Document 50GogzbQB30vzE2zDedxvBak0

esp AR22--6 HT oe DuPont [RgeV l=oely]I<Te Product Stewardship Update Presented to The United States Environmental Protection Agency : 3 November 25, 2002 & | Q T. S. Bingman, R. C. Buck, S. H. Korzeniowski, J. C. Stadler | 38 Chemica ottinsEmierprse po Some Santasd: ppyg 1 Company Sanitized Presentation Outline Introduction - Agenda, desired outcomes - Research approach overview - Overall DuPont Timeline & Milestones Toxicology & Descriptive Biology Update - Intermediate : Telomer BA - Polymers : Telomer Urethane, Telomer Acrylate - Surfactants : Telomer Phosphate - Overall Summary & Draft Hazard Assessment Exposure & Risk Characterization - Consumer & Occupational Exposure - Risk Characterization Environmental Fate & Effects - Environmental Compartments - Environmental Effects - Environmental Fate Summary, Conclusions, Discussion & Questions Chemical Solutions Enterprise Company Sanitized. Does not contain TSCA CBI. AR-226 25 Nov. 2002 2 DuPont PS Effort : Product Focused 25 Nov. 2002 DuPont CCAS & Haskell Laboratory Analytical Product & Substrate Analysis Toxicology , Exposure & Fate work methods development and analysis Chemical "Standards" External Labs Academic Collaboration Environmental Fate & Effects Physical / chemical properties Environmental compartments Fate (abiotic & biotic) Effects : aquatic, terrestrial 14C Labeled Material DuPont CCER d Communication DuPont Chemical Solutions Enterprise Product Stewardship Business Process Environmental Risk Assessment input DuPont Haskell Laboratory Toxicology Repeated Dose / One Generation Reproduction / Developmental Pharmacokinetics Dermal Inhalation 14C Labeled Material Human Health Risk Assessment Exposure Product Trails Mass Balance Human & Environmental Exposure Assessment Risk Characterization DuPont CRG Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 3 DuPont Product Stewardship Key Communications 2001 - Present 25 Nov. 2002 2001 : Feb : DuPont meets with U.S. EPA to review Tox & EFE Plans & Results April : DuPont presents Tox Studies at Society of Toxicology (SOT) Annual meeting DuPont meets with Environment & Health Canada May : DuPont meets with DEFRA, UK Env. Agency Oct : DuPont presents initial data at Soc. Of Env. Tox & Chemistry (SETAC) Meeting Dec : DuPont meets with U.S. EPA 2002 : April : DuPont presents Tox Study Data at SOT Annual meeting May : DuPont meets with UK Env. Agency; Dutch RIKZ / Univ. Amsterdam June : DuPont meets with Environment & Health Canada Nov. : DuPont presents at North America SETAC Meeting DuPont meets with U.S. EPA Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 4 25 Nov. 2002 DuPont Fluorotelomer Product Groups: Intermediates, Surfactants, Polymers 1) Intermediates Sales Products CF2=CF2 (TFE) F(CF2CF2)nI (Telomer A) n = 2-8 F(CF2CF2)nCH2CH2I (Telomer B) 2) Surfactants / "Molecules" Anionic - Phosphate, Carboxylate, Sulfonate Nonionic - Ethoxylate Betaine F(CF2CF2)nCH2CH2OH (Telomer BA) Straight Chain Alkyl F(CF2CF2)nCH2CH2OC(O)C(R)=CH2 Zonyl TM (R=CH3) ; Zonyl TAN (R=H) 3) Polymers Acrylic Ester Amide Urethane Urea 5 Test Compounds Represent Large Per Cent of Product Line Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 5 25 Nov. 2002 Repeated-Dose Study Plan Overview 5 Test Compounds Structures Represent Majority of DuPont Product Line Products Intermediate Telomer BA Polymer Telomer Urethane Telomer Acrylate Surfactant Telomer Phosphate Telomer Ethoxylate Repeated-Dose Studies Rat Model 90 Day Subchronic Oral Study One-Generation Reproduction Developmental Toxicity We continue to fill in our database, as we committed 1 May 2001. Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 6 DuPont Toxicology Studies Timeline* 2000 2001 2002 2003 Test Material Work 3Q 4Q 1Q 2Q 3Q 4Q 1Q 2Q 3Q 4Q 1Q 2Q 3Q T elomer 90 Day Oral Repeat Dose, 1Gen Repro Urethane (Rat) Polymer Developmental Study (Rat) Dermal Permeation (Rat) 90-Day Follow-Up Study Telomer BA 90 Day Range-Finding Study Intermediate 90 Day Oral Repeat Dose + 1Gen Repro (Rat) Developmental Study Rangefinder Genetic Toxicity: In Vitro Chrom Ab Developmental Study (Rat) T elomer 90 Day Range Finding Ethoxylate 90 Day Oral Repeat Dose,1Gen Repro Surfactant (Rat) Developmental Study Rangefinder Developmental Study (Rat) T elomer 90 Day Range Finding Phosphate 90 Day Oral Repeat Dose (Rat) Surfactant 1Gen Reproduction Study (Rat) Developmental Range Finder Developmental Study (Rat) 28 Day Dermal Repeat Dose (Rat) 14-Day Inhalation Repeat Dose (Rat) T elomer 90-Day Range Finding Acrylate 90 Day Oral Repeat Dose,1Gen Repro Polymer (Rat) Developmental Study Rangefinder Developmental Study (Rat) Work Complete Work Underway Projected Timing 25 4Q Nov. 2002 Chemical Solutions Enterprise * This is a proposed timeline and subject to change. DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 7 25 Nov. 2002 DuPont Toxicity Studies : Rat Model Multiple Routes of Exposure Oral - 90-day subchronic, reproductive, and developmental toxicity - Dosing by gavage, male and female rats - Full battery of tissues examined Dermal - In vitro tests for dermal penetration - rat and human skin - In vivo tests - 28 day study, male rats Inhalation - 14/28 day study, male rats Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 8 Intermediate : Telomer BA Study Summary & Timeline F(CF2CF2)nCH2CH2OH n= 3 -6 Test Material Telomer BA Intermediate Study 90 Day Range-Finding Study 90 Day Oral Repeat Dose + 1Gen Repro (Rat) Developmental Study Rangefinder Genetic Toxicity: In Vitro Chrom Ab Developmental Study (Rat) 2000 2001 3Q 4Q 1Q2Q3Q4Q Work Complete 90 Day Subchronic Oral : Dose Levels : 25, 100, 250 mg/kg/day NOEL 25 mg/kg/day Primary Target : Teeth Reproductive Toxicity : Dose Levels : 25, 100, 250 mg/kg/day NOEL 25 mg/kg/day not a selective reproductive toxin Developmental Toxicity : Dose Levels : 25, 200, 500 mg/kg/day NOEL 200 mg/kg/day not a selective developmental toxin Chemical Solutions Enterprise Company Sanitized. Does not contain TSCA CBI. AR-226 25 Nov. 2002 9 25 Nov. 2002 Polymer : Telomer Urethane Study Summary & Timeline F(CF2CF2)nCH2CH2OH (Telomer BA) n = 3 - 6 Straight Chain Alkyl Telomer Urethane Polymer Aqueous Dispersion with surfactant Test Material T elomer Urethane Polymer Work 90 Day Oral Repeat Dose + 1Gen Repro (Rat) Developmental Study (Rat) Dermal Permeation (Rat) Nasal Lesion - Follow-Up Study 2000 2001 2002 2003 3Q 4Q 1Q2Q3Q4Q1Q2Q3Q4Q1Q2Q3Q4Q Work Complete Work Underway 90 Day Subchronic Oral: Dose Levels : 50, 250, 1000 mg/kg/day Reproductive Toxicity: Dose Levels : 50, 250, 1000 mg/kg/day Developmental Toxicity: Dose Levels : 50, 250, 1000 mg/kg/day LOEL 50mg/kg/day Primary Target : Nose No effects on reproduction at any dose not a selective reproductive toxin No abnormalities or birth defects at any dose not a selective developmental toxin Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 10 Polymer : Telomer Urethane 90 Day Oral Study (Rat) : Follow-Up 25 Nov. 2002 Purpose: to determine the cause and establish a no-effect level for nasal lesions (olfactory epithelial degeneration and necrosis) Primary questions to address -Are the lesions caused by telomer urethane polymer or surfactant? Reproducible? -Can a NOEL be established? Study Design 3 dose groups: telomer urethane polymer product, surfactant, and control Animals dosed with equivalent of high dose in 90 day study Sacrifice and evaluate nasal tissue at 2, 4 and 13 weeks as needed Follow with 3 dose level study with either surfactant or polymer Study started: 11/01/02 Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 11 In Vitro Dermal Permeation with Telomer Urethane 25 Nov. 2002 Purpose: To determine the permeability of the agent through rat and human skin Draft Guideline: OECD, 1999; ECETOC, 1993 In vitro technique employing glass (static) diffusion cells have been shown to predict percutaneous absorption of various chemicals in vivo Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 12 25 Nov. 2002 Static Diffusion Cell : In Vitro Dermal Permeation donor compartment sampling port