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William A. Telliard Director, Analytical Methods EPA Office of Water September 2005

History and Status of Methods for Oil and Grease and the Federal Advisory Committee on Detection and Quantitation Approaches. William A. Telliard Director, Analytical Methods EPA Office of Water September 2005. Status of EPA Methods for “Oil and Grease”. Regulatory definition.

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William A. Telliard Director, Analytical Methods EPA Office of Water September 2005

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  1. History and Status of Methodsfor Oil and Grease and the Federal Advisory Committee on Detection and Quantitation Approaches William A. Telliard Director, Analytical Methods EPA Office of Water September 2005

  2. Status of EPA Methods for “Oil and Grease”

  3. Regulatory definition • The EPA Administrator identified "oil and grease" as a "conventional pollutant" under Section 304(a)(1) of the Clean Water Act. The list of five conventional pollutants is codified at 40 CFR 401.16 and consists of: • Biochemical oxygen demand (BOD), • total suspended solids (TSS), • fecal coliform, • pH, and • oil and grease • Oil and grease is regulated in more than 10,500 National Pollutant Discharge Elimination System (NPDES) permits and in effluent guidelines for more than 650 industrial subcategories within more than 25 industrial categories.

  4. Regulatory History of the Phase-out of Chlorofluorocarbons • The Montreal Protocol on Substances that Deplete the Ozone Layer regulates the use of chlorofluorocarbons (CFCs), with a phase-out by 1996 • The Clean Air Act Amendments of 1990 (CAAA) commit EPA to phase out manufacture and import of CFCs and other controlled substances • For special exempted uses, including laboratory use, the phase-out deadline was extended to 2005 • On April 6, 2004, EPA proposed the withdrawal of Method 413.1 from 40 CFR 136, because it uses CFC-113. Final action is expected in mid-2005.

  5. EPA Method Development Efforts • EPA is collaborating with ASTM to develop I-R method ASTM D7066-04 • EPA is collaborating with ASTM on the use of deuterated solvents in methods for oil and grease and for TPH • EPA conducted method development studies for oil and grease methods beginning in 1992 that resulted in the development of: Method 1664A n-Hexane Extractable Material (HEM; Oil and Grease) and Silica Gel Treated N-Hexane Extractable Material (SGTHEM; Non-polar Material) by Extraction and Gravimetry

  6. Efforts to Replace CFC-113 – Phase 1 • In 1991-1992, EPA examined other solvents, including: • n-Hexane • n-Hexane + MTBE (80/20) • Methylene chloride • Perchloroethylene • DuPont-123 • Using "real-world" samples from: • 39 Plants • 24 Industrial categories • 41 Aqueous wastes • 30 Solid wastes

  7. Phase 1 “Real World” Sample Types

  8. Phase 2 - Solvents and Techniques • CFC-113 • CFC-113 + silica gel adsorption • n-Hexane • n-Hexane + silica gel adsorption • Cyclohexane • Cyclohexane + silica gel adsorption

  9. Phase 2 - Industrial Categories Non-Petroleum Sources: 4 Meat Product Plants 2 Coil Coating Plants 2 Miscellaneous Foods 2 Textile Manufacturers 2 Leather Tanning Plants 1 Metal Molding and Casting 1 Meat Processing Plant 1 Soap & Detergent Manuf. 1 POTW Petroleum Sources: 3 Metal Finishing Plants 3 Shore Reception Facilities 2 Petroleum Refineries 2 Transportation Facilities 2 Drum Reconditioning Fac. 2 Organic Chemical Plants 1 Industrial Laundry

  10. Guidance Available from EPA’s Web Site • Analytical Method Guidance for EPA method 1664A Implementation and Use (40 CFR part 136) • Frequently Asked Questions EPA Methods for Testing Oil and Grease In Water and the Use of Ozone Depleting Substances • Fact Sheet • Errata Sheet www.epa.gov/waterscience/methods

  11. Infra-red (I-R) Methods for O&G and TPH • Present EPA I-R methods are: • Method 413.2 for determination of oil and grease in water and wastes • Method 418.1 for determination of TPH in water and wastes • Neither method is approved for use at 40 CFR part 136 • Hexane will not work as a solvent for I-R analysis • EPA is collaborating with ASTM to develop I-R method ASTM D7066-04

  12. ASTM D7066-04 • Title: Standard Test Method for Dimer/Trimer of Chlorotrifluoroethylene (S-316) Recoverable Oil and Grease and Nonpolar Material by Infrared Determination • Commonly known as “Oil and Grease, and TPH, by Flon I-R” • Applicable to water, primarily intended for wastewater • Flon S-316 used as the extraction solvent • Proprietary • Manufactured by Asahi Chemical Company • Detection by fixed-wavelength I-R at 3.4 μm(2930 cm-1)

  13. Background • Developed to replace EPA Method 418.1, which employs Freon-113 as the extraction solvent • Also measures substances that volatilize and are lost in gravimetric methods such as EPA Method 1664A • Method 1664A uses n-hexane for the extraction solvent • n-Hexane boils at 68 °C • Any substance that boils below about 120°C will be partially or totally lost in the solvent evaporation step

