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Status of Methods and Method Regulationsin EPA’s Water Programs

ASTM D19 Meeting

Cocoa Beach, Florida

January, 2006

Dale Rushneck, Interface, Inc.

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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

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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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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%

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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)

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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

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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

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Sampling Collection, Handling, and Preservation

The proposal revised sample collection, handling, and preservation requirements, including:

Raising the maximum holding temperature from 4oC to 6.00oC

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

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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

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Turbidity Update

EPA reproposed use of an alternative primary turbidity calibration standard (AMCO-AEPA-1 or AMCO-Clear)

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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.

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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.

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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 Technology’s 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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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

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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

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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

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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 Technology’s method for Radium-226 and Radium-228 in Drinking Water by Gamma-ray Spectrometry

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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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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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Detection/quantitation FACA Committee

EPA created a Federal Advisory Committee Act (FACA) committee to attempt to resolve issues surrounding detection and quantitation in EPA’s wastewater programs

Main FACA committee has held three meetings Main FACA committee has established several workgroups

– Policy workgroup– Technical workgroup

Workgroup for single-laboratory studies Workgroup for inter-laboratory studies

Details at EPA’s FACA Committee web site:

http://www.epa.gov/waterscience/methods/det/

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