U. S. Environmental Protection Agency Draft, August 13, 2003 Technical Subgroup on Incineration Test Methods for Telomers Introduction The PFOA ECA Plenary session held on July 10, 2003, approved an action plan for the Telomer Workgroup to form a Technical Subgroup on Incineration test methods. This subgroup will assess the adequacy of available incineration test methods to provide data on telomer degradation and the concurrent formation of by products that may result during the process on incineration. Where needed, specific approaches to address the unique characteristics of telomers and telomer based polymers will be incorporated into the test protocol( s).

Goals / Objectives The goals of this Technical Subgroup on Incineration Test Methods for Telomers are:

1) Identify scope and goals of proposed incineration testing 2) Develop a testing protocol, supporting: a. Thermogravimetric analysis to define gasification temperature per ASTM E1641. b. Laboratory Scale Thermal Degradation Test: per the 3M protocol [ OPPT 2003 0012 0151] as developed by the University of Dayton 3) Identify intermediate temperatures at which to run the test, so as to satisfy other incineration regimes ( e. g., across a variety of incinerator types; sub optimal operating scenarios).

4) Develop methods that will yield the temperature needed to provide 99.99% destruction of each telomer test substance at a residence time of 2 seconds in the high temperature zone.

5) Identify a list of representative telomers and/ or other telomer treated materials for incineration testing.

6) Report back to the Telomer Workgroup regarding incineration testing details that could be incorporated into an Enforceable Consent Agreement ( ECA) for testing specific telomer chemicals and/ or other telomer treated materials.

Meetings Meetings will be held at EPA Headquarters in Washington, DC. The initial meeting will be from 9: 00 to noon on Thursday, August 14, 2003. Attendance may be via conference call or in person. Meeting materials will be distributed one week in advance of the meeting. U. S. Environmental Protection Agency Draft, August 13, 2003 Technical Subgroup on Incineration Test Methods for Telomers Tentative Agenda   First Meeting Thursday, August 14, 2003 9: 00 AM to Noon EPA East, Room 4225 1201 Constitution Avenue, NW Washington, DC 20460   Discussion of Goals / Objectives   Comments on Adequacy of Existing Incineration Test Protocol   Key Protocol Elements ° Test Temperatures ° Residence time ° Other S Proposed Methods Modifications S Polymers/ chemicals to be tested & criteria for choosing selected materials S Data Quality Considerations   Next Steps Telomer Research Program Proposal Draft, 8 August, 2003 Technical Subgroup on Incineration Test Methods for Telomers Introduction The PFOA ECA Plenary session held on July 10, 2003, approved an action plan for the Telomer Workgroup to form a Technical Subgroup on Incineration test methods. This subgroup will assess the adequacy of available incineration test methods so as to inform a technical assessor on the details of Telomer thermal degradation and the potential concurrent formation of PFOA. Where needed, specific approaches to address the unique characteristics of Telomers and Telomer based polymers will be agreed upon.

Goals / Objectives The goals of this Technical Subgroup on Incineration Test Methods for Telomers are:

1. Identify the scope and goals of proposed incineration testing work toward agreement on a testing protocol that would determine if incineration of Telomers is a potential source of PFOA at operating conditions that are representative of relevant types of waste incinerators.

2. Work toward identifying a list of representative Telomers and/ or other Telomer treated materials for incineration testing.

3. Work toward identifying temperatures at which to run the test( s) to represent operating conditions for relevant types of waste incinerators.

4. Work toward developing a testing protocol using well accepted laboratory scale incineration testing practices and suitable sampling and analytical techniques.

5. Report back to the Telomers Workgroup regarding the testing details that could be incorporated into an Enforceable Consent Agreement ( ECA) for testing specific Telomer chemicals and/ or other Telomer treated materials.

Meetings Meetings will be held at EPA Headquarters in Washington, DC. The initial meeting will be from 9: 00 to noon on Thursday, August 14, 2003. Attendance may be via conference call or in person. Meeting materials will be distributed one week in advance of the meeting. Telomer Research Program Proposal Draft, 8 August, 2003 Technical Subgroup on Incineration Test Methods for Telomers Tentative Agenda  First Meeting Thursday, August 14, 2003 9: 00 AM to Noon EPA East, Room 4225 1201 Constitution Avenue, NW Washington, DC 20460   Discussion of Goals / Objectives   Review of Recent Related Incineration Studies   Key Elements of Proposed Test Protocol   Test Temperatures   Residence time   Sampling & Analysis   Other   Criteria for choosing Telomer chemicals to be tested   Data Quality Considerations   Next Steps TRP Telomer Research Program TRP Environmental Fate :

Incineration 14 August 2003 14 August 2003, page 2 Telomer Research Program Incineration : Approach

TRP has agreed to study the applicability of incineration to its Telomertreated products and related articles in the U. S. in a " Desk Study"

First, understand U. S. disposal methods for waste carpet, textile and paper and in what uses incineration is applicable

Second, review the U. S. incinerator conditions to understand typical operating temperatures

The " Desk Study" will frame the Experimental Study

The Experimental Study will

Investigate incineration of telomer based substances under laboratoryscale conditions representative of relevant incinerator operations in the U. S. to quantitatively determine emission levels of PFOA. 14 August 2003, page 3 Telomer Research Program Incineration : Desk Study

Based on:

Public Information

U. S. EPA, " Municipal Solid Waste in The United States : 2000 Facts & Figures", EPA530 R 02 001,

June 2002 ( www. epa. gov/ epaoswer/ non hw/ muncpl/ report 00/ report 00. pdf)

Carpet America Recovery Effort, EPA/ Industry " Memorandum of Understanding for Carpet Stewardship" Appendix A, January 2002 ( www. carpetrecovery. org/ about/ mou. asp)

Industry Knowledge

Uses of Telomer based Products : carpet, paper, textiles

" Desk Study" Objectives

Understand U. S. waste disposition by means of disposal and type

to determine what telomer treated articles and substances are likely to be incinerated

Review U. S. Municipal Waste Combustors and Medical Waste Incinerators

typical incinerator operating conditions

use to define study approach and experimental conditions 14 August 2003, page 4 Telomer Research Program Incineration : Desk Study

Municipal Solid Waste Disposition1

55% to landfill

30% recovered

15% to combustion 1 " Municipal Solid Waste in The United States: 2000 Facts & Figures" 14 August 2003, page 5 Telomer Research Program Incineration : Desk Study

U. S. disposal methods

carpet1

is landfilled or recycled

less than 1% of total carpet waste is incinerated

textiles, including medical textiles, are incinerated2

paper is incinerated2 1 Carpet America Recovery Effort, " Memorandum of Understanding for Carpet Stewardship," Appendix A 2 U. S. EPA, " Municipal Solid Waste in The United States: 2000 Facts & Figures" 14 August 2003, page 6 Telomer Research Program Incineration : Desk Study

U. S. Municipal Waste Combustors ( MWCs)

According to the Integrated Waste Services Association ( IWSA), there are 102 waste to energy facilities operating large MWCs in the U. S. 1

Additional information from IWSA indicates 3 categories of large MWCs:

Mass Burn: 70 Facilities, 23 million tons processed/ year

Refuse Derived Fuel ( RDF): 19 Facilities, 6.7 millions tons processed/ year

Modular: 13 Facilities, 400,000 tons processed/ year

Further information from IWSA shows that large MWCs account for 90% of MWC capacity in the U. S.

1  IWSA, " Fast Facts about Waste to Energy" ( www. wte. org/ facts. html) 14 August 2003, page 7 Telomer Research Program 1  U. S. EPA, Municipal Waste Combustion Assessment: Technical Basis for Good Combustion Practice, EPA 600/ 8 89 063, August 1989 2  U. S. EPA, Decision Maker's Guide to Solid Waste Management, Volume II, 1995.

3  Donnelly, J. R. Waste incineration sources: refuse. In: Buonicore, A. J.; Davis, W. T., eds., Air Pollution Engineering Manual. Air and Waste Management Association.

New York, NY: Van Nostrand Reinhold, 1992,. pp. 263 275.

Municipal Waste Combustors

U. S. emission standards for MWCs include Good Combustion Practices ( GCP)

In multi unit study1, MWCs operating under GCP had secondary stage temperatures ranging from 885 º C to 1071 º C

Volume II of EPA's " Decision Maker's Guide to Solid Waste Management" 2 reports that many incinerators for municipal solid waste are designed to operate in the combustion zone at 1800 º F [ 982 º C] to 2000 º F [ 1093 º C]

In his section on " Waste Incineration Sources: Refuse in Air Pollution Engineering Manual," J. R. Donnelly3 explains that combustion gas in traveling grate mass burn units are maintained at about 1800 º F [ 982 º C] to ensure complete combustion of organic compounds" prior to passing to the boiler 14 August 2003, page 8 Telomer Research Program Medical Waste Incinerators

In Air Pollution Control and Waste Incineration for Hospitals and Other Medical Facilities,

Louis Theodore1 states that 3 types of incinerators are primarily used for medical waste:

controlled air incinerators, multiple chamber incinerators, & rotary kiln incinerators.

All three types of medical waste incinerators ( MWIs) use two chambers.

The ignition or primary chamber

The second chamber is designed to complete the combustion process Controlled Air Multiple Chamber Rotary Kiln2 Primary Chamber 400 to 980 º C 540 to 980 º C 760 º C Second Chamber 980 to 1200 º C 980 to 1200 º C 980 º C 1  Theodore, L.: Air Pollution Control and Waste Incineration for Hospitals and Other Medical Facilities, Van Nostrand Reinhold, New York, 1990, pp 313 320.

2  Note: Rotary kilns for other types of waste may be operated at much higher temperatures.

3  U. S. EPA, Exposure and Human Health Reassessment of 2,3,7,8 Tetrachlorodibenzo p Dioxin ( TCDD) and Related Compounds, Part I: Estimating Exposure to Dioxin

Like Compounds Volume 2: Sources of Dioxin Like Compounds in the United States, Chapter 3, EPA/ 600/ P 00/ 001Bb, Draft Final Report, September 2000 EPA notes that 97% of MWIs are controlled air modular furnaces and 1%

are rotary kilns3 14 August 2003, page 9 Telomer Research Program Incineration Study Proposal

Test Objective

Investigate incineration of telomer based substances under laboratory scale conditions representative of typical municipal waste combustor ( MWC) operations in the U. S. to quantitatively determine emission levels of PFOA 14 August 2003, page 10 Telomer Research Program Incineration Study Proposal

Test Materials

Paper

A single representative composite mixture of the LOI telomer based polymeric products which are applied to paper, as solids, in equal proportions

Textiles, including medical textiles

A single representative composite mixture of the LOI telomer based polymeric products which are applied to textiles, as solids, in equal proportions 14 August 2003, page 11 Telomer Research Program Incineration Study Proposal

Experimental Apparatus  General Description

a batch charged continuous flow reactor system

The test sample is gasified and transported to a high temperature reactor.

In the high temperature reactor, the sample vapors are subjected to controlled conditions of residence time, temperature, and excess air.

Combustion products are collected for quantitative analysis. 14 August 2003, page 12 Telomer Research Program Incineration Study Proposal

Experimental Conditions

Telomer based polymeric product solids will be subjected to laboratoryscale incineration using the experimental apparatus

Two test levels are proposed for the high temperature reactor:

900 ° C for two seconds residence time ( municipal)

1000 ° C for two seconds residence time ( medical, municipal)

Three replicates for each test level ( combination of test feed and temperature).

Additionally, a blank run under each experimental condition

The amount of test material in feed will be large enough to assure ability to detect compounds of interest in the emissions, but small enough to assure sufficient excess oxygen to be representative of MWC conditions. 14 August 2003, page 13 Telomer Research Program Incineration Study Proposal

Sampling & Analysis

Monitored exhaust gas parameters are proposed to include :

flow rate, oxygen ( O2), carbon dioxide ( CO2), and carbon monoxide ( CO).

Exhaust gas

will be collected on suitable sorbent cartridge( s) and / or in aqueous solution trap( s) for off line analysis to quantify PFOA.

PFOA Determination : sampling and analysis methods

adapt and validate available methods for this study 14 August 2003, page 14 Telomer Research Program Incineration Study Proposal

Sampling

Sorbent Cartridge

OSHA Versatile Sampler ( OVS)

analyze for PFOA

Aqueous Solution

use one or more impingers containing aqueous solution

analyze for PFOA

analyze for fluoride ion to assist in performing a fluoride balance across the experimental system.

Analysis Method for PFOA

via off line LC/ MS/ MS at a qualified commercial laboratory operating under suitable data quality guidelines. 14 August 2003, page 15 Telomer Research Program Incineration Study Proposal

Study Materials Characterization

elemental analysis to determine carbon, hydrogen, nitrogen, chlorine,

fluorine and oxygen by difference.

PFOA content 14 August 2003, page 16 Telomer Research Program Incineration : Next Steps

We are willing to discuss in a technical work group how to conduct incineration studies leading toward an ECA for the work U. S. Environmental Protection Agency Draft, August 13, 2003 Anticipated Attendees for Telomer Incineration Subgroup Meeting John Heinze, Environmental Health Research Foundation ( by phone) Erin Russell, Clariant ( by phone) Hiroyuki Iwai, Daikin Satoshi Komatsu, Daikin Ed Lampert, Daikin Yukiko Nishiyama, Daikin Randy Roussel, Daikin Maggie Martin, Daikin Robert Giraud, DuPont Bob Buck, DuPont Steve Korzeniowski, DuPont W. Michael McCabe ( DuPont) Lisa Walton, W. L. Gore Lisa Campbell, Bergeson & Campbell ( Gore) Mike Wernke, BBL Sciences ( Clariant) ( by phone) John Blouin, EPA/ EETD Eric Stewart, EPA/ ORD Greg Fritz, EPA/ EETD Ward Penberthy, EPA/ CCD Ed Heithmar, EPA/ ORD Rich Leukroth, EPA/ CCD Wendy Hoffman, EPA/ EETD Nhan Nguyen, EPA/ EETD ( Observer: Julie Eble, CPS [ TRP]) ( Observer: Katie Smythe, RAND [ TRP]) ( Observer: David Menotti, Shaw Pittman [ Asahi]) ( Observer: Bill Beers, OMNOVA Solutions) NAME felomer Incineration Technical Subgroup Meeting ORGANIZATION TELEPHONE # E MAIL ADDRESS August 14, 2003 cb~ , Ø6 6' z , ø%, e iui 5a/ vsA~ Kmatsu Y~ t4I~ 7 AJy~ tm~

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E~ 4 1/ o'/~ ~ jig~ i. ~ 7~ 11\~ ~ e1q   i~~ U. S. Environmental Protection Agency Draft, August 13, 2003 Technical Subgroup on Biodegradation Test Methods for Telomers Introduction The PFOA ECA Plenary session held on July 10, 2003, approved an action plan for the Telomer Workgroup to form a Technical Subgroup on Biodegradation Test Methods. This subgroup will assess the adequacy of available biodegradation test methods to inform telomer degradation and to develop, where needed, new test methods or approaches to address the unique characteristics of telomers and telomer based polymers.

Goals / Objectives The goals of this Technical Subgroup on Biodegradation Test Methods for Telomers are:

1) Develop an approach for testing to determine the rate and extent of biodegradation of representative telomers and telomer based polymers to PFOA and other degradation products.

( 2) Modify existing, or develop new protocol( s) for biodegradation testing of telomers and telomer based polymers in:

( a) aerobic and anaerobic soils, ( b) aerobic and anaerobic aquatic sediment systems, ( c) activated sludge wastewater treatment systems, and ( d) anaerobic sludge digestors ( 3) Report back to the Telomers Workgroup regarding the details of testing standards for incorporation into an Enforceable Consent Agreement ( ECA) for testing representative telomers and telomer based polymers of interest.

Meetings The first meeting of the Subgroup will be held at EPA Headquarters in Washington, DC on Thursday, August 14, 2003, from 1: 00 to 4: 00 PM. Attendance may be via conference call or in person. Meeting materials will be distributed one week in advance of the meeting U. S. Environmental Protection Agency Draft, August 13, 2003 Technical Subgroup on Biodegradation Test Methods for Telomers Tentative Agenda  First Meeting Thursday, August 14, 2003 1: 00 PM to 4: 00 PM EPA East, Room 4225 1201 Constitution Avenue, NW Washington, DC 20460   Review of Subgroup Goals / Objectives   Discussion of Utility of Existing Biodegradation Test Protocols for Evaluation of Telomers and Telomer Based Polymers   Consideration of Key Protocol Elements ° Test Conditions/ Procedures ° Test Duration ° Mass Balance ° Analytical Procedures ° Other   Identification of Test Methods Modification Needs   Data Quality Considerations   Test Method Development Schedule   Next Steps Telomer Research Program Proposal Draft, August 9, 2003 Telomer Biodegradation Test Methods Technical Subgroup Goals / Objectives The goals of the Technical Subgroup on Biodegradation Test Methods for Telomer based materials are to:

1) Develop a study approach that will determine whether and to what extent representative telomer based substances undergo biodegradation to PFOA.

2) Evaluate biodegradation test method( s) / protocol( s) for telomer based substances which   are relevant to the environmental compartments into which telomer based substances enter from use and disposal ( i. e. sludge, soil, and water )   and address aerobic and/ or anaerobic biodegradation pathways 3) Report back to the Telomers Workgroup regarding the outcome of these discussions regarding the approach and test details for incorporation into an Enforceable Consent Agreement ( ECA) for testing representative telomer based substances of interest.

Proposed Revised Agenda  Review of Subgroup Goals and Objectives  Logic for Telomer Environmental Fate Testing including  E Fate Testing Decision Trees  Relevant Environmental Compartments and corresponding Study Approaches  Experimental Design  Overview & Discussion :  Approach to testing telomer based polymeric products  Analytical Tools & Data Quality  Technical Hurdles & Approaches to E Fate Studies in Relevant Environmental Compartments  Specific Studies for Detailed Discussion  Adsorption   Desorption Studies  Biodegradation studies relevant to Aerobic Sewage Treatment and Soil  Test Method Development Schedule  Summary/ Conclusions & Path Forward TRP Telomer Research Program Biodegradation Approach Proposal 14 August 2003 2003 08 14 , page 2 Telomer Research Program Biodegradation Technical Session Discussion Outline

Study Objectives & Approach

Technical Review & Discussion

Part 1: Environmental Fate Testing Logic

Part 2: Experimental Design Discussion

Summary/ Conclusions & Path Forward 2003 08 14 , page 3 Telomer Research Program Objective

Do Telomer based Polymeric Products biodegrade to PFOA?

Literature references1 indicate that non polar polymers are not expected to biodegrade in the environment

TRP recognizes that data is needed to inform this question and offers a study approach where both Telomer based Polymeric Products and Telomer based Polymers are investigated

Proposed Studies

address partitioning and biotransformation in relevant environmental compartments

start with laboratory studies that are simple and inform the question of whether telomer based polymeric products and telomer based polymers have the potential to transform to PFOA

use these to determine whether and what longer duration or complex studies may be needed

use test design principles from established study guidelines 1  see presentation Appendix 1 2003 08 14 , page 4 Telomer Research Program Approach

Focuses on relevant releases during the lifecyle of telomer based products and articles

Products and treated articles were chosen using criteria such as market end use, chemistry type/ class, chemical volume, article type, and potential for human exposure. TRP Telomer Research Program Technical Review 2003 08 14 , page 6 Telomer Research Program Technical Review Outline

Part 1: Environmental Fate Testing Logic

1A: E Fate Assessment Studies Design

1B: E Fate Testing Decision Trees

1C: Potential Release/ Emission Scenarios

Relevant Environmental Compartments

Relevant E Fate Testing Approach

Part 2: Experimental Design Discussion

General Overview

Technical Hurdles for E Fate Tests in Relevant Environmental Compartments*

Part 3: Summary/ Conclusions & Path Forward ° Includes all of the analytical method development issues and need for test design modifications 2003 08 14 , page 7 Telomer Research Program 80% Water 20% Telomer Polymer ° Aqueous Dispersion of .

° Polymeric Particles 100 200 nm with...

° Hydrocarbon Surfactant( s)

What is a Typical Telomer based Polymeric Product's Composition ?

Telomer Polymeric Product Variables

wt.% active ingredient in product (~ 20%)

wt.% fluorine

wt.% telomer raw materials

wt.% eight fluorinated carbon chain C8F17

PFOA ( from product analysis)

Mol. Wt.  Typically > 10,000 Daltons

polyacrylates

polyurethanes 2003 08 14 , page 8 Telomer Research Program Part 1A:

Environmental Fate Testing Logic E Fate Assessments Studies Design Technical Review 2003 08 14 , page 9 Telomer Research Program Determine Relevant Environmental Compartments ( i. e., air, water, soil, sediments)

Determine Appropriate Abiotic and Biotic Degradation Tests Based on Environmental Compartments of Concern ( E Fate Decision Trees)

Evaluate Results and Determine If Needs for Testing Are Complete Logic Flow Chart for E Fate Assessments 2003 08 14 , page 10 Telomer Research Program Determine Relevant Environmental Compartments ( i. e., air, water, soil, sediments)

Determine Appropriate Abiotic and Biotic Degradation Tests Based on Environmental Compartments of Concern ( E Fate Decision Trees)

Evaluate Results and Determine If Needs for Testing Are Complete Logic Flow Chart for E Fate Assessments 2003 08 14 , page 11 Telomer Research Program Factors for Determining Relevant Environmental Compartments

Use/ Applications

Physical Chemical Properties

Emissions/ Entry Point 2003 08 14 , page 12 Telomer Research Program Uses / Applications Carpet Paper Textiles ° To identify environmental compartments to which there are releases 2003 08 14 , page 13 Telomer Research Program Physical Chemical Properties

Physical Chemical Properties:

Water solubility

Vapor Pressure

UV Visible Absorption

Hydrolysis as a Function of pH

Test to determine surface film formation

( e. g., surface tension, specific gravity, etc.)

compositional characterization

molecular weight, chemical structure, functional groups, charge, density .

Activated Sludge Sorption Isotherm

Soil / Sludge Adsorption/ Desorption

Henry's Law Constant

Log Kow 2003 08 14 , page 14 Telomer Research Program Emissions / Entry Point into the Environment

Sewage Treatment Plant ( STP)

Soil

Land Applied Sludge

Landfill

Air

Water

Sewage Treatment Plant ( STP) discharge

Other Discharges to Water 2003 08 14 , page 15 Telomer Research Program Part 1B:

Environmental Fate Testing Logic E Fate Testing Decision Trees Technical Review 2003 08 14 , page 16 Telomer Research Program Determine Relevant Environmental Compartments ( i. e., air, water, soil, sediments)

Determine Appropriate Abiotic and Biotic Degradation Tests Based on Environmental Compartments of Concern ( E Fate Decision Trees)

Evaluate Results and Determine If Needs for Testing Are Complete Logic Flow Chart for E Fate Assessments 2003 08 14 , page 17 Telomer Research Program Environmental Entry Points Air Water STP Soil Sewage treatment plant Significant Effluent?

Entry via Air Entry via Soil Entry via Water ( e. g., Air, non point sources, etc.) Entry via STP Sludge Adsorption or Sedimentation?

"

Aerobic Sewage Treatment Test Yes High HLC? High Land Applied Sludge ( Look at soil) Look at Air Look at H2O Entry Points into Environment Air Soil Water STP Code: Indirect Photolysis in Soil Land Applied Sludge  I Inherent Biodegradability Low/ Mod.

Sludge/ Landfill E Fate Testing Decision Tree : STP

Anaerobic Biodegradation of Organic Compounds in Sludge Entry via Air Entry via Soil Entry Points into Environment Air Soil Water STP Code: Indirect Photolysis in Soil  E Fate Testing Decision Tree : Soil Land Applied Sludge Sludge/ Landfill Significant Effluent?

Entry via Water ( e. g., Air, non point sources, etc.) Entry via STP Sludge Adsorption or Sedimentation?

"

Aerobic Sewage Treatment Test Yes High HLC? High Land Applied Sludge ( Look at soil) Look at Air Look at H2O Low/ Mod.

Soil* Adsorption?

High HLC? Mobile in soil and partitions to water;

i. e., potential mobility to groundwater High Low Low Aerobic and/ or Anaerobic Transformations in Soil OECD 307 Aerobic and/ or Anaerobic Transformations in Soil Look at Air

Inherent Zahn Wellens /

.3200) I Inherent Biodegradability: Anaerobic Biodegradation of Organic Compounds in Sludge Entry via Air Entry via Soil Entry Points into Environment Air Soil Water STP Code: Indirect Photolysis in Soil  E Fate Testing Decision Tree : Air Land Applied Sludge Sludge/ Landfill Significant Effluent?

Entry via Water ( e. g., Air, non point sources, etc.) Entry via STP Sludge Adsorption or Sedimentation?

"

Aerobic Sewage Treatment Yes High HLC? High Land Applied Sludge ( Look at soil) Look at Air Look at H2O I

Inherent Biodegradability:

EMPA Test ( OPPTS 835.3200) Low/ Mod.

Soil* Adsorption?

High HLC? Mobile in soil and partitions to water;

i. e., potential mobility to groundwater High Low Low Aerobic and/ or Anaerobic Transformations in Soil OECD 307 Aerobic and/ or Anaerobic Transformations in Soil Look at Air UV/ Vis Abs.

> 290 nm?

Direct Photolysis In Air Indirect Photolysis In Air > 2 days in Air?

Assess LRT Potential Wet/ Dry Deposition Potential?

Yes No Yes or No Yes Yes Look at soil Yes

Inherent Zahn Wellens /

.3200) I Inherent Biodegradability: Anaerobic Biodegradation of Organic Compounds in Sludge Entry via Air Entry via Soil Air Soil Water WWTP Code: Indirect Photolysis in Soil  E Fate Testing Decision Tree : Water Land Applied Sludge Sludge/ Landfill Significant Effluent? Entry via STP Sludge Adsorption or Sedimentation?

"

Aerobic Sewage Treatment Yes High HLC? High Land Applied Sludge ( Look at soil) Look at Air Entry via Water ( e. g., Air, non point sources, etc.)

Look at H2O

Inherent Biodegradability:

Zahn Wellens ( OPPTS 835.3200) Low/ Mod.

Soil* Adsorption?

High HLC? Mobile in soil and partitions to water;

i. e., potential mobility to groundwater High Low Low Aerobic and/ or Anaerobic Transformations in Soil OECD 307 Aerobic and/ or Anaerobic Transformations in Soil Look at Air UV/ Vis Abs.

> 290 nm?

Direct Photolysis In Air Indirect Photolysis In Air > 2 days in Air?

Assess LRT Potential Wet/ Dry Deposition Potential?

Yes No Yes or No Yes Yes Look at soil Yes Sediment Adsorption or Sedimentation?

Forms Film at H2O Surface?

Modified River Die Away Test ( Biodegradability) Indirect Photolysis OPPTS 835.5270 Direct Photolysis OPPTS 835.2210 ( uv/ vis abs > 290 nm)

Yes Aerobic and Anaerobic Transformations in Aquatic Sediments Systems OECD 308 High Entry Points into Environment

Inherent Zahn Wellens /

.3200) I Inherent Biodegradability: Anaerobic Biodegradation of Organic Compounds in Sludge Significant Effluent?

Entry via Air UV/ Vis Abs.

> 290 nm?

Direct Photolysis In Air Indirect Photolysis In Air > 2 days in Air?

Assess LRT Potential Wet/ Dry Deposition Potential?

Yes No Yes orNo Yes Yes Soil* Adsorption?

High HLC? Mobile in soil and partitions to water;

i. e., potential mobility to groundwater Entry via Soil High Low Low Aerobic and/ or Anaerobic Transformations in Soil OECD 307 Aerobic and/ or Anaerobic Transformations in Soil Sediment Adsorption or Sedimentation? HLC? High Forms Film at H2O Surface?

Entry via Water ( e. g., Air, non point sources, etc.)

Modified River Die Away Test ( Biodegradability) Indirect Photolysis OPPTS 835.5270 Direct Photolysis OPPTS 835.2210 ( uv/ vis abs > 290 nm)

Yes Aerobic and Anaerobic Transformations in Aquatic Sediments Systems OECD 308 High Entry via STP Sludge Adsorption or Sedimentation?

"

Aerobic Sewage Treatment Test Yes High HLC? High Land Applied Sludge ( Look at soil) Look at Air Look at Air Look at soil Look at H2O Look at Air Yes Look at H2O Entry Points into Environment Air Soil Water STP Code: Indirect Photolysis in Soil Land applied sludge I Inherent Biodegradability Low/ Mod.

Sludge/ Landfill E Fate Testing Decision Tree Anaerobic Biodegradation of Organic Compounds in Sludge 2003 08 14 , page 23 Telomer Research Program Part 1C:

Environmental Fate Testing Logic Relevant Environmental Compartments for Telomer based Polymers Technical Review 2003 08 14 , page 24 Telomer Research Program These are the areas to be discussed in this biodegradation work session Telomer based Polymers : Routes in to the Environment

STP

from " down the drain" disposal : sludge , wastewater

Soil

Land applied sludge from WWTP

from disposal of treated articles ( carpet, textiles, paper) to landfill

Water

no direct discharge to water; indirect considered via STP and Soil

Incineration

addressed in separate ECA process workstream

Air

addressed by TRP mill release and pilot study work Significant Effluent?

Entry via Air UV/ Vis Abs.

> 290 nm?

Direct Photolysis In Air Indirect Photolysis In Air > 2 days in Air?

Assess LRT Potential Wet/ Dry Deposition Potential?

Yes No Yes orNo Yes Yes Soil* Adsorption?

High HLC? Mobile in soil and partitions to water;

i. e., potential mobility to groundwater Entry via Soil High Low Low Aerobic and/ or Anaerobic Transformations in Soil OECD 307 Sediment Adsorption or Sedimentation? HLC?

Forms Film at H2O Surface?

Entry via Water ( e. g., Air, non point sources, etc.)

Die Away Test ( Biodegradability)

Modified River Indirect Photolysis OPPTS 835.5270 Direct Photolysis OPPTS 835.2210 ( uv/ vis abs > 290 nm)

Yes Aerobic and Anaerobic Transformations in Aquatic Sediments Systems OECD 308 High Entry via STP Sludge Adsorption or Sedimentation?

"

Aerobic Sewage Treatment Test Yes High HLC? High Land Applied Sludge ( Look at soil)

Look at Air Look at soil Look at H2O Yes Look at H2O Entry Points into Environment Air Soil Water STP Code: Indirect Photolysis in Soil Land applied sludge I Inherent Biodegradability Low/ Mod.

Sludge/ Landfill E Fate Testing Decision Tree Anaerobic Biodegradation of Organic Compounds in Sludge 2003 08 14 , page 26 Telomer Research Program Telomer based Polymers Environmental Entry Point  STP

Telomer based Polymers will go down the drain, so the Sewage Treatment Plant is a relevant environmental compartment.

Polymers will likely significantly adsorb to sludge and/ or settle in sludge,

thus concentrations in the aqueous effluent are predicted to be low.

Therefore, water & sediments are not expected to be significant compartments in this.

Assuming sludge will potentially be land applied, then soil is a relevant environmental compartment.

Aerobic transformation in Soil is a relevant test since Telomer based Polymers will likely be adsorbed to sludge and sludge is often applied to soil.

Expected lack of mobility in soil would support not conducting testing for anaerobic transformation in soil for the land applied sludge scenario. 2003 08 14 , page 27 Telomer Research Program Soil* Adsorption?

Aerobic/ Anaerobic Transformations in Soil HLC?

Entry via Soil High Low Entry via STP Sludge Adsorption or Sedimentation?

Aerobic Sewage Treatment Test High HLC? Entry Points into Environment Significant Effluent? STOP Low/ Mod. No Land Applied Sludge STP Down the Drain Inherent Biodegradability Zahn Wellens/ EMPA Test 2003 08 14 , page 28 Telomer Research Program Telomer based Polymers Environmental Entry Point  Landfill

For Telomer based Polymers that go to a landfill, soil is a relevant environmental compartment.

Polymers will likely significantly adsorb to soil, or remain adsorbed to disposed treated articles ( carpet, paper, textile). As such, leaching to groundwater beneath the landfill is not expected.

Aerobic and Anaerobic Transformations in Soil are relevant tests since landfills are layered over time ( e. g., soil layering to reduce odor is common)

This testing would represent a worst case for biotransformation potential in a landfill since anoxic,

dessicant conditions, which are common to landfills, will not allow for further biotransformations when these conditions are present. Therefore, a landfill simulation is not necessary providing these recommended tests are conducted.

Indirect photolysis is irrelevant for the landfill scenario due to:

timing for land covering ( i. e., typically daily to limit odor)

textiles, carpet, etc. have likely been previously exposed to UV/ Vis light during the product lifetime, thus potential for photo reactivity will be determined in the article testing studies. 2003 08 14 , page 29 Telomer Research Program Landfill Entry Points into Environment Soil* Adsorption?

Aerobic/ Anaerobic Transformations in Soil HLC?

Entry via Soil High Low Article Disposal 2003 08 14 , page 30 Telomer Research Program Telomer Polymers Environmental Entry Point  Air

For Telomer Polymers entering the environment via a wastewater treatment process, land applied sludge, and landfills, emissions to air are expected to be insignificant.

Before developing a hypothesis for potential air emissions, we should first evaluate the findings from the following studies:

Mill Pilot Study to determine potential for Telomer Polymers entering the Air via Process emissions.

Incineration studies

Article Aging Studies 2003 08 14 , page 31 Telomer Research Program Determine Relevant Environmental Compartments ( i. e., air, water, soil, sediments)

Determine Appropriate Abiotic and Biotic Degradation Tests Based on Environmental Compartments of Concern ( E Fate Decision Trees)

Evaluate Results and Determine If Needs for Testing Are Complete Logic Flow Chart for E Fate Assessments 2003 08 14 , page 32 Telomer Research Program Part 2:

Experimental Design Discussion Introduction &

Proposed Study Plan Technical Review 2003 08 14 , page 33 Telomer Research Program Environmental Compartments and Biodegradation Testing

Telomer based polymers may be released to the environment

in sewage treatment plants ( stp) adsorbed to sludge

in soil via sludge amendment to agricultural soils

in soil ( landfill) from sludge or disposal of treated articles ( carpets,

textiles, paper)

Biodegradation testing of telomer based polymers

has to address the compartments given above

has to be based on suitable test protocols

has to address the analytical methods for the different matrices as well as the detection limits needed for the intended purpose 2003 08 14 , page 34 Telomer Research Program Analytical Measurement Limitations

Method Development & Demonstration needed for

extraction/ recovery from test matrices: sludge and / or soil

What we can measure :

Fluoride ( ion selective electrode)

PFOA : LC/ MS/ MS

Total Organic fluorine ( Wickbold torch)

Chemical specific measurement methods for telomer based polymers are not available

may not be able to determine mass balance and transformation pathway( s)

without radiolabeled test substance( s)

radiolabeled substance( s) would require substantial R& D effort 2003 08 14 , page 35 Telomer Research Program Proposed Study Plan

Telomer based Polymeric Products and " Isolated" Polymers

Inherent Biodegradation in Sludge

Aerobic Sewage Treatment Study

Soil Aerobic / Anaerobic Biodegradation Study 2003 08 14 , page 36 Telomer Research Program Study Proposal Inherent Biodegradation in Sludge

Inherent Biodegradability data will inform whether there is potential for biotransformation in an Aerobic Sewage Treatment Plant ( STP).

OECD 302B Zahn Wellens 28 day Study as study design guideline

high inoculum to substance ratio

means the test conditions are more favorable for biodegradation than typical environmental conditions

Inherent study is more favorable than actual STP conditions

if the study substance does not form PFOA, it would not be expected to form PFOA in an STP

if the study substance does form PFOA, it may or may not form PFOA in an STP 2003 08 14 , page 37 Telomer Research Program Study Proposal Inherent Biodegradation in Sludge Begin work on .

Two Telomer based Products and Two Telomer based polymers isolated from them

Products will be from the 12 that are included in the TRP LOI

Two isolated polymers from the two Products

to understand whether the polymer alone undergoes transformation

characterization of the products and isolated polymers will be done

will enable method development and demonstration Then  .

Conduct studies on the remaining 10 Telomer based Polymeric Products 2003 08 14 , page 38 Telomer Research Program Study Proposal Inherent Biodegradation in Sludge

Study Endpoints

PFOA

Fluoride [ F]

LOD's & LOQ's for each endpoint need to be established

Methods

extraction methods for PFOA need to be demonstrated in the test system

Timing

protocol is being developed to begin work as soon as practical 2003 08 14 , page 39 Telomer Research Program Proposed Study Plan

Telomer based Polymeric Products and " Isolated" Polymers

Inherent Biodegradation in Sludge

Aerobic Sewage Treatment Study

Soil Aerobic / Anaerobic Biodegradation Study 2003 08 14 , page 40 Telomer Research Program Aerobic Sewage Treatment Study:

Proposal for Discussion

Partitioning and biodegradation in an aerobic sewage treatment system

The value of this test is to determine :

Partitioning to Sludge versus Water

Need to understand sorption to sludge and sedimentation in advance of the study

Biodegradation under STP conditions

It is anticipated that

entry into water via STP may not be a significant route into the environment for telomer based polymers

telomer based polymers would likely be adsorbed to and / or settled in sludge

based upon OECD 303A test guideline

the simulation test guideline recommends the biodegradation test to be run at relevant concentrations in a dynamic system

test duration up to 9 weeks

this system mimics the residence time of a STP

hydraulic retention time 6h

sludge retention time 8 10 d 2003 08 14 , page 41 Telomer Research Program Aerobic Sewage Treatment Study:

Proposal for Discussion

Study Material( s)

define based upon results from the Inherent and Sorption Studies

Study Endpoints

sludge : total organic fluorine; PFOA by extraction

water : total organic fluorine; PFOA; fluoride [ F]

Overall mass balance may be accomplished by total organic fluorine 2003 08 14 , page 42 Telomer Research Program Technical Hurdles: Activated Sludge Sorption Guideline

Reliable Analytical Methods

Need methods with sufficient accuracy to be able to extract and measure test substance in the solution and/ or the adsorbed phase Issues

Reliable Analytical Methods

Total Organic Fluorine is only available tool but is non specific

14C labeled polymer would be optimal to conduct this study, but this would require significant R& D. 2003 08 14 , page 43 Telomer Research Program Technical Hurdles: Aerobic Sewage Treatment Study Guideline

Dosage of Test Substance

For insoluble substances, reduce to 5 mg/ L DOC or even less, but only if a suitable analytical method is available

Test at relevant substance concentrations

Measurement of Biodegradability

DOC ( Dissolved Organic Carbon)

measurements are used to assess bioelimination ( bioadsorption plus biodegradation).

Mass Balance

Partitioning of the test substance is determined in both the liquid and solid phases. Issues

Dosage of Test Substance

Non chemical Specific Analytical limitation for cold studies

14C labelled polymer would be optimal ,

but would require significant R& D.

Measurement of Biodegradability

Analyze for PFOA in test system

Mass Balance

Total Organic Fluorine : a non chemical specific endpoint. 2003 08 14 , page 44 Telomer Research Program Proposed Study Plan

Telomer based Polymeric Products and " Isolated" Polymers

Inherent Biodegradation in Sludge

Aerobic Sewage Treatment Study

Soil Aerobic / Anaerobic Biodegradation Study 2003 08 14 , page 45 Telomer Research Program Aerobic and Anaerobic Transformations in Soil:

Proposal for Discussion

Soil will be a relevant environmental compartment

Telomer based Polymers will likely partition to sludge, which likely will be land applied to some extent.

Telomer based Polymers will likely end up in landfills on disposed articles.

Test Objective : to determine whether PFOA is formed as a result of anaerobic and aerobic biodegradation in soil

develop a study plan based upon OECD 307 and 304 study design guidelines

Begin with a Screening Study for biodegradation in soil

120 days duration

batch test in a biometer flasks 2003 08 14 , page 46 Telomer Research Program Aerobic and Anaerobic Transformations in Soil:

Proposal for Discussion

Study Materials

two telomer based polymers

Study Endpoint : PFOA analysis in the test system 2003 08 14 , page 47 Telomer Research Program Technical Hurdles:

Aerobic and Anaerobic Transformation in Soil Guideline

Analytical Methods

Applicable to all chemical substances which have analytical methods available with sufficient accuracy and sensitivity

Biodegradability & Mass Balance

Labelled ( 14C) material required for determining transformation pathways,

rates and mass balance Issues

Analytical Methods

Non chemical Specific Analytical limitation for cold studies

14C labelled polymer would be optimal , but would require significant R& D.

Biodegradability & Mass Balance

Analyze for PFOA in test system

Total Organic Fluorine : a nonchemical specific endpoint. TRP Telomer Research Program Summary/ Conclusions & Path Forward 2003 08 14 , page 49 Telomer Research Program Summary and Conclusion

The proposed study approach

is based on a step wise progression based upon relevant routes into the environment, and building upon knowedge gained

considers feasible and workable biotransformation and partitioning studies that address the central question of EPA

is based on modification of available biodegradation test methods

utilizes available analytical methods

such as for PFOA in different matrices ( sludge, soil, surface water) and agreed LODs &

LOQs

takes in to consideration the ability to conduct work in a timely manner

is consistent with and additive to the TRP Letter of Intent ( LOI) U. S. Environmental Protection Agency Draft, August 13, 2003 Anticipated Attendees for Telomer Biodegradation Subgroup Meeting Rich Purdy Treye Thomas, CPSC John Heinze, Environmental Health Research Foundation ( by phone) Volker Koch, Clariant Hiroyuki Iwai, Daikin Satoshi Komatsu, Daikin Ed Lampert, Daikin Yukiko Nishiyama, Daikin Randy Roussel, Daikin Maggie Martin, Daikin Bob Buck, DuPont Bill Berti, DuPont John Gannon, DuPont Steve Korzeniowski, DuPont W. Michael McCabe ( DuPont) Bill Hardie, W. L. Gore Richard Baillie, W. L. Gore Erin Russell, Clariant ( by phone) Mike Wernke, BBL Sciences ( Clariant) ( by phone) David Lynch, EPA/ EETD Bob Boethling, EPA/ EETD Andy Mamantov, EPA/ EETD Greg Fritz, EPA/ EETD Laurence Libelo, EPA/ EETD Ward Penberthy, EPA/ CCD Eric Weber, EPA/ ORD Tim Collette. EPA/ ORD Ed Heithmar, EPA/ ORD Rich Leukroth, EPA/ CCD Wendy Hoffman, EPA/ EETD ( Observer: Barbara Smyser, CPS [ TRP]) ( by phone) ( Observer: Katie Smythe, RAND [ TRP]) ( Observer: David Menotti, Shaw Pittman [ Asahi]) ( Observer: Bill Beers, OMNOVA Solutions) PFOA ECATeloiner Biodegradation Technical Subgroup Meeting August 14, 2003 ~ ll kovr/ e i~_~? L. óc', a

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Goals / Objectives The goals of this Technical Subgroup on Incineration Test Methods for Fluoropolymers are:

1) Identify the scope and goals of proposed incineration testing 2) Develop a testing protocol, supporting: a. Thermogravimetric analysis to define gasification temperature per ASTM E1641. b. Laboratory Scale Thermal Degradation Test: per the 3M protocol [ OPPT 2003 0012 0151] as developed by the University of Dayton 3) Identify intermediate temperatures at which to run the test, so as to satisfy other incineration regimes ( e. g., across a variety of incinerator types; sub optimal operating scenarios).

4) Develop methods that will yield the temperature needed to provide 99.99% destruction of each fluoropolymer test substance at a residence time of 2 seconds in the high temperature zone.

5) Identify a list of representative fluoropolymers and/ or other materials for incineration testing.

6) Report back to the Fluoropolymers Workgroup regarding the details of testing details that could be incorporated into an Enforceable Consent Agreement ( ECA) for testing fluoropolymers and/ or fluoropolymer treated materials.

Meetings Meetings will be held at EPA Headquarters in Washington, DC. The initial meeting will be from 9: 00 to 4: 00 on Tuesday, August 19, 2003. Attendance may be via conference call or in person. Meeting materials will be distributed one week in advance of the meeting. U. S. Environmental Protection Agency Draft, August 13, 2003 Technical Subgroup on Incineration Test Methods for Fluoropolymers Tentative Agenda   First Meeting Tuesday, August 19, 2003 9: 00 AM to 4: 00 PM EPA East, Room 4225 1201 Constitution Avenue, NW Washington, DC 20460   Discussion of Goals / Objectives   Comments on Adequacy of Existing Incineration Test Protocol   Key Protocol Elements ° Test Temperatures ° Residence time ° Other S Proposed Methods Modifications S Polymers/ chemicals to be tested & criteria for choosing selected materials S Data Quality Considerations   Next Steps Fluoropolymer Manufacturing Group Proposal Draft, August 7, 2003 Technical Subgroup on Incineration Test Methods for Fluoropolymers Introduction The PFOA ECA Plenary session held on July 10, 2003, approved an action plan for the Fluoropolymer Workgroup to form a Technical Subgroup on Incineration Test Methods. This subgroup will assess the adequacy of available incineration test methods so as to inform a technical assessor on the details of fluoropolymer thermal degradation and the potential concurrent formation of PFOA. Where needed, specific approaches to address the unique characteristics of fluoropolymers will be agreed upon.

Goals / Objectives The goals of this Technical Subgroup on Incineration Test Methods for Fluoropolymers are:

1) Identify the scope and goals of proposed incineration testing Determine if incineration of fluoropolymers is a potential source of PFOA at operating conditions that are representative of relevant types of waste incinerators.

2) Identify a list of representative fluoropolymers and/ or other materials for incineration testing.

3) Identify temperatures at which to run the test( s) to represent operating conditions for relevant types of waste incinerators.

4) Develop a testing protocol using well accepted laboratory scale incineration testing practices and suitable sampling and analytical techniques.

5) Report back to the Fluoropolymers Workgroup regarding the details of testing details that could be incorporated into an Enforceable Consent Agreement ( ECA) for testing fluoropolymers and/ or fluoropolymer treated materials.

Meetings Meetings will be held at EPA Headquarters in Washington, DC. The initial meeting will be from 9: 00 to 4: 00 on Tuesday, August 19, 2003. Attendance may be via conference call or in person. Meeting materials will be distributed one week in advance of the meeting. Fluoropolymer Manufacturing Group Proposal Draft, August 7, 2003 Technical Subgroup on Incineration Test Methods for Fluoropolymers Tentative Agenda  First Meeting Tuesday, August 19, 2003 9: 00 AM to 4: 00 PM EPA East, Room 4225 1201 Constitution Avenue, NW Washington, DC 20460  Discussion of Goals / Objectives  Review of Recent Fluoropolymer Related Incineration Studies  Key Elements of Proposed Test Protocol   Test Temperatures   Residence time   Sampling & Analysis   Other  Polymers/ chemicals to be tested & criteria for choosing selected materials  Data Quality Considerations  Next Steps Technical Subgroup on Incineration Test Methods for Fluoropolymers Incineration Testing Proposal August 19, 2003 August 19, 2003 presentation to Technical Subgroup on Incinerator Test Methods for Fluoropolymers 2 Overall Objective Determine if incineration of fluoropolymers is a potential source of PFOA to the environment August 19, 2003 presentation to Technical Subgroup on Incinerator Test Methods for Fluoropolymers 3 Discussion Objective ° Work toward agreement on key elements of test program to enable development of test protocol and ECA for incineration testing August 19, 2003 presentation to Technical Subgroup on Incinerator Test Methods for Fluoropolymers 4 Discussion Outline 1. Identify representative materials for incineration testing 2. Review relevant incineration conditions 3. Present key elements of proposed test program a. Test objective b. Test program phases c. Test materials d. Experimental apparatus e. Experimental conditions f. Sampling and analysis 4. Discuss next steps August 19, 2003 presentation to Technical Subgroup on Incinerator Test Methods for Fluoropolymers 5 1. Identify representative materials for incineration testing August 19, 2003 presentation to Technical Subgroup on Incinerator Test Methods for Fluoropolymers 6 Fluoropolymer Industry Overview Isolation/ Drying Extrusion / pelletization Molding process Tubing/ Hose Films Molded Fittings/ valves Wire & Cable Insulation Metal liners

pumps, pipes, valves Fibers Stabilization Concentration Formulation/

Coating/ casting / process Sintering/ baking Un sintered products Cookware Industrial Filter bags Coated parts Fibrous gaskets Clay absorbents Isolation/

Drying Molding/ sintering/

curing/ post curing process W& C insulation Hose/ Tubing Pipe liners Membranes O rings/ seals Additives Dry  non melt resins/ gums Molding unsintered products Thread sealant tapes Resin Manufacturer Resin Processor Polymerization APFO Dry melt resins Monomers Aqueous Dispersions August 19, 2003 presentation to Technical Subgroup on Incinerator Test Methods for Fluoropolymers 7 Representative Classes ° Dry melt resins 1. FEP, PFA, THV, ETFE, HTE ° Dry non melt resins/ gums 2. PTFE ( perfluorinated)

3. Fluoroelastomers ( nonperfluorinated)

° Aqueous dispersions 4. PTFE, FEP, PFA, THV August 19, 2003 presentation to Technical Subgroup on Incinerator Test Methods for Fluoropolymers 8 Proposed Test Materials ° Four composite mixtures ( one per class):

1. Dry melt resins ( FEP, PFA, THV, ETFE, HTE)

2. PTFE 3. Fluoroelastomers 4. Aqueous dispersions ( PTFE, FEP, PFA, THV)

° Each composite will be mixture of representative fluoropolymers, as solids, in equal proportions across producers for each class August 19, 2003 presentation to Technical Subgroup on Incinerator Test Methods for Fluoropolymers 9 2. Review relevant incineration conditions August 19, 2003 presentation to Technical Subgroup on Incinerator Test Methods for Fluoropolymers 10 Municipal Waste Combustors ( MWCs)

in U. S.  20001,2,3,4 0.4 13 Modular 30 102 Total 6.7 19 Refused Derived Fuel ( RDF) 23 70 Mass Burn Annual Capacity ( million T/ year)

No. of Facilities Type Note: 90% of U. S.

MWC capacity is at Large MWCs (~ 60% of facilities)

1  EPA, " Municipal Solid Waste in The United States : 2000 Facts & Figures", EPA530 R 02 001, June 2002 2  Integrated Waste Services Association ( IWSA), " Fast Facts about Waste to Energy" and other information 3  Eastern Research Group, " 2000 National Inventory of Large Municipal Waste Combustion Units", June 12, 2002 4  EPA, " Emission Guidelines for Existing Small Municipal Waste Combustion Units", 65 FR76380, Dec. 6, 2000 August 19, 2003 presentation to Technical Subgroup on Incinerator Test Methods for Fluoropolymers 11 MWC Operating Conditions ° Many incinerators for municipal solid waste are designed to operate in the combustion zone at 1800 ° F [ 982 ° C] to 2000 ° F [ 1093 ° C] 1 ° Combustion gases in traveling grate mass burn units are maintained " at about 1800 ° F [ 982 ° C] to ensure complete combustion of organic compounds" prior to passing to the boiler2 ° U. S. standards for MWCs include Good Combustion Practices ( GCP)

  " The ability of an MWC to achieve combustion temperatures that are adequate to destroy organics is a fundamental requirement of GCP". 3 ° Refuse derived fuel in a unit in the GCP study ( Mid Connecticut) 3 is combusted at furnace temperature > 1800 ° F [ 982 ° C] 4 1  U. S. EPA, Decision Maker's Guide to Solid Waste Management, Volume II, 1995 2  Donnelly, J. R. Waste incineration sources: refuse. In: Buonicore, A. J.; Davis, W. T., eds., Air Pollution Engineering Manual. Air and Waste Management Association. New York, NY: Van Nostrand Reinhold, 1992,. pp. 263 275 3  U. S. EPA, Municipal Waste Combustion Assessment: Technical Basis for Good Combustion Practice, EPA 600/ 8 89 063, August 1989 4 http:// www. nu. com/ energy/ stations/ south. asp August 19, 2003 presentation to Technical Subgroup on Incinerator Test Methods for Fluoropolymers 12 Modular MWC Temperatures1,2 Secondary Chamber Temperature Oswego Co., NY Red Wing,

MN Start of campaign 1012 Mid range secondary temperature 951 End of campaign 995 Low secondary temperature 885 Mean secondary temperature 954  1071 1  U. S. EPA, Municipal Waste Combustion Assessment: Technical Basis for Good Combustion Practice, EPA 600/ 8 89 063, August 1989, pp. 4 30  4 32; temperatures during which CO emissions met GCP standard 2  Note modular units are more commonly used at small MWC facilities August 19, 2003 presentation to Technical Subgroup on Incinerator Test Methods for Fluoropolymers 13 Medical Waste Incinerators ° Three types of incinerators are primarily used for medical waste: controlled air incinerators,

multiple chamber incinerators, & rotary kiln incinerators1   All three types of medical waste incinerators ( MWIs) use two chambers Controlled Air Multiple Chamber Rotary Kiln Primary Chamber 400 to 980 ° C 540 to 980 ° C 760 ° C Secondary Chamber 980 to 1200 ° C 980 to 1200 ° C 980 ° C EPA notes that 97% of MWIs are controlled air modular furnaces and 1%

are rotary kilns2 ° " any unit which presently has a residence time less than two seconds at 1000 C ( 1832 F)

does not meet the requirement for good combustion under the new regulations" 3 1  Theodore, L. Air Pollution Control and Waste Incineration for Hospitals and Other Medical Facilities, Van Nostrand Reinhold,

New York, 1990, pp 313 320..