for analysis pinch clamp membrane Receptor compartment Saline receptor fluid optional water jacket Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 13 25 Nov. 2002 Polymer : Telomer Urethane In-vitro Dermal Permeation Methods - 20 l product solution was applied to rat epidermal membrane - Total of 1234 g fluorine in contact with rat skin for 6 hours - 3 ml receptor fluid analyzed for total fluorine using Wickbold torch method Results - Total fluorine in receptor fluid was below the limit of detection (LOD) of 0.052 ppm; less than 0.013 % of urethane polymer permeated the rat skin - Input for exposure and risk characterization Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 14 Polymer : Telomer Acrylate Chemistry Aqueous emulsion polymerization of monomer composition : - F(CF2CF2)nCH2CH2OC(O)CH=CH2 n = 4 - 6 CBI Information has been redacted 25 Nov. 2002 - MW > 40,000 Test Substance for Acute Studies : product = aqueous dispersion of polymer in water with surfactants Test Substance for Repeated Dose Studies: - solid polymer washed free of surfactants, composition before and after washing verified as the same Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 15 Polymer : Telomer Acrylate Toxicology Information Acute Toxicity*: Oral Rat: ALD > 11,000 mg/kg Inhalation Rat: 4 hr: ALC = 590 mg/m3 Skin Irritation: Non-irritating Eye Irritation: Moderate, reversible irritation Sensitization: Not an irritant or sensitizer in multiple human patch tests Aquatic Toxicity* Rainbow Trout : 96Hr. LC50 = 181 mg/L Daphnia Magna : 48Hr. EC50 = 234 mg/L Algae : 72Hr. EC50 = 36.2 mg/L 25 Nov. 2002 * data generated on aqueous dispersion product Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 16 Polymer : Telomer Acrylate Subchronic Oral Study Range-Finder 25 Nov. 2002 Test material: Telomer Acrylate Polymer Solids in water vehicle Doses: - 0, 1, 10, 100, 1000 mg/kg/day - 100% active test substance No clinical signs or body weight effects after 45 days at any dose Total fluorine levels assessed, steady-state appears to occur around 20 days into dosing Fluorine levels in blood are low Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 17 Polymer : Telomer Acrylate Study Summary & Timeline Test Material T elomer Acrylate Polymer Work 90-Day Range Finding 90 Day Oral Repeat Dose,1Gen Repro (Rat) Developmental Study Rangefinder Developmental Study (Rat) 2002 2003 1Q2Q3Q4Q1Q2Q3Q4Q Work Complete Work Underway 25 Nov. 2002 90 Day Subchronic Oral: Dose Levels : 10, 100, 1000 mg/kg/day Reproductive Toxicity: Dose Levels : 10, 100, 1000 mg/kg/day Developmental Toxicity: Dose Levels : 10, 100, 1000 mg/kg/day Genetic Toxicity : In Progress In Progress In Progress Negative Ames, Chom Ab Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 18 Surfactant : Telomer Phosphate Chemistry F(CF2CF2)nCH2CH2OH (Telomer BA) n = 3 - 6 P2O5, H2O, isopropanol, NR3 [F(CF2CF2)nCH2CH2O]xP(O)(ONR3H)3-x X = 1-3 Products by Process BL, B Telomer Distributions tailored to end-use Mixture of Mono-, Bis- and Pyro- Phosphate Esters Study material contains 25 wt% isopropanol as co-solvent Chemical Solutions Enterprise Company Sanitized. Does not contain TSCA CBI. AR-226 25 Nov. 2002 19 25 Nov. 2002 Test Material T elomer Phosphate Surfactant Surfactant : Telomer Phosphate Timeline Work 90-Day Range Finding 90 Day Oral Chronic Repeat Dose (Rat) 1Gen Reproduction Study (Rat) Developmental Range Finder Developmental Study 28 Day Dermal Repeat Dose (Rat) 14 Day Inhalation Repeat Dose (Rat) 2000 2001 2002 2003 3Q 4Q 1Q2Q3Q4Q1Q2Q3Q4Q1Q2Q3Q4Q Work Complete Work Underway 90 Day Subchronic Oral: Dose Levels : 10, 60, 300 mg/kg/day (35% a.i.) Reproductive Toxicity: Dose Levels : 75, 500, 3500 mg/kg/day (20% a.i.) Developmental Toxicity: Dose Levels : 625, 1250, 2500 mg/kg/day (20% a.i.) Genetic Toxicity : Female NOEL = 60 mg/kg/day Male : NOEL < 10 mg/kg/day Target : liver In Progress In Progress Negative Ames Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 20 Surfactant : Telomer Phosphate Toxicology Information Acute Toxicