMENT OF ENVIRONMENTAL PROTECTION BUREAU OF WATER STANDARDS AND FACILITY REGULATION PWS Name: Address: SAFE DRINKING WATER ACT INORGANIC/ORGANIC CHEMICAL AND RADIOLOGICAL ANALYSIS SDWA-4 INSERT AN X IN THE APPROPRIATE BOX IF: 1. An MCL is exceeded - 2. A VOC or SOC is detected - Phone: PWS ID TRANS SAMPLE PERIOD MMDDYY TO MMDDYY 03 to ANALYSIS CONTAM ID CONTAMINANT NAME METHOD RESULT 1 LLD 2 CE 2 MMDDYY LOCATION / ENTRY POINT SAMPLE LAB ID NAME MMDDYY TYPE* TIME ID # LAB NAME: PHONE: APPROVED BY: DATE: NOTE: 1 tify DEP in writing of any MCL violation within 24 hours of its determination. 2 Report LLD and CE for radiological analysis only. *SAMPLE TYPE KEY C - CHECK SAMPLE D - REGULAR DISTRIBUTION SAMPLE E - ENTRY POINT SAMPLE P - PLANT SAMPLE R - RAW WATER SAMPLE S - SPECIAL SAMPLE M - MAXIMUM RESIDENCE SAMPLE White Data Processing Yellow DEP District Pink Water Supplier Goldenrod Laboratory / December 20, 2008 / Page 7

11 DATA FIELD SMALL BOX IN UPPER RIGHT HAND CORNER PWS NAME, ADDRESS and PHONE NUMBER PWS ID TRANSACTION CODE SAMPLE PERIOD CONTAMINANT ID CONTAMINANT NAME ANALYSIS METHOD ANALYSIS RESULT EXPLANATION ELEVATED RESULTS enter an X if the result of any sample exceeds the MCL value. Enter the name and address of the public water system to which these samples apply. Also, enter the phone number of the contact person for the water system. Enter the 7-digit public water system identification number to which these samples apply. FAILURE TO ENTER THE PWS ID WILL RESULT IN THE WATER SUPPLIER NOT RECEIVING CREDIT FOR CONDUCTING THE MONITORING. If you do not know the PWS ID number, and the PWS cannot provide it to you, contact the local DEP or CHD office or check DEP s web site. The local DEP or CHD office assigns all PWS ID numbers. Enter as 03 (pre-printed on the SDWA-4). Enter the beginning date (MMDDYY) and end date (MMDDYY) for the sampling period during which the sample results apply. For annual (or 3, 6, or 9 year) monitoring, the monitoring period is the calendar year in which the sampling is conducted. Example: For the July-Sept 2005 quarter, enter to For the year 2008, enter to Enter the 4-digit contaminant identification code for the parameter being reported. Gross Alpha Radium Uranium Radium Enter the name of the contaminant being reported: gross alpha, radium-226, radium-228, or uranium. Enter the DEP 3-digit code of the approved analysis method used to analyze the samples (see Section 4). Enter the result of each sample analyzed to at least 3 decimal places if the result is a valid detect. The decimal point must be entered directly in the result field. If any result is less than the EPA specified method detection limit, report the result as zero (0). te that the EPA detection limit is a whole number. Be sure to use the proper units. Report ALL results in pci/l. A. Gross Alpha: Report all results in pci/l. Always report the unadjusted gross alpha result (contaminant code 4002). If the gross alpha result, or the gross alpha result plus the counting error, exceeds 15 pci/l, the same or equivalent sample should also be analyzed for uranium / December 20, 2008 / Page 8

12 DATA FIELD ANALYSIS RESULT (CONT.) EXPLANATION Gross Alpha (cont.): If uranium is analyzed so that an adjusted gross alpha value may be determined, report the uranium result separately. Do not subtract the uranium result from the gross alpha particle activity to obtain an adjusted gross alpha value. te: If a non-evaporative technique was used in the gross alpha analysis, radon, in addition to uranium, should be measured and reported. B. Radium-226: Report all results in pci/l. If the gross alpha result is to be substituted for radium-226, do not report a value for radium-226. C. Radium-228: Report all results in pci/l. NOTE: DO NOT REPORT COMBINED RADIUM. D. Uranium: Report all results in pci/l. If the uranium analysis produces results in terms of activity (pci/l), report the total or combined uranium value as the result. If the uranium analysis produces results in terms of mass (μg/l) rather than activity (pci/l), convert the uranium mass to activity using the following formula: uranium result μg/l X 0.67 pci/μg = uranium result pci/l. If the gross alpha result is to be substituted for uranium, do not report a value for uranium. LOWER LIMIT OF DETECTION (LLD) Report the measured LLD for each radiological contaminant. If the LLD is above the EPA specified method detection limit, the result is not valid and should not be reported. If high TDS caused interferences, you may need to run the sample for a longer count time to achieve an acceptable LLD. For questions or concerns regarding the LLD, contact Pa DEP Bureau of Laboratories. COUNTING ERROR (CE) ANALYSIS DATE LOCATION/ENTRY POINT ID LOCATION/ENTRY POINT NAME Report the counting error for gross alpha analyses only. The measured gross alpha value plus the counting error is equal to a confidence interval of 95%. Enter the date (MMDDYY) on which the sample analysis was performed or if the analysis spanned more than one day, the date on which the sample analysis result was obtained. Example: Enter April 21, 2005 as Enter the 3-digit Entry Point ID number assigned to the sampling point by the local DEP or CHD office. If the water supplier has not provided this ID number to you, then contact the water supplier or the local DEP or CHD office. Entry Point ID numbers always begin with 1 (e.g., 100, 102, 103 ). Enter the name of the Entry Point at which the sample was collected / December 20, 2008 / Page 9

13 DATA FIELD SAMPLE DATE SAMPLE TYPE SAMPLE TIME LAB ID LAB NAME AND PHONE APPROVED BY EXPLANATION Enter the date (MMDDYY) on which the sample was collected. Example: Enter August 14, 2005 as Enter the appropriate letter code which corresponds to the type of sample collected as follows: C = Check: Confirmation samples taken in response to repeat or initial samples that are detected at a level in excess of the MCL. E = Entry Point: Samples taken at the entry point to the distribution system. S = Special: A supplier may wish to collect and have analyzed special samples to meet his own need, or may be required by DEP or a CHD to take samples to fulfill a special requirement. For example, a PWS may be asked to take delinquent samples after a monitoring period has ended. Such samples must be coded S to distinguish them from routine E samples which may be taken during the same period. R = Raw Water: A supplier may wish to collect and have analyzed samples of raw water to meet their particular need, such as new source sampling. Such samples will not be credited toward routine monitoring requirements. P = Plant: Performance monitoring samples that are collected after the radionuclide treatment process, but before the entry point sampling location. Enter the time the sample was collected in Military Time. Example: Enter 1:30 PM as 1330 Enter the 5-digit PA Certification Identification Code assigned to the laboratory that actually analyzed the samples. The ID number must be entered for results to be accepted. Enter the name and phone number of the laboratory analyzing the samples. Signature of responsible official and date signed / December 20, 2008 / Page 10

14 SECTION 4: SUMMARY OF CODES FOR REPORTING NATURAL RADIOLOGICALS te: The analyses listed in this table are current as of 40CFR March 12, Please note that there are additional online methods approved for these analyses that are not included in the tables below. Refer to the current version of 40 CFR for a listing of all approved methods. PARAM NAME Gross Alpha by Evaporation PARAM ID 4002 (unadjusted gross alpha) ANALYSIS METHOD EPA Prescribed Procedures for Measurement of Radioactivity in Drinking Water (EPA/600/ ) August ANALYSIS METHOD AVAILABILITY (NTIS): PB DEP METHOD CODE 401 Interim Radiochemical Methodology for Drinking Water (EPA 600/ ) (revised) March 1976 Page 1 (NTIS): PB EPA Radiochemistry Procedures Manual (EPA 520/ ) December 1987 (NTIS): PB Radiochemical Analytical Procedures for Analysis of Environmental Samples, March 1979 Page 1 (NTIS): EMSL LV SM Standard Methods for the Examination of Water and Wastewater, 13th (1971) Edition American Water Works Assn. (AWWA) - Included in 13th Edition of Standard Methods (1971) SM 7110 B - Standard Methods for the Examination of Water and Wastewater, 17th (1989), 18th (1992), 19th (1995) and 20th (1998) Editions American Water Works Assn. (AWWA) - Included in 17th (1989), 18th (1992), 19th (1995) and 20th (1998) Editions of Standard Methods USGS R Methods for the Determination of Radioactive Substances in Water and Fluvial Sediments U.S. Geological Survey - Found in Chapter A5 of Book 5, Techniques of Water- Resources Investigations of the USGS (1977) / December 20, 2008 / Page 11

15 PARAM NAME PARAM ID ANALYSIS METHOD ANALYSIS METHOD AVAILABILITY DEP METHOD CODE Gross Alpha by Coprecipitation 4002 (unadjusted gross alpha) EPA Radiochemistry Procedures Manual (EPA 520/ ) December 1987 (NTIS) - PB SM 7110 C - Standard Methods for the Examination of Water and Wastewater, 18th (1992),19th (1995) and 20th (1998) Editions American Water Works Assn. (AWWA) - Included in 18th (1992), 19th (1995) and 20th (1998) Editions of Standard Methods Radium 226 using Radon Emanation Technique 4020 EPA Prescribed Procedures for Measurement of Radioactivity in Drinking Water (EPA/600/ ) August 1980 (NTIS) - PB Interim Radiochemical Methodology for Drinking Water (EPA 600/ ) (revised) March 1976 Page 16 (NTIS) - PB EPA Ra-04 Radiochemistry Procedures Manual (EPA 520/ ) December 1987 (NTIS) - PB Radiochemical Analytical Procedures for Analysis of Environmental Samples, March 1979 Page 19 (NTIS) - EMSL LV SM 305 Standard Methods for the Examination of Water and Wastewater, 13th (1971) Edition American Water Works Assn. (AWWA) - Included in 13th Edition of Standard Methods (1971) SM 7500-Ra C Standard Methods for the Examination of Water and Wastewater, 17th (1989), 18th (1992), 19th (1995) and 20th (1998) Editions American Water Works Assn. (AWWA) - Included in 17th (1989), 18th (1992), 19th (1995) and 20th (1998) Editions of Standard Methods / December 20, 2008 / Page 12

16 PARAM NAME PARAM ID ANALYSIS METHOD ANALYSIS METHOD AVAILABILITY DEP METHOD CODE ASTM D Annual Book of ASTM Standards, Vol and (1999) ASTM International any year containing the cited version of the method may be used. USGS R Methods for the Determination of Radioactive Substances in Water and Fluvial Sediments U.S. Geological Survey - Found in Chapter A5 of Book 5, Techniques of Water- Resources Investigations of the USGS (1977) DOE Ra-04 EML Procedures Manual, 28th (1998) or 27th (1990) Editions, Volumes 1 and 2; either edition may be used. Department of Energy (DOE) - In the 27th edition, Method Ra-04 is listed as Ra-05. Available through the Environmental Measurements Laboratory of DOE Determination of Ra-226 and Ra-228 (Ra-02), January 1980, Revised June 1982 Radiological Sciences Institute Center for Laboratories and Research - Method written by the NY State Dept. of Health Radium 226 using Radiochemical Methodology 4020 EPA Prescribed Procedures for Measurement of Radioactivity in Drinking Water (EPA/600/ ) August 1980 (NTIS) - PB Interim Radiochemical Methodology for Drinking Water (EPA 600/ ) (revised) March Page 13 (NTIS) - PB EPA Ra-03- Radiochemistry Procedures Manual (EPA 520/ ) December 1987 (NTIS) - PB SM Standard Methods for the Examination of Water and Wastewater, 13th (1971) Edition American Water Works Assn. (AWWA) - Included in 13th Edition of Standard Methods (1971) / December 20, 2008 / Page 13

17 PARAM NAME PARAM ID ANALYSIS METHOD ANALYSIS METHOD AVAILABILITY DEP METHOD CODE SM 7500-Ra B - Standard Methods for the Examination of Water and Wastewater, 17th (1989), 18th (1992),19th (1995) and 20th (1998) Editions American Water Works Assn. (AWWA) - Included in 17th (1989), 18th (1992), 19th (1995) and 20th (1998) Editions of Standard Methods ASTM D Annual Book of ASTM Standards, Vol and (1999) ASTM International any year containing the cited version of the method may be used. USGS R Methods for the Determination of Radioactive Substances in Water and Fluvial Sediments U.S. Geological Survey - Found in Chapter A5 of Book 5, Techniques of Water- Resources Investigations of the USGS (1977) Radium 226 using Gamma-ray Spectrometry 4020 Determination of Radium-226 and Radium-228 in Drinking Water by Gamma-ray Spectrometry Using HPGE or Ge(Li) Detectors, Revision 1.2, December 2004 Environmental Resources Center, Georgia Institute of Technology 416 Radium 228 using Radiochemical Methodology 4030 EPA Prescribed Procedures for Measurement of Radioactivity in Drinking Water (EPA/600/ ) August PB Interim Radiochemical Methodology for Drinking Water (EPA 600/ ) (revised) March Page 24 - PB EPA Ra-05 - Radiochemistry Procedures Manual (EPA 520/ ) December PB Radiochemical Analytical Procedures for Analysis of Environmental Samples, March Page 19 - EMSL LV / December 20, 2008 / Page 14

18 PARAM NAME PARAM ID ANALYSIS METHOD ANALYSIS METHOD AVAILABILITY DEP METHOD CODE SM 7500-Ra D - Standard Methods for the Examination of Water and Wastewater, 17th (1989), 18th (1992),19th (1995) and 20th (1998) Editions American Water Works Assn. (AWWA) - Included in 17th (1989), 18th (1992), 19th (1995) and 20th (1998) Editions of Standard Methods USGS R Methods for the Determination of Radioactive Substances in Water and Fluvial Sediments U.S. Geological Survey - Found in Chapter A5 of Book 5, Techniques of Water- Resources Investigations of the USGS (1977) Determination of Ra-226 and Ra-228 (Ra-02), January 1980, Revised June 1982 Radiological Sciences Institute Center for Laboratories and Research - Method written by the NY Dept. of Health Determination of Ra-228 in Drinking Water (August 1980) State of NJ, Dept of Environmental Protection - Method written by the State of NJ, Dept. of Env. Prot. Radium 228 using Gamma-ray Spectrometry 4030 Determination of Radium-226 and Radium-228 in Drinking Water by Gamma-ray Spectrometry Using HPGE or Ge(Li) Detectors, Revision 1.2, December 2004 Environmental Resources Center, Georgia Institute of Technology 416 Uranium using Radiochemical Methodology 4006 EPA Prescribed Procedures for Measurement of Radioactivity in Drinking Water (EPA/600/ ) August PB SM 7500-U B - Standard Methods for the Examination of Water and Wastewater, 17th (1989), 18th (1992), 19th (1995) and 20th (1998) Editions American Water Works Assn. - Included in 17th (1989), 18th (1992), 19th (1995) and 20th (1998) Editions of Standard Methods / December 20, 2008 / Page 15

19 PARAM NAME PARAM ID ANALYSIS METHOD ANALYSIS METHOD AVAILABILITY DEP METHOD CODE Uranium using Fluorometric Methodology 4006 EPA Prescribed Procedures for Measurement of Radioactivity in Drinking Water (EPA/600/ ) August PB SM 7500-U C - Standard Methods for the Examination of Water and Wastewater, 17th (1989) Edition American Water Works Assn. - Included in 17th (1989) Edition of Standard Methods ASTM D Annual Book of ASTM Standards, Vol and (1999) ASTM International any year containing the cited version of the method may be used. USGS R and R Methods for the Determination of Radioactive Substances in Water and Fluvial Sediments U.S. Geological Survey - Found in Chapter A5 of Book 5, Techniques of Water- Resources Investigations of the USGS (1977) DOE U-04 - EML Procedures Manual, 28th (1998) or 27th (1990) Editions, Volumes 1 and 2; either edition may be used Department of Energy (DOE) - Available through the Environmental Measurements Laboratory of DOE Uranium using ICP-MS Methodology 4006 EPA Determination of Trace Elements in Waters and Wastes by Inductively Coupled Plasma-Mass Spectrometry" Revision 5.4 which is published in "Methods for the Determination of Metals in Environmental Samples - Supplement I," EPA 600-R , May PB SM Standard Methods for the Examination of Water and Wastewater, 20th (1998) Edition American Water Works Assn. - Included in 20th (1998) Edition of Standard Methods / December 20, 2008 / Page 16

20 PARAM NAME PARAM ID ANALYSIS METHOD ANALYSIS METHOD AVAILABILITY DEP METHOD CODE ASTM D Annual Book of ASTM Standards, Vol and (1999) version of D is available. ASTM International any year containing the cited version of the method may be used. Uranium using Alpha Spectrometry 4006 EPA Radiochemistry Procedures Manual (EPA 520/ ) December PB Radiochemical Analytical Procedures for Analysis of Environmental Samples, March Page 33 - EMSL LV SM 7500-U C - Standard Methods for the Examination of Water and Wastewater, 18th (1992), 19th (1995) and 20th (1998) Editions American Water Works Assn. - Included in 18th (1992), 19th (1995) and 20th (1998) Editions of Standard Methods ASTM D , 02 - Annual Book of ASTM Standards, Vol and (2002) ASTM International any year containing the cited version of the method may be used. USGS R Methods for the Determination of Radioactive Substances in Water and Fluvial Sediments U.S. Geological Survey - Found in Chapter A5 of Book 5, Techniques of Water- Resources Investigations of the USGS (1977) DOE U-02 - EML Procedures Manual, 28th (1997) or 27th (1990) Editions, Volumes 1 and 2; either edition. Department of Energy (DOE) - Available through the Environmental Measurements Laboratory of DOE Uranium by Laser Phosphorimetry 4006 ASTM D , 02 - Annual Book of ASTM Standards, Vol and (2002) ASTM International any year containing the cited version of the method may be used / December 20, 2008 / Page 17

21 SECTION 5: MONITORING REQUIREMENTS FOR NATURAL RADIOLOGICALS Initial Monitoring Schedule: Systems serving: > 3,300 persons start January 1, to 3,300 persons start January 1, 2006 < 500 persons start January 1, 2007 New entry points associated with new sources must begin quarterly monitoring the quarter after they start serving the public. Important Monitoring tes: If sampling more than once per year, compliance is based on the running annual average (RAA). Report quarterly all of the entry point results. For initial monitoring, systems may composite the first 4 quarters, but it is not recommended. Repeat monitoring schedules are based on the previous monitoring results. Repeat monitoring frequencies are summarized in Table 5.1. Monitoring must occur for each contaminant at each entry point. Repeat monitoring for radium-226 and radium-228 is based on the previous cycle s combined radium-226/radium-228 value. For entry points where treatment has been installed, quarterly performance monitoring and annual compliance monitoring must be conducted for the treated contaminant / December 20, 2008 / Page 18

22 Table 5-1: Monitoring Requirements: All Community Water Systems 1 Contaminants Gross Alpha (GA), Radium- 226, Radium-228, and Uranium GA may be substituted for Radium-226 if GA plus the Counting Error (CE) is < 5 pci/l GA may be substituted for Uranium if GA plus the CE < 15 Initial Monitoring Frequency 4 consecutive quarters at each entry point 2 Shortened Sampling Option: If the first two quarterly samples for each contaminant at each EP is non-detect, the final two quarters are waved. Repeat Monitoring Frequency 3 (Begins January 2008) If RAA of quarterly results, or if single repeat sample results are: < Detection limit: 9-year monitoring > Detection limit to < ½ MCL: 6-year monitoring > ½ MCL (but < the MCL): 3-year monitoring te: If more than 1 sample collected during a quarter when on quarterly or more than 1 sample during year when on 3, 6, or 9 year frequency, average all samples. Monitoring Year The required repeat monitoring year is based on: The most recent sampling year The new monitoring frequency. See Table 5-2 for complete explanation. Increased Monitoring: If any single sample exceeds the MCL level, the system must sample quarterly, beginning with the next calendar quarter, until 4 consecutive quarters are below the MCL level. It is a Violation if: MCL RAA of quarterly monitoring exceeds the MCL 4 Any single repeat sample result exceeds 4 times the MCL level. M/R Major: samples collected and/or reported during a monitoring period Minor: Some, but not all samples collected during a monitoring period 1 Bottled water systems, vended water systems, retail water facilities, and bulk water hauling systems (BVRB) must sample each EP for gross alpha, radium-226, radium-228, and uranium every 4 years. 2 If average of 4 quarters > MCL, then continue quarterly monitoring until 4 consecutive quarterly results are < MCL. 3 Annual monitoring is required at entry points where treatment has been installed for radionuclide removal. 4 For gross alpha, this refers to RAA of adjusted results whenever possible. Table 5-2: Required Monitoring Year Based on the results of initial monitoring, DEP s data system will store the next required monitoring year for each contaminant. The contaminant must be sampled in this required year. Sampling early will not reset the monitoring frequency unless the result value is > the MCL. After each repeat monitoring year, the monitoring frequency and next required monitoring year are reset. You can use the table on the next page to help you determine the next monitoring year / December 20, 2008 / Page 19