  14. Other Solvent Tested • Asahkilin AK-225 is a mixture of: • 3,3-Dichloro-1,1,1,2,2,-pentafluoropropane (HCFC-225ca) and • 1,3-Dichloro- 1,1,2,2,3,-pentafluoropropane (HCFC-225cb) • AK-225 was found unacceptable because of high background in the I-R caused by hydrogen on the molecule and impurities in the solvent

  15. Sample Collection and Processing Steps • Sample size: 250 mL • Acidify to ~pH 2 with H2SO4 or HCl • Refrigerate at <4 °C from collection to analysis (caution not to freeze) • Serially extract 3x with 15-mL portions of Flon S-316 in separatory funnel • Dry extract over sodium sulfate • Adjust extract final volume to 50 mL • Place aliquot in cuvette and read in I-R

  16. Calibration • Calibration standards are a mixture of: • Octanoic acid (to simulate polar materials) • Isooctane (to simulate petroleum hydrocarbons) • Calibration solutions • 25, 50, 100, 250, and 500 μg/mL in Flon S-316 • Equivalent to 5, 10, 20, 50, and 100 mg/L in water • Each solution tested in I-R and response recorded • Calibration linearity tested as <15% RSD of calibration factors; if 15% exceeded, recalibrate with fresh calibration solutions

  17. Quality Control • Initial demonstration of capability, a 7-replicate initial precision and recovery (IPR) test • Average recovery for the 7 replicates must be in range of 59 – 100% • RSD of 7 replicates must be less than 8% • Laboratory control sample (LCS) with each batch of 20 samples • Recovery must be in range of 59 – 100% • Method blank with each batch of 20 samples • Oil and grease and TPH must be less than 5 mg/L, or 1/10 the concentration found in the sample, whichever is less

  18. Quality Control (continued) • Matrix spike/matrix spike duplicate (MS/MSD) • Recovery • Must be in range of 69 – 100% for oil & grease • Must be in range of 35 – 100% for TPH • Precision • Can use MS/MSD or sample duplicate • RPD for MS/MSD or duplicate must be less than 8% • Independent reference material • From different source than the source of calibration standards • Suggested to be analyzed at least once per quarter

  19. Validation • Initial testing at Wilkes Enterprises and in several other laboratories • Validated in an interlaboratory study • Multiple matrices • Reagent water • Can producer wastewater • Oil re-processor wastewater • Meat-packing industry wastewater • Samples were collected in large-volume containers, divided into aliquots, and spiked at Hampton Roads Sanitary District laboratory (HRSD)

  20. Interlaboratory Validation (continued)

  21. Interlaboratory Study Results • Bias with Flon S-316 or AK-225 was approximately -40% • Precision with Flon S-316 or AK-225 approximately 8% RSD • High background with AK-225 • ASTM D 7066 balloted and approved in 2004

  22. EPA/ASTM Study of Deuterated Solvents • In late 2004, the European Union (EU) banned use of Flon S-316 because of its potential ozone-depleting properties. ASTM D7066-04 uses Flon S-316 as the extraction solvent • EPA, the U.S. Navy, and the U.S. Coast Guard need test methods for oil and grease and for TPH that can be used in U.S. and international waters • EPA suggested use of a deuterated solvent as a replacement for Flon S-316 and Freon 113 in methods for oil and grease and for TPH

  23. Potential Advantages of Deuterated Solvents • The absorption maximum is shifted from 2930 cm-1 for substances containing carbon-hydrogen bonds to approximately 2200 cm-1 for substances containing only carbon-deuterium bonds • For deuterated solvents, the residual signal at 2930 cm-1 is small, thus allowing measurement of substances containing carbon-hydrogen bonds, such as oil and grease, and TPH

  24. Potential Disadvantages of Deuterated Solvents • Deuterated solvents cannot be made at 99.9999% isotopic purity and, therefore, will contain some impurities with carbon-hydrogen bonds • It is thought that the replacement of 1 or 2 deuterium atoms with hydrogen atoms will shift the absorption maximum toward 2930 cm-1 only slightly • Cost – typically 100 times the cost of normal solvents

  25. Candidate Solvents • Deuterated n-hexane (C6D14) • Isotopic purity: 98% • Cost: estimated at $15-20 per mL, in volume • Deuterated methylene chloride (C2D2Cl2) • Isotopic purity: 99.9% (also available in 99.96% purity) • Cost: estimated at $3-5 per mL, in volume • Deuterated toluene: (C7D9) • Isotopic purity: 99.5% (also available in 99.94% purity) • Cost: estimated at $2-4 per mL, in volume

  26. Cost Savings That Could Be Implemented • Reduce sample volume to 100 mL • Extract 3x with 3 mL of solvent (9 mL total) • Dry extract over sodium sulfate • Adjust final volume to 10 mL • Solvent cost per analysis would be approximately • $150-200 for deuterated n-hexane (prohibitive) • $30-50 for deuterated methylene chloride • $20-40 for deuterated toluene • U.S. Navy plans to test the 3 solvents, and to test the higher purity versions, if purity is a problem