2  U. S. EPA, Exposure and Human Health Reassessment of 2,3,7,8 Tetrachlorodibenzo p Dioxin ( TCDD) and Related Compounds,

Part I: Estimating Exposure to Dioxin Like Compounds Volume 2: Sources of Dioxin Like Compounds in the United States, Chapter 3,

EPA/ 600/ P 00/ 001Bb, Draft Final Report, September 2000 3  Van Remmen, T. Evaluation of the available air pollution control technologies for achievement of the MACT requirements in the newly implemented new source performance standards ( NSPS) and emission guidelines ( EG) for hospital and medical/ infectious waste incinerators, Waste Management, 1998, Vol. 18, p. 394 August 19, 2003 presentation to Technical Subgroup on Incinerator Test Methods for Fluoropolymers 14 Proposed Test Conditions ° MWIs typically operate with secondary chamber residence times of 2 seconds at > 1000 oC ° > 90% of municipal solid waste is combusted in MWCs typically operating with secondary stage temperatures ~ 982 oC1 ( res time ~ 2 seconds)

° Plan testing at MWC conditions   Conservatively propose 900 oC at 2 sec residence time 1 Typical secondary stage temperatures for mass burn & RDF units ~ 982 oC based on available information August 19, 2003 presentation to Technical Subgroup on Incinerator Test Methods for Fluoropolymers 15 3. Summarize key elements of test program August 19, 2003 presentation to Technical Subgroup on Incinerator Test Methods for Fluoropolymers 16 Test Program Objective ° Investigate incineration of fluoropolymers under laboratory scale conditions representative of typical municipal waste combustor operations in the U. S. to quantitatively determine emission levels of PFOA August 19, 2003 presentation to Technical Subgroup on Incinerator Test Methods for Fluoropolymers 17 Phases of Test Program 1. Development and approval of Test Protocol/ Quality Assurance Project Plan ( QAPP)

2. Thermogravimetric analysis of test materials 3. Preliminary gasification & combustion tests for test materials 4. Verification of quantitative transport of PFOA 5. Other method development as needed 6. Combustion tests at specified operating condition( s)

7. Data reduction and report development August 19, 2003 presentation to Technical Subgroup on Incinerator Test Methods for Fluoropolymers 18 Proposed Test Materials ° Four composite mixtures ( one per class):

1. Dry melt resins ( FEP, PFA, THV, ETFE, HTE)

2. PTFE 3. Fluoroelastomers 4. Aqueous dispersions ( PTFE, FEP, PFA, THV)

° Each composite will be mixture of representative fluoropolymers, as solids, in equal proportions across producers for each class August 19, 2003 presentation to Technical Subgroup on Incinerator Test Methods for Fluoropolymers 19 Experimental Apparatus ° General Description   a batch charged continuous flow reactor system ° The test sample is gasified and transported to a high temperature reactor ° In the high temperature reactor, the sample vapors are subjected to controlled conditions of residence time,

temperature, and excess air ° Combustion products are collected for quantitative analysis August 19, 2003 presentation to Technical Subgroup on Incinerator Test Methods for Fluoropolymers 20 Experimental Conditions ° Each test feed will be subjected to laboratory scale incineration using the experimental apparatus ° Temperature: 900 ° C for 2 seconds residence time ° Three replicates for each test level ( combination of test feed and temperature)

° Also, a blank run for each operating condition ° Amount of test material fed will be large enough to assure ability to detect PFOA in the emissions, but small enough to assure sufficient excess oxygen to be representative of typical MWC conditions August 19, 2003 presentation to Technical Subgroup on Incinerator Test Methods for Fluoropolymers 21 Planned Sampling & Analysis ° Exhaust gas parameters to be monitored:

  flow rate, oxygen ( O2) 1, carbon dioxide ( CO2), and carbon monoxide ( CO)

° Exhaust gas   will be collected on suitable sorbent cartridge( s) and / or in aqueous solution trap( s) for off line analysis to quantify PFOA ° Sampling and analysis methods   adapt & validate available PFOA methods for this study   investigate total organic fluorine analysis of exhaust gas2 1  O2 in exhaust gas is planned to be monitored via calculation based on air input flow 2  Exhaust gas analysis for fluoride ion is planned August 19, 2003 presentation to Technical Subgroup on Incinerator Test Methods for Fluoropolymers 22 Sampling & Analysis Methods ° Sample exhaust gas   Sorbent Cartridge ° OSHA Versatile Sampler ( OVS)

° analyze for PFOA   Aqueous Solution ° use one or more impingers containing aqueous solution ° analyze for PFOA ° Analyze exhaust gas for PFOA   via off line LC/ MS/ MS at a qualified commercial laboratory operating under suitable data quality guidelines ° Analyze exhaust for fluoride ion to assist in performing fluoride balance across experimental system August 19, 2003 presentation to Technical Subgroup on Incinerator Test Methods for Fluoropolymers 23 Test Materials Characterization ° elemental analysis to determine carbon,

hydrogen, nitrogen, chlorine, fluorine and oxygen by difference ° total organic fluorine August 19, 2003 presentation to Technical Subgroup on Incinerator Test Methods for Fluoropolymers 24 4. Discuss Next Steps U. S. Environmental Protection Agency Draft, August 13, 2003 Anticipated Attendees for Fluoropolymer Incineration Subgroup Meeting John Heinze, Environmental Health Research Foundation ( by phone) Takayuki Nakamura, Daikin TWG ( fluoro technical) Edward Lampert, Daikin Yukiko Nishiyama, Daikin Satoshi Komatsu, Daikin Maggie Martin, Daikin Robert Giraud, DuPont Noel Misa, Asahi Glass FMG ( strategic/ business) Lynne Harris, SPI Phil Taylor, University of Dayton ( Expert) Lisa Walton, W. L. Gore Lisa Campbell, Bergeson & Campbell ( Gore) John Blouin, EPA/ EETD Eric Stewart, EPA/ ORD Ward Penberthy, EPA/ CCD Ed Heithmar, EPA/ ORD Rich Leukroth, EPA/ CCD Wendy Hoffman, EPA/ EETD Nhan Nguyen, EPA/ EETD PFOA ECA Fluoropolymer Incineration Technical Subgroup Meeting August 19, 2003 NAME ORGANIZATION TELEPHONE # E MAIL ADDRESS ae~~~ iJ(&

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Subsequent meetings propose to focus on test methods for aged articles.

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pelletization Molding process Resin Manufacturer Resin Processor Tubing/ Hose Films Molded Fittings/ valves Wire & Cable Insulation Metal liners  pumps, pipes, valves Fibers APFO Monomers Fluoropolymer Industry Overview Stabilization Concentration Formulation/

Coating/ casting / process Sintering/ baking Un sintered products Aqueous Dispersions Cookware Industrial Filter bags Coated parts Fibrous gaskets Clay absorbents Dry melt resins Isolation/

Drying Molding/ sintering/ curing/ post curing process W& C insulation Hose/ Tubing Pipe liners Membranes O rings/ seals Additives Dry  non melt resins/ gums Molding unsintered products Thread sealant tapes Fluoropolymer Aged Articles 8   Melt/ Extrusion  polymer is melted to create finished polymer   Polymer drying  polymer is dried to create finished polymer   Liquid Dispersion  finished polymer is an aqueous dispersion Fluoropolymer Aged Articles 9 Fluoropolymer Aged Articles 10 Fluoropolymer Aged Articles 11 Fluoropolymer Aged Articles 12 Commercial Food Preparation Cookware Architectural Fabrics Clay Absorbents Fibrous Gaskets Fluoropolymer Aged Articles 13 Fluoropolymer Aged Articles 14 1 Fluoropolymer Aged Articles 15 Fluoropolymer Aged Articles 16 Fluoropolymer Aged Articles 17 U. S. Environmental Protection Agency Draft, August 13, 2003 Anticipated Attendees for Aged Fluoropolymer Articles Technical Subgroup Meeting Rich Purdy Treye Thomas, CPSC John Heinze, Environmental Health Research Foundation Bill Buxton, DuPont TWG George Millet, Dyneon TWG Joan Sylvain Baughan, Keller & Heckman ( Expert) David Rurak, DuPont FMG David Sarvadi, Keller & Heckman Allen Weidman, SPI/ FMG Takayuki Nakamura, Daikin TWG ( fluoro technical) Edward Lampert, Daikin Yukiko Nishiyama, Daikin Satoshi Komatsu, Daikin Maggie Martin, Daikin Lisa Walton, W. L. Gore Susan Youngren, Bergeson & Campbell ( Gore) Conrad ( Skip) Flessner, EPA/ EETD Greg Fritz, EPA/ EETD Zhishi Guo, EPA/ ORD Barbara Leczynski, EPA/ CCD Ward Penberthy, EPA/ CCD Ross Highsmith, EPA/ ORD Ed Heithmar, EPA/ ORD Rich Leukroth, EPA/ CCD Jasbir Sarna, EPA/ EETD Wendy Hoffman, EPA/ EETD ( Observer: David Menotti, Shaw Pittman [ Asahi]) PFOA ECA Fluoropolymer Aged Articles Technical Subgroup Meeting August 29,2003 NAME ORGANIZATION TELEPHONE # E MAIL ADDRESS IØd, t~ D~ J~. ce~~% c, r zo~ co~~(~ i'i ~ c~ vr, e~( 4va4o ~

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Goals The goals of the Telomer and Fluoropolymer Monitoring Subgroup( s) are:

1) Develop an understanding of how environmental sampling and monitoring fit into the overall objective of understanding how PFOA and PFOA precursors are released into the environment, their fate and transport once released, and routes of human and environmental exposure.

2) Identify specific questions that can be addressed by environmental sampling and monitoring.

3) Assess how current LOI environmental sampling and monitoring complements ( 2) above, and whether additional sampling/ monitoring may be necessary.

4) Report back to the PFOA ECA Monitoring Technical Workgroup in September 2003.

Meetings Meetings will be held at EPA Headquarters in Washington, DC. The first meeting of the subgroup is scheduled from 9: 00 to 4: 00 on August 15, 2003, to discuss telomer monitoring. The second subgroup is scheduled from 9: 00 to 4: 00 on August 21, 2003, to discuss fluoropolymer monitoring. All parties are encouraged to attend in person, if possible, but teleconference facilities will be arranged for those unable to travel. EPA requests that all interested parties submit any presentation or discussion material for general distribution one week prior to the meetings. U. S. Environmental Protection Agency Draft, August 13, 2003 Environmental Monitoring Technical Subgroups Tentative Agenda   First Meetings Telomer Monitoring Subgroup Friday, August 15, 2003 9: 00 AM to 4: 00 PM Fluoropolymer Monitoring Subgroup Thursday, August 21, 2003 9: 00 AM to 4: 00 PM EPA East, Room 4225 1201 Constitution Avenue, NW Washington, DC 20460 1. Discussion of how environmental sampling and monitoring fit into the overall objective of understanding how PFOA and PFOA precursors are released into the environment, their fate and transport once released, and routes of human and environmental exposure.

2. Identification of specific questions that can be addressed by environmental sampling and monitoring.

3. Assessment of how current LOI activities complement the goals and questions identified by the parties in ( 1) and ( 2).

4. Identification of potential additional environmental sampling and monitoring activities that could achieve the goals and answer the questions identified by the parties in ( 1) and ( 2).

5. Identification of next steps. TRP Telomer Research Program Monitoring Subgroup 15 August 2003 15 August 2003, page 2 Telomer Research Program TRP Approach

TRP is Committed to Processes which

Focus on relevant releases and exposures during the life cycle of telomer based products and articles

Products and treated articles were chosen using criteria such as market end use, chemistry type/ class, chemical volume, article type, and potential for human exposure.