23 Table Instructions: 1. Find the row that corresponds to the most recent required monitoring year for each contaminant. For initial monitoring, the most recent required year is based on population, as shown below. 2. Move across the row to the column that corresponds to the required frequency for each contaminant to find your next required monitoring year. 3. Repeat for each contaminant at each entry point. Next Required Monitoring Year Most Recent Required Required to take 1 Required to take 1 Required to take 1 Monitoring Year 1 sample every 3 years sample every 6 years sample every 9 years (from Table 2, Column (from Table 2, Column (from Table 2, Column 2) sample in: 2) sample in: 2) sample in: 2005 (Initial Mon. for >3,300) (Initial Mon. for pop n >500 to <3,300) (Initial Mon. for <500) If an EP must continue quarterly monitoring (per column 6 of Table 1), the year in which the EP achieves four quarters below the MCL becomes the Most Recent Required Monitoring Year. The flowcharts on the following pages display the monitoring requirement for gross alpha, radium-226, radium-228, and uranium / December 20, 2008 / Page 20

24 FIGURE 5.1 INITIAL MONITORING GROSS ALPHA, RADIUM-226, RADIUM-228, AND URANIUM START Repeat this flowchart for each contaminant: Gross alpha, combined radium-226/228 (Ra- 226 and Ra-228 are analyzed separately) and uranium. Repeat this flowchart for each entry point Monitor quarterly for contaminant starting the quarter after new EP goes into use (or initial monitoring period begins) NOTE: Depending on the results, gross alpha values can be substituted for radium-226 and uranium (see Figure 4 for substitution determination). Substiution values are used to determine compliance. Also, if gross alpha exceeds the MCL, adjusted gross alpha should be determined and used for compliance (see Figure 2) Did system opt to composite each contaminant for 4 consecutive quarters? Analyze each contaminant each quarter First 2 quarters below the detection limit for any contaminants? Composite result > 1/2 MCL for any contaminant Composite result > MCL? Go to Repeat Monitoring Flowchart for each contaminant that was below the detection limit. Continue with 2 additional quarters of sampling for the contaminants that were above the detection limit RAA > MCL Continue quarterly sampling for 2 additional quarters Initial Complete: Proceed to Repeat Monitoring Flowchart (Figure 3) Did DEP request add'l quarterly samples? MCL Violation Continue quarterly monitoring (do not composite) RAA > MCL? RAA > MCL Four consecutive quarterly results at or below the MCL value? Initial Complete : Proceed to Repeat Monitoring Flowchart (Figure 3) / December 20, 2008 / Page 21

25 FIGURE 5.2: ADJUSTED GROSS ALPHA DETERMINATION te: When analyzing gross alpha, a system may choose to also analyze uranium. DEP determines an adjusted gross alpha value using the following procedure. Unadjusted gross alpha value from laboratory Did lab measure and report uranium in same monitoring period as gross alpha? Use unadjusted gross alpha result for compliance determinations Did laboratory measure and report radon in the same monitoring period as gross alpha? te: If the laboratory used a non-evaporative procedure to analyze gross alpha, radon should be measured and reported. 1 PADWIS subtracts uranium from unadjusted gross alpha Subtract uranium result and radon result from unadjusted gross alpha Calculated adjusted gross alpha value used for compliance and determination of next monitoring frequency 1 A non-evaporative procedure does not remove radon during analysis / December 20, 2008 / Page 22