  27. Additional Information For additional information contact: William A. Telliard, Director Analytical Methods Engineering and Analysis Division (4303T) Office of Science and Technology, Office of Water U.S. Environmental Protection Agency, Ariel Rios Building 1200 Pennsylvania Ave, NW Washington, DC 20460 Email: telliard.william@epa.gov but not after January 6, 2006

  28. Federal Advisory Committee on Detection and Quantitation Approaches and Uses in Clean Water Act Programs

  29. Why an Advisory Committee? • Longstanding concerns about how an MDL or ML is calculated and used in laboratory and regulatory programs • Proposed MDL and ML changes to 40 CFR part 136 in 2003 • Definition • Procedures

  30. Reaction to MDL/ML Proposal • 136 comments • Some supportive, most not. Theme: • We could do better • Let’s try a different approach, such as a collaborative consultation? • Decided to: • Withdraw proposed changes • Commission a situation assessment by a neutral facilitator

  31. Situation Assessment Process: Interviews By Interest • Environmental Community • Regulatory Community • Lab Community • Regulated Community • Organizations • Federal Agencies

  32. The Issues: Their history with the issues Key technical and policy questions Technical issues over which there has been disagreement and how they affect policy A potential consultative process: EPA role Goals, purpose and product Definition of success Participants Information needs and process design Interview Questions

  33. Common Issues From the Situation Assessment • Variability and reliability of results within labs, between labs and over time • Need to address background contamination, matrix and recovery effects, false positive and negative rates • What results should be reported – MDL? ML? • Need for common set of terms and definitions • Inconsistent uses of detection and quantitation limits by federal, state and local regulators; inconsistencies among EPA programs - CWA, RCRA, SDWA

  34. Scope of a Consultative Process Reach agreement on: • Definition of terms • One or more specific approaches for detection and quantitation for CWA • Interpretation and uses of the numbers

  35. Desired Product • Revised detection and quantitation approaches • acceptable to most or all • easy to carry out • practical and • cost-effective • Produce accurate, consistent and uniform results • Useful for future rulemaking

  36. Conditions of Success • EPA: • formally and fully committed, • works with internal partners to speak as one on behalf of EPA. • provides travel to entities that cannot otherwise participate. • A balance of the interests are at the table. • Independent technical expertise is available to the Committee to create a level playing field. • A product can be delivered in a year or so.

  37. Recommended Consultative Process Consensus-based Process Chartered Under FACA

  38. Det/Quant FACA Formation • January 26, 2005 - public meeting to report findings in the Situation Assessment • Solicited nominations for a Federal Advisory Committee through February 2005 • Committee chartered under FACA May 9, 2005 • Facilitator began to work with 21 members

  39. What is FACA? • Federal Advisory Committee Act • Enacted in 1972 • Established a system governing the creation, operation, and termination of Executive Branch advisory committees

  40. Purpose of FACA • Provide a structure for the establishment of groups to provide advice to the Federal government • Maximize public access to advisory committee deliberations and minimize the influence of special interest groups

  41. General FACA Requirements • Provide advice and recommendations — do not make decisions • Advisory committees are to be fairly balanced in terms of the points of view represented and the functions to be performed • The recommendations of an advisory committee are to be the result of the committee’s independent judgment

  42. General Requirements • Charter filed with Congress which sets out: • Scope • Objectives, and • Membership of the committee. • Designated Federal Officer (DFO) is appointed

  43. Requirements for Meetings • Designated Federal Officer (DFO) must be present at all meetings • Advisory committee meetings are required to be open to the public, with limited exceptions. • Meeting notices and agendas must be published in the Federal Register. • Any member of the public is permitted to file a written statement with the advisory committee.

  44. Membership • Members are appointed and may be removed by the EPA Administrator or his designee • Members serve at the discretion of the Administrator

  45. Limitations • Advisory Committees provide only advice and recommendations • Decision making and implementation authority remains with EPA • The DFO has the authority to close a meeting when it is in the public interest to do so

  46. Work Groups • A group made up of only a few committee members to analyze relevant issues and facts, draft proposed position papers, or conduct research (often include individuals who are not members of the chartered committee) • Exempt from FACA's openness and balance requirements, but EPA encourages working groups to hold open meetings and balance membership where feasible • Documents are available to the public under FACA only if they are presented to the chartered committee

  47. First Meeting June 21-22, 2005 • Facilitated by Triangle Associates • Mike Shapiro opened the meeting • Mary Smith chaired and represented EPA • Member/Group Interest Statements • “What is important to me/my group?” • Purpose, Roles, Ground Rules, Goals • Formed and Charged Technical Workgroup

  48. Committee Composition Environmental Labs EPA Industry State Government Facilitator Environmental Community POTWs

  49. Purpose of this Advisory Committee Provide group advice and consensus recommendations on approaches for the development of detection and quantitation procedures, and uses of these procedures in Clean Water Act programs.

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