Focus on fate and monitoring studies based on release and exposure analyses and considerations

Consider testing and measurements in an iterative, step wise approach triggered by improved knowledge gained 15 August 2003, page 3 Telomer Research Program Understanding Potential Environmental and Human Exposure PFOA Sources Potential Sources Study / Work Plan Approach 1) Telomer Industrial Production   U. S. Telomer production facilities   DuPont, Daikin 2) Industrial Use ( Mill)   Mill Release Simulation Model   Mill Pilot Study   Telomer Product Analysis 3) Use of Treated Articles   Telomer Treated Articles & In Use Studies : carpet, textiles, paper 4) Disposal of Treated Articles   Biodegradation   Incineration 15 August 2003, page 4 Telomer Research Program TRP Monitoring Work Objective

To understand and characterize current PFOA releases from carpet, textile and paper industrial manufacture uniquely attributable to telomer based polymeric products in order to provide information on potential PFOA environmental and occupational exposures 15 August 2003, page 5 Telomer Research Program Exposure Assessment Characterize Fate & Transport Properties Release Estimate Mill Monitoring Pilot Study Mill Release Model Characterize Potential Environmental &

Occupational Exposure 15 August 2003, page 6 Telomer Research Program Telomer Production Carpet Mill Consumer :

Commercial &

Residential Disposal ° landfill ° recycle USE TREATED ARTICLES DISPOSAL PRODUCTION Where the Telomer Polymeric Product is Applied to the Article Product Trail Example: Carpet 15 August 2003, page 7 Telomer Research Program Wet Application ° immersion ° spray ° foam Drying " Input" Substrate ° carpet ° textile fabric ° paper ° Bath concentration ° Application Rate ° Water ° Air Potential Environmental Releases ° Solid Waste ° Trimming Waste Treated Article Telomer Polymeric Product Application Process Telomer Product Application Process ° Processing equipment is uniform across industries, has been used for many years, and is well understood 15 August 2003, page 8 Telomer Research Program Telomer Polymeric Product Application Process for Carpet, Textiles, & Paper Treated Article Solid mg/ g Water mg/ L Air pg/ m3 Potential Environmental Releases Amount Used X ES EW EA Mass Balance : Amount Used = X + ES + EW + EA Characterize Environmental Releases from Article Manufacture : Mass Balance 15 August 2003, page 9 Telomer Research Program Mill Release Model : Product Input Variables

Telomer Polymeric Product Variables

wt.% active ingredient in product (~ 20%)

wt.% fluorine

wt.% telomer raw materials

wt.% eight carbon fluorinated chain C8F17

PFOA ( from product analysis)

80% Water 20% Telomer Polymer ° Aqueous Dispersion of .

° Polymeric Particles 100 200 nm with...

° Hydrocarbon Surfactant( s) 15 August 2003, page 10 Telomer Research Program Mill Release Model : Process Input Variables

Mill Process Variables

average daily product usage ( kg/ day)

number of user locations

application bath concentration g/ L

wt.% application bath to wastewater ( EW)

wt.% PFOA to air ( EA)

wt.% PFOA to solid waste ( ES) Integrate to Predict Total U. S. Environmental Releases & Concentrations 15 August 2003, page 11 Telomer Research Program Mill Release Model

From these Product & Process input variables

PFOA releases to water, air and solid waste can be estimated for each " user" site, including predicted environmental concentrations ( PEC's) for air and water.

Overall U. S. releases predicted

This is critical information required in order to define " fitness for purpose" for PFOA sampling and analysis methods. 15 August 2003, page 12 Telomer Research Program Mill Monitoring Pilot Study :

Represents Real Commercial Processing

To Follow the Release Modeling  ...

A controlled, realistic Study to Verify the Release Model with measured data

pilot production line

capability for water and exhaust air sampling

based upon demonstrated capability to determine VOC emissions for textile, carpet and paper chemicals

free from other contribution sources, past or present

to assess only the telomer contribution and eliminate non telomer contributions

begin with total organic fluorine analysis to verify overall mass balance

then... chemical specific determination : PFOA, 8 2 Telomer B Alcohol

need to develop and validate sampling and analysis methods 15 August 2003, page 13 Telomer Research Program Experimental Design How the Design Meets the Challenges Representative : The process being monitored is representative of the majority of currently operating carpet,

textile and paper mills. The technology used in is well established and stable.

Telomer Specific : Controlled introduction of telomer product will help to specifically pin point contributions from telomer based polymeric products used in the industrial processes. Acceptability : The facility and process to be used is certified as suitable for use in regulation of VOC emissions under EU production rules.

  Monitor a pilot scale mill process that has been certified for VOC testing under EU regulations.

  Controlled introduction of a telomerbased polymeric product( s)

  Begin with a product that will be broadly representative of telomer based polymeric products used throughout the textile industry. Use total organic fluorine to verify mass balance.

  The monitoring will be conducted in air,

water, and waste, using methods that will be specific for PFOA and F in these media on the LOI products. Relevant : We will monitor in air, water and waste using methods for PFOA, total organic fluorine and fluoride F,

such that the data will inform questions about potential environmental and occupational exposures.

Mill Monitoring Pilot Study 15 August 2003, page 14 Telomer Research Program Mill Monitoring Pilot Study :

Represents Real Commercial Processing

Pilot Facility

Equipment

industry standard, scaled down version of what is actually used in the mill

pad or spray application and dryer

used industry wide for research and development

well accepted as indicative and representative of real mill processing

Sampling

application bath : before and after application

exhaust air : OSHA versatile air sampler

treated article

work area air

Analysis

total organic fluorine, 8 2 Telomer B Alcohol, PFOA 15 August 2003, page 15 Telomer Research Program Mill Monitoring Pilot Study : Mass Balance Application ° Pad ° Spray ° Foam % wet pick up " untreated" " treated" Dryer " Roll Up"

Aqueous Application Bath ( g/ L)

Amount Used X Mass Balance : Amount Used = X + EW + EA + ES Potential Environmental Releases ° Water EW ° Air EA ° Solid Waste ES 15 August 2003, page 16 Telomer Research Program Mill Monitoring Pilot Study : Demonstration Phase

To demonstrate the test methodology & test system

Use open literature reference to prepare a representative acrylic polymer used for treating polyester textile fabric of known composition and residual raw material profile

also use this composition spiked with 8 2 Telomer B Alcohol

use total organic fluorine to see if meaningful measurements in air,

water and treated substrate can be demonstrated to achieve mass balance 15 August 2003, page 17 Telomer Research Program TRP Monitoring Work

These Studies will address PFOA:

environmental & occupational exposures

from Telomer based Polymeric Products

used in Carpet, Textile & Paper Industrial Processes in

air

water

solid / land Characterize Fate & Transport Properties Release Estimate Mill Monitoring Pilot Study Mill Release Model Characterize Potential Environmental &

Occupational Exposure U. S. Environmental Protection Agency Draft, August 13, 2003 Anticipated Attendees for Telomer Monitoring Subgroup Meeting Friday, August 15, 2003 Bob Griffin, Little Hocking Water Association Rich Purdy Treye Thomas, CPSC John Heinze, Environmental Health Research Foundation Rob Bilott, WV Plaintiffs ( by phone) David Menotti, Asahi Glass Takayuki Nakamura, Daikin Randy Roussel, Daikin Satoshi Komatsu, Daikin Ed Lampert, Daikin Yukiko Nishiyama, Daikin Maggie Martin, Daikin Bob Buck, DuPont John Gannon, DuPont Steve Korzeniowski, DuPont Tim Bingman, DuPont Alan Vicory, Ohio River Valley Water Sanitation Commission Linda Aller, Bennett & Williams Steve Williams, Ohio EPA Libretta Stennes, Steptoe & Johnson ( DuPont) W. Michael McCabe ( DuPont) Bill Hardie, W. L. Gore Richard Baillie, W. L. Gore Erin Russell, Clariant ( by phone) Phil Oshida, EPA/ CCD Laurence Libelo, EPA/ EETD Conrad ( Skip) Flessner, EPA/ EETD Ross Highsmith, EPA/ ORD John Blouin, EPA/ EETD Barbara Leczynski, EPA/ CCD Ward Penberthy, EPA/ CCD Linda Sheldon, EPA/ ORD Tim Collette, EPA/ ORD Ed Heithmar, EPA/ ORD Rich Leukroth, EPA/ CCD Wendy Hoffman, EPA/ EETD ( Observer: Katie Smythe, RAND [ TRP]) ( Observer: Bill Beers, OMNOVA Solutions) PFOA ECA Telomer Monitoring Technical Subgroup Meeting August 15, 2003 NAME ORGANIZATION TELEPHONE # E MAIL ADDRESS ¶ ~ c~

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Goals The goals of the Telomer and Fluoropolymer Monitoring Subgroup( s) are:

1) Develop an understanding of how environmental sampling and monitoring fit into the overall objective of understanding how PFOA and PFOA precursors are released into the environment, their fate and transport once released, and routes of human and environmental exposure.

2) Identify specific questions that can be addressed by environmental sampling and monitoring.

3) Assess how current LOI environmental sampling and monitoring complements ( 2) above, and whether additional sampling/ monitoring may be necessary.

4) Report back to the PFOA ECA Monitoring Technical Workgroup in September 2003.

Meetings Meetings will be held at EPA Headquarters in Washington, DC. The first meeting of the subgroup is scheduled from 9: 00 to 4: 00 on August 15, 2003, to discuss telomer monitoring. The second subgroup is scheduled from 9: 00 to 4: 00 on August 21, 2003, to discuss fluoropolymer monitoring. All parties are encouraged to attend in person, if possible, but teleconference facilities will be arranged for those unable to travel. EPA requests that all interested parties submit any presentation or discussion material for general distribution one week prior to the meetings. U. S. Environmental Protection Agency Draft, August 13, 2003 Environmental Monitoring Technical Subgroups Tentative Agenda   First Meetings Telomer Monitoring Subgroup Friday, August 15, 2003 9: 00 AM to 4: 00 PM Fluoropolymer Monitoring Subgroup Thursday, August 21, 2003 9: 00 AM to 4: 00 PM EPA East, Room 4225 1201 Constitution Avenue, NW Washington, DC 20460 1. Discussion of how environmental sampling and monitoring fit into the overall objective of understanding how PFOA and PFOA precursors are released into the environment, their fate and transport once released, and routes of human and environmental exposure.

2. Identification of specific questions that can be addressed by environmental sampling and monitoring.

3. Assessment of how current LOI activities complement the goals and questions identified by the parties in ( 1) and ( 2).

4. Identification of potential additional environmental sampling and monitoring activities that could achieve the goals and answer the questions identified by the parties in ( 1) and ( 2).

5. Identification of next steps. ECA Technical Subgroup Monitoring What is the overall objective of the ECA process?

° Enhance our understanding of sources of PFOA in the environment and the pathways by which human exposure to PFOA is occurring. Goal for Today ° Understand the role of environmental sampling and monitoring in characterizing the manufacturing contribution to PFOA levels in the environment How do you typically answer the question?

° Primarily use modeling with limited sampling to provide model inputs and limited sampling to verify model results Examples where EPA supports Modeling ° Federal New Source Review Program ° State permitting programs ° Residual Risk program ° Hazardous Waste Combustor assessments ° RCRA Corrective Action Sampling Limitations ° Limited geographic coverage ° Limited time perspective ° Doesn't provide timely results ° Environmental sampling is very challenging from a data quality perspective   weather impact   variable emissions   sample repeatability   other variables and adjustments ° Inefficient Underlying Question ° Are today's widely accepted models " useful" and effective in predicting PFOA environmental distribution?

° Useful?

