1. Office of Water Status of Methods and Method Regulations in EPAs Water Programs ASTM D19 Meeting Cocoa Beach, Florida January, 2006 Dale Rushneck, Interface, Inc.

2. Office of Water Methods Update Proposal EPA proposed revisions and updates to wastewater and drinking water methods and monitoring regulations on April 6, 2004 (69 FR 18166) The proposal addressed: ! Wastewater Methods ! Other Updates to Wastewater Regulations ! Drinking Water Methods ! Request for Comments on Guidance Document A final rule is anticipated in Spring 2006

3. Office of Water Wastewater Methods EPA proposed: ! Three chemical ATPs for general use in NPDES monitoring: – ASTM International Method D6508 for determination of anions by capillary ion electrophoresis – Lachat QuikChem Method 10-204-00-1-X for determination of total cyanide using MICRODIST – Kelada-01 method for determination of total and available cyanide using UV-digestion, flash distillation and colorimetry ! One chemical ATP for use in the pulp and paper industry – NCASI Method CP–86.07 for determination of chlorinated phenolics by In situ Acetylation and GC/MS

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5. EPA Method 245.7 – Mercury by CVAFS EPA proposed EPA Method 245.7, Mercury in Water by Cold Vapor Atomic Fluorescence Spectrometry. The Association of Metropolitan Sewerage Agencies (AMSA) petitioned the Agency to approve Method 245.7 as an alternative to EPA Method 1631. ! However, EPA 245.7 omits the gold traps. EPA conducted a inter-laboratory study of Method 245.7 in 2001. ! Method detection limit = 5 ng/L. ! Average recovery = 85 – 105% in reagent water. ! Relative standard deviation (RSD) in reagent water <15%. ! Average recovery in industrial and municipal effluent = 64 – 120%

6. Office of Water Previously Proposed Methods EPA reproposed methods from a 10-18-95 proposal. ! The methods have been used through interim approvals since that time, so reproposal allowed EPA to receive comments on their use. Approval of the methods would harmonize approved revisions of drinking water and wastewater versions of inorganic methods, and would formalize approval of new technologies for wastewater monitoring, including: ! Inductively Coupled Plasma-Mass Spectrometry (e.g., EPA 200.8) ! Stabilized Temperature Graphite Furnace Atomic Absorption Spectroscopy (i.e., EPA 200.9) ! Ion Chromatography (e.g., EPA 300.0, EPA 218.6)

7. Office of Water VCSB Methods for Wastewater EPA proposed updated revisions of methods approved from voluntary consensus standards bodies (VCSBs). ! Eighty-five (85) revised Standard Methods ! Seventy (70) revised ASTM International methods EPA proposed two new ASTM International methods. ! D6888-03: Standard Test Method for Available Cyanide with Ligand Displacement and Flow Injection Analysis (FIA) Utilizing Gas Diffusion Separation and Amperometric Detection ! D6919-03: Determination of Dissolved Alkali and Alkaline Earth Cations and Ammonium in Water and Wastewater by Ion Chromatography

8. Office of Water Method Flexibility for Wastewater EPA proposed and requested comment on increased flexibility in methods used for wastewater monitoring. Under the proposal, analysts would be allowed to modify a method provided that: ! The analyte measured is not method-defined ! The chemistry of the method or the determinative technique are not changed ! The performance meets specified performance requirements and is documented

9. Office of Water Sampling Collection, Handling, and Preservation The proposal revised sample collection, handling, and preservation requirements, including: ! Raising the maximum holding temperature from 4 o C to 6.00 o C ! Revising preservation procedures for Cr(VI) and extending the holding time from 24 hours to 28 days ! Suggesting metals samples be preserved in the lab, not the field ! Removing requirement for icing metals samples for shipment ! Updating holding time requirements based on new studies

10. Office of Water Cyanide Preservation Based on comments and on ASTM D19 discussions, EPA is revising cyanide preservation to: ! Remove ascorbic acid as a preservative ! Add sodium borohydride and sodium arsenite as preservatives EPA is revising preservation requirements to address interferences from: ! Sulfur ! Sulfide ! Thiocyanate ! Aldehydes ! Carbonates ! Chlorine and hypochlorite

11. Office of Water Turbidity Update EPA reproposed use of an alternative primary turbidity calibration standard (AMCO-AEPA-1 or AMCO-Clear)

12. Office of Water Withdrawal of MCAWW Methods EPA proposed to withdraw 109 Methods for Chemical Analysis of Water and Wastes (MCAWW) from 40 CFR part 136, or replace them with newer versions of the same numbered method. ! The majority are single-analyte 200-Series methods for metals. ! Older methods for metals are largely supplanted by multi- analyte methods such as 200.7, 200.8, and 200.9, or newer VCSB methods that utilize the same analytical techniques as the methods to be withdrawn. ! MCAAW methods contain minimal QC requirements compared to VCSB and newer EPA methods.

13. Office of Water Withdrawal of MCAWW Methods (cont.) EPA proposed to withdraw Method 413.1, and other Freon-based oil and grease methods ! Freon is presently banned for testing oil and grease, and total petroleum hydrocarbons (TPH), in wastewater. ! EPA has been accepting data from tests using old Freon (made or imported prior to 2002) until Freon-base methods are withdrawn. ! After withdrawal, hexane-based methods would serve as the sole standard for oil and grease measurements. ! EPA may propose ASTM S-316-based method in future.

14. Office of Water New Drinking Water Methods EPA proposed four new chemical ATPs for drinking water monitoring: ! ASTM Method D6508 for the determination of anions by capillary ion electrophoresis ! Industrial Test Systems (ITS) free chlorine test strip method ! OI Analytical Method 1677-DW for determination of available cyanide by ligand exchange and amperometry ! Georgia Institute of Technologys method for The Determination of Radium-226 and Radium-228 in Drinking Water by Gamma- ray Spectrometry Using HPGE or Ge(Li) Detectors

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16. New Drinking Water Methods (cont.) EPA proposed the addition of EPA Method 327.0 to 40 CFR 141.74 for the measurement of chlorine dioxide residuals. EPA proposed updated revisions of methods approved from voluntary consensus standards bodies (VCSBs). ! Fifty-two (52) revised Standard Methods ! Twenty-four (24) revised ASTM International methods EPA proposed two new ASTM International methods ! D6888-03: Standard Test Method for Available Cyanide with Ligand Displacement and Flow Injection Analysis (FIA) Utilizing Gas Diffusion Separation and Amperometric Detection ! D6919-03: Determination of Dissolved Alkali and Alkaline Earth Cations and Ammonium in Water and Wastewater by Ion Chromatography

17. Office of Water Comments EPA received over 100 comments on the proposal from: ! Wastewater and drinking water utilities ! Academics ! Industry or trade groups ! Method developers ! VCSBs ! State regulatory agencies ! Citizens

18. Office of Water Notice of Data Availability – 2/16/05 (70 FR 7909) The NODA announced the availability of new information on methods for wastewater analyses (40 CFR 136): ! A microdistillation procedure for cyanide and its ability to recover particulate forms of cyanide ! Total Kjeldahl nitrogen (TKN) analyses ! Mercury analyses ! Total suspended solids analyses ! Microtox ! Method 624 for volatiles ! Waters Method D6508

19. Office of Water NODA (cont.) The NODA also provides new information on drinking water analyses (40 CFR 141) regarding: ! Interferences affecting Syngenta Method AG-625 Revised versions of VCSB methods proposed in 2004: ! ASTM D6888-04 for available cyanide ! ASTM D5673-03 for metals by ICP/MS ! ASTM D4658-03 for sulfide Revisions to Georgia Institute of Technologys method for Radium- 226 and Radium-228 in Drinking Water by Gamma-ray Spectrometry

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21. Wastewater Methods Under Development Method 1668A - PCB congeners by GC/HRMS ! Awaiting method detection limit data from EPA Regional labs Method 1614 - PBDE congeners by GC/HRMS ! Method being revised to incorporate 15-m column and temperature-programmed injector to improve precision and recovery of BDE 209 Nonylphenol and alkylphenol ethoxylates by GC/MS ! Development in collaboration with ASTM International ! Development by EPA Region V laboratory

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23. Wastewater Methods Under Development (cont) Methods to support studies of pollutants discharged from Publicly Owned Treatment Works (POTWs) ! Based on study by USGS – Organo-chlorine and organo-phosphate pesticides by GC/HRMS – Herbicides by GC/HRMS – Antibiotics by LC/MS/MS – Drugs by LC/MS/MS – Steroids and hormones by GC/HRMS Kinetic test procedure for prediction of coal mine drainage

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25. Detection/quantitation FACA Committee EPA created a Federal Advisory Committee Act (FACA) committee to attempt to resolve issues surrounding detection and quantitation in EPAs wastewater programs ! Main FACA committee has held three meetings ! Main FACA committee has established several workgroups – Policy workgroup – Technical workgroup 6 Workgroup for single-laboratory studies 6 Workgroup for inter-laboratory studies Details at EPAs FACA Committee web site: http://www.epa.gov/waterscience/methods/det/

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