26 FIGURE 5.3: REPEAT MONITORING: GROSS ALPHA PARTICLE ACTIVITY, RADIUM-226, RADIUM-228, and URANIUM START Repeat this flowchart for each contaminant, gross alpha, combined radium- 226/228 (Ra-226 and Ra-228 are analyzed separately) and uranium, to determine the repeat monitoring frequency after initial monitoring and after each subsequent sampling event Repeat this flowchart for each entry point NOTE: Gross alpha, depending on the result, can be substituted for radium-226 and uranium (see Figure 4 for substitution determination). Substiution values are used to determine compliance and the next monitoring frequency. Also, if uranium is reported, it will be subtracted from uranium to give an "adjusted" gross alpha result. Previous result < the detection limit? Previous result < 1/2 the MCL? Previous result < the MCL Test for contaminant every 9 years Test for contaminant every 6 years Test for contaminant every 3 years MCL Value exceeded: Quarterly monitoring beginning the quarter after the exceedance te: If gross alpha exceeds the MCL, adjusted gross alpha must be determined and used for compliance (see Figure 2) RAA > MCL? MCL Violation Four consecutive quarters below the MCL? In compliance, determine next monitoring frequency based on RAA Continue quarterly monitoring / December 20, 2008 / Page 23

27 FIGURE 5.4: GROSS ALPHA SUBSTITUTION Measure gross alpha Is gross alpha value < 15 pci/l May not substitute gross alpha for uranium and radium-226 Is gross alpha + counting error < 15 pci/l May substitute gross alpha value for uranium May not substitute gross alpha for radium-226 Is gross alpha + counting error < 5 pci/l May substitute gross alpha for radium / December 20, 2008 / Page 24

28 SECTION 6: REPORTING REQUIREMENTS FOR MAN-MADE RADIOLOGICALS This section applies to all CWSs that are designated by DEP to be vulnerable to beta particle and/or photon radioactivity or designated as using waters contaminated by effluent from a nuclear facility. Table 1: MCL, Screening Level, and EPA Detection Limits Contaminant Screening Level or EPA Method MCL Equivalent Dose Detection Limit Gross Beta - Vulnerable 50 pci/l 4 pci/l Gross Beta - Contaminated 15 pci/l 4 pci/l Tritium 20,000 pci/l 1,000 pci/l Strontium-90 8 pci/l 2 pci/l Iodine-131 Beta particle and photon radioactivity Monitoring Summary: 4 mrem/yr 1 pci/l Varies by constituent Systems designated as vulnerable to beta particle or photon activity must monitor for gross beta, tritium, and strontium-90 in addition to the gross alpha monitoring required for all community water systems. Systems designated as using waters contaminated by effluents from a nuclear facility must sample for these same contaminants in addition to iodine-131. Vulnerable systems must collect quarterly samples for gross beta and annual samples for tritium and strontium-90. Monitoring can be reduced to every 3 years. Monitoring details are discussed in Section 8 of this manual. Systems designated as using water contaminated by effluents must collect monthly samples for gross beta, quarterly samples for tritium and strontium-90, and a composite of 5 consecutive daily samples each quarter for iodine-131. The MCL for beta particle and photon radioactivity is 4 millirem/yr (mrem/yr) and is based on the annual dose equivalent to the total body or any internal organ. DEP will determine the annual dose equivalent for each of the major radioactive constituents listed and determine the total summed dose. The same or equivalent sample must be analyzed for the major radioactive constituents whenever any of the following occurs: o o o o Gross beta exceeds the screening level Strontium-90 exceeds 8 pci/l Tritium exceeds 20,000 pci/l Iodine-131 exceeds 3.37 pci/l Contact DEP for additional information and reporting instructions whenever individual constituent analysis for beta particle and photon radioactivity is required / December 20, 2008 / Page 25

29 Important Reporting tes: 1. Report all results on an SDWA-4 form. Enter the result of each sample analyzed to at least 3 decimal places if the result is a valid detect. Do not round. 2. Report the results within either the first 10 days following the month in which the result is determined or the first 10 days following the end of the required monitoring period, whichever is shorter. 3. All laboratory results must meet EPA detection limits. 4. Any result that is less than the EPA detection limit (shown above) should be reported as zero (0). To be a valid detect, the value must be greater than the EPA detection limit and greater than or equal to the laboratory detection limit. Example: Laboratory detection limit = 3 pci/l but the EPA detection limit = 4 pci/l Gross beta result = pci/l; this is a valid detect. 5. Report all results in pci/l. 6. Do not convert activity values (pci/l) to dose values (mrem/yr). PADWIS will perform this calculation. 7. The rule allows for the subtraction of naturally occurring potassium-40 from gross beta results. If potassium-40 is analyzed, report in pci/l. Alternatively, elemental potassium may be analyzed and reported in mg/l. PADWIS will convert this value to activity before subtracting it from the gross beta result. PADWIS will then calculate the adjusted gross beta value by subtracting the potassium-40 contribution. 8. If beta particle activity minus potassium-40 exceeds the screening level (50 or 15 pci/l), notify the water system and DEP immediately (within 1 hour). If potassium-40 is not analyzed, notification to the water system and DEP is still required based on the gross beta result. The same sample must be analyzed to determine the major radioactive constituents present. When analysis of the major radioactive constituents is required, report the activity results for each constituent detected in pci/l. If an isotopic-specific method is used, such as for cesium-134 or radioactive iodine, the same or equivalent sample must also be analyzed for the gamma emitting radionuclides using an approved method. 9. Composite Analysis Reporting: Compositing is only allowed at entry points that have been designated as using waters contaminated by effluent from a nuclear facility. After the composite sample is analyzed, report the result on separate SDWA-4 forms by submitting one form for each sample (i.e. quarterly sample or monthly sample) in the composite / December 20, 2008 / Page 26

30 Report the sample date on the form as the actual sample collection date for the quarterly or monthly sample. Report the sample period on the form for the quarter in which it was sampled. For data tracking purposes, DEP s data system needs four quarters of data or three monthly samples, depending on the contaminant, even though the result will be the same in each quarter. Example: Quarterly composite result for strontium-90 at EP 101: pci/l Report the composite result on four separate SDWA-4 forms: SDWA-4 Form 1: Result = pci/l; Sample Date 02/09/2005 SDWA-4 Form 2: Result = pci/l; Sample Date 05/17/2005 SDWA-4 Form 3: Result = pci/l; Sample Date 08/23/2005 SDWA-4 Form 4: Result = pci/l; Sample Date 10/15/ / December 20, 2008 / Page 27

31 DATA FIELD SMALL BOX IN UPPER RIGHT HAND CORNER PWS NAME, ADDRESS and PHONE NUMBER PWS ID TRANSACTION CODE SAMPLE PERIOD CONTAMINANT ID EXPLANATION ELEVATED RESULTS enter an X if the result of any sample exceeds the MCL value. Enter the name and address of the public water system to which these samples apply. Also, enter the phone number of the contact person for the water system. Enter the 7-digit public water system identification number to which these samples apply. FAILURE TO ENTER THE PWS ID WILL RESULT IN THE WATER SUPPLIER NOT RECEIVING CREDIT FOR CONDUCTING THE MONITORING. If you do not know the PWS ID number, and the PWS cannot provide it to you, contact the local DEP or CHD office or check DEP s web site. The local DEP or CHD office assigns all PWS ID numbers. Enter as 03 (pre-printed on the SDWA-4) Enter the beginning date (MMDDYY) and end date (MMDDYY) for the sampling period during which the sample results apply. For annual monitoring, the monitoring period is the calendar year in which the sampling is conducted. Example: For the April-June 2007 quarter, enter to For the year 2007, enter to Enter the 4-digit contaminant identification code for the parameter being reported. Gross Beta 4100 Tritium 4102 Strontium Iodine Major Radioactive Constituents contact DEP for additional information CONTAMINANT NAME ANALYSIS METHOD ANALYSIS RESULT Enter the name of the contaminant being reported: gross beta, tritium, strontium-90, iodine-131, etc. Enter the 3-digit code of the approved analysis method used to analyze the samples (see Section 7). Enter the result of each sample analyzed to at least 3 decimal places if the result is a valid detect. Do not round. The decimal point must be entered directly in the result field. If any result is less than the EPA specified method detection limit, report the result as zero (0). te that the EPA detection limit is a whole number. Be sure to use the proper units. Report ALL results in pci/l / December 20, 2008 / Page 28