  Conservative estimates   Predict general distribution patterns over time   Good for longer term averages ( rather than short term exposure assessments) Discussion of various EPA and USGS models for PFOA Environmental Assessment From Manufacturing Facilities 1. Characterize emissions and source parameters from facility 2. Simulate/ measure fate and transport of emissions to air, water and land 3. Assess Environmental Exposure Potential Conceptual Model Air Emissions Aqueous discharge River Unsaturated soil Groundwater Ambient air Modeling Tools Air Emissions Aqueous discharge River ISCST3 Model:

Ambient air and deposition modeling PRZM Model for unsaturated soil MODFLOW Model for groundwater transport PDM Model Air Dispersion Model ° Industrial Source Complex Short Term Model version 3 ( ISCST3)

° Used to estimate concentrations of chemicals in ambient air and surface deposition rate ° Developed, updated and evaluated by Air Branch ( OAQPS) of EPA ° Description and methodology included in " Guideline on Air Quality Models", Federal Register Appendix W of 40 CFR Part 51 ISCST3 Model Appropriate For:

° Continuous, industrial releases from point sources ° Emissions from dilute air streams ° Materials with long half lives Therefore, ISCST3 should be appropriate for PFOA Model Inputs ° Meteorological Data ° Terrain elevation maps ° Stack Parameters   Location ( coordinates)

  Height   Temperature   Stack gas vertical velocity   Diameter   Emission rates for each compound ° Property information for deposition modeling   particle size and density   scavenging coefficients ° Plot Plan   Exact locations of all sources   Property line   Building locations and heights Mass emission rate as vapor and small particles Prevailing wind Vertical Term Air Transport Process Dispersion ° Plume rises ( UP)

° Plume moves downwind ( OVER)

° Plume disperses ( OUT)

° Part of plume intersects with ground level Wet and Dry Deposition Air Dispersion Model Output Emissions exit point sources at site as vapor and particulate Some material reaches ground level, but stays in air = ambient air concentrations Some material lands on the ground =

deposition rate Calculations of Deposition Rate ° Dry Weather Deposition   Includes particles that are heavy enough to fall out due to gravity   Based on specific size and density of particles in emissions ° Wet Weather Deposition   Includes particles and vapor that are removed from the air by falling precipitation   Based on site specific precipitation information   Based on compound specific " scavenging coefficients"

° Total Deposition   Sum of dry and wet   Results given as grams/ m2 yr Modeling Tools Air Emissions Aqueous discharge River ISCST3 Model:

Ambient air and deposition modeling PRZM Model for unsaturated soil MODFLOW Model for groundwater transport PDM Model Groundwater Concentrations From Deposition Modeling ° USEPA Pesticide Root Zone Model ( PRZM 3.12b)

  Used in EPA pesticide programs   Cited on Office of Pesticide Programs website:

http:// www. epa. gov/ oppefed1/ models/ water/ index. htm ° Simulates chemical movement in unsaturated soil and estimates concentrations at top of groundwater table ° Documentation for version 3 available from USEPA National Exposure Research Laboratory in Athens, GA PRZM Model Appropriate For:

° Continuous load application of air deposited chemicals ° Unsaturated soil systems ° Materials with a range of half lives and adsorption properties Therefore, PRZM should be appropriate for PFOA PRZM ° Input to PRZM   Chemical data ° " Application rate" = deposition rate from ISCST3 modeling ° Sorption rate ° Half life in soil   Soil profile data   Climatic data ° Output from PRZM   Estimated concentration at top of groundwater table Modeling Tools Air Emissions Aqueous discharge River ISCST3 Model:

Ambient air and deposition modeling PRZM Model for unsaturated soil MODFLOW Model for groundwater transport PDM Model Conceptual Model for deposition to groundwater Groundwater adsorption and desorption Unsaturated soil zone 3 dimensional advective transport Groundwater Transport Model ° USGS Modular Three Dimensional Groundwater Flow Model ( MODFLOW)

° Used since 1986

° Used to simulate groundwater transport ° Assumes no material loss during transport MODFLOW Model Appropriate For:

° Simulating groundwater flow in a wide variety of hydro geologic conditions ° Hydro geologic systems influenced by multiply stresses and boundary conditions ° Conservative estimate chemical transport in groundwater Therefore, MODFLOW should be appropriate for PFOA MODFLOW Input   Stratigraphy   Hydraulic conductivity   Meteorological data   Groundwater recharge   System stresses ( e. g., production well pumping)

Site specific and regional geologic and hydrogeologic data MODFLOW Output ° Groundwater surface map calibrated to actual field measurements ° Groundwater flow direction and rate ° Groundwater discharge locations Modeling Tools Air Emissions Aqueous discharge River ISCST3 Model:

Ambient air and deposition modeling PRZM Model for unsaturated soil MODFLOW Model for groundwater transport PDM Model EPA Probabilistic Dilution Model ( PDM)

° Part of EPA Exposure Fate Assessment Screening Tool (

EFAST to support EPA assessments of the potential exposures to new chemicals under Section 5 of TSCA.

° PDM predicts how many days per year a chemical exceeds a target concentration level in an ambient water body will be exceeded after being discharged from an industrial facility. PDM Model Appropriate For:

° Continuous chemical loading from discharge point/ outfall into a water body ° Water bodies with known reach characteristics ° Most Chemicals Therefore, PDM should be appropriate for PFOA PDM Required Inputs ° Input   Name, NPDES number, and location of industrial plant   Receiving stream 11 digit Reach Number   Reach Number of the river segment to be analyzed   Number of release days per year   Loading ( kg/ day)

  Effluent flow rate from the plant   Target Concentration ° Output   Mean monthly surface water concentration for River Reach proximal to facility What we have learned from field studies .. Modeling Tools Air Emissions Aqueous discharge River ISCST3 Model:

Ambient air and deposition modeling PRZM Model for unsaturated soil MODFLOW Model for groundwater transport PDM Model Comparison of Modeled Air Deposition Modeled to Top of Groundwater ( TOG)

versus Field Measurements Air Deposition kg/ hectare/ yr PRZM Model Result ( TOG)

ug/ L Field Measurement ( TOG) ug/ L 0.1 20 * 23 * 4 sample mean Soil Model Summary ° Correlation of Air deposition with ground water interface concentration Good ° Is the model useful?

  Conservative estimate Consistent   Predicts general distribution Yes   Good for longer term average Yes Modeling Tools Air Emissions Aqueous discharge River ISCST3 Model:

Ambient air and deposition modeling PRZM Model for unsaturated soil MODFLOW Model for groundwater transport PDM Model Comparison of Groundwater Flow Model Results versus Field Measurements ° Results were compared to measured groundwater elevations in 84 monitor wells within the model domain ° The model results display an excellent correlation with field measurements from monitor wells   Mean error is less than 2 feet, or less than 1% Groundwater Model Summary ° Correlation of Model predicted groundwater elevations with monitor well groundwater elevations Good ° Is the model useful?

  Conservative estimate Consistent   Predicts groundwater flow Yes   Good for long term average Yes Modeling Tools Air Emissions Aqueous discharge River ISCST3 Model:

Ambient air and deposition modeling PRZM Model for unsaturated soil MODFLOW Model for groundwater transport PDM Model Comparison of Down river Modeled Concentration versus Actual Measurement Modeled River Concentration Range ( ug/ L) Measured River Concentration Range ( ug/ L)

0.2   1.0 0.1   1.1 River Model Summary ° Correlation between river water model and measured concentrations Good ° Is the model useful?

  Conservative estimate Consistent   Predicts general distribution Yes   Good for longer term average Yes Modeling Tools Air Emissions Aqueous discharge River ISCST3 Model:

Ambient air and deposition modeling PRZM Model for unsaturated soil MODFLOW Model for groundwater transport PDM Model Comparison of ISCST3 Air Modeling versus Actual Groundwater Measurements Modeled Air Concentration ug/ m3 Mean Water Concentration ug/ L 0.6   0.8 8.8 0.4   0.6 8.3 0.2   0.4 1.9 < 0.2 1.4 Demonstrates trend; not intended to reflect precise prediction Impressions From the Air/ Water Comparison ° There is a trend in the data ( higher deposition correlates with higher groundwater measurement)

° For many reasons, a direct correlation is not possible, but air modeling results can define where sampling should occur and where it is not needed ISCST3 Air Model Summary ° Correlation with ground water Good ° Correlation with air concentrations Unknown ° Is the model useful?

  Conservative estimate Unknown   Predicts general distribution Yes   Good for longer term average ° Concentration Unknown ° Distribution Yes Open Issue ° Does Air Dispersion Model ( ISCST3)

provide conservative estimates of ambient air concentrations????

° Plan to resolve   Develop and validate sampling and analysis method   Design a verification plan   Execute plan Overall Conclusions ° These environmental models are useful and effective for characterizing the contribution of manufacturing to PFOA levels in the environment ° The role of monitoring is to provide model input data and, where appropriate, verify model outputs Recommendations ° Verify modeled ambient air concentrations ° PFOA Contribution Determination   APFO Manufacturing ° Models and current monitoring plans are sufficient   Fluoropolymer manufacturing ° Models and current monitoring plans are sufficient   Fluoropolymer processing ° Need to complete the dispersion processor material balance ( covered in LOI)

° The material balance output can be used for modeling input Goal for Today ° Understand the role of environmental sampling and monitoring in characterizing the manufacturing contribution to PFOA levels in the environment U. S. Environmental Protection Agency Draft, August 13, 2003 Anticipated Attendees for Fluoropolymer Monitoring Subgroup Meeting Thursday, August 21, 2003 Bob Griffin, Little Hocking Water Association Rich Purdy Treye Thomas, CPSC John Heinze, Environmental Health Research Foundation Rob Bilott, WV Plaintiffs ( by phone) Alan Vicory, Ohio River Valley Water Sanitation Commission Linda Aller, Bennett & Williams Steve Williams, Ohio EPA George Millet, Dyneon TWG Mike Santoro, 3M ( Expert) Bob Sussman, Latham & Watkins ( 3M) David Rurak, DuPont FMG John Gannon, DuPont, Environmental Fate & Effect ( Expert) Cathie Barton, DuPont, Air Modeling Charlie Zarzecki, DuPont, Air Modeling Andrew Hartten, DuPont, Water/ Soil Monitoring David Sarvadi, Keller & Heckman Libretta Stennes, Steptoe & Johnson ( DuPont) Takayuki Nakamura, Daikin Randy Roussel, Daikin Satoshi Komatsu, Daikin Ed Lampert, Daikin Yukiko Nishiyama, Daikin Maggie Martin, Daikin Allen Weidman, SPI/ FMG Lisa Walton, W. L. Gore Lisa Campbell, Bergeson & Campbell ( Gore) Phil Oshida, EPA/ CCD Laurence Libelo, EPA/ EETD Conrad ( Skip) Flessner, EPA/ EETD Ross Highsmith, EPA/ ORD John Blouin, EPA/ EETD Barbara Leczynski, EPA/ CCD Ward Penberthy, EPA/ CCD Linda Sheldon, EPA/ ORD Tim Collette, EPA/ ORD Ed Heithmar, EPA/ ORD Rich Leukroth, EPA/ CCD Wendy Hoffman, EPA/ EETD ( Observer: David Menotti, Shaw Pittman [ Asahi]) PFOA ECA Fluoropolymer Monitorin Technical Subgroup Meeting August 21,2003 NAME ORGANIZATION TELEPHONE # E MAIL ADDRESS ~  ask ,~ matscc / 4~ z(~~ iwt& b ~ DiA .2é~ S/ wrr, o er ` I ZJz; k~ k~ yxs~ Cv* y(~ ker~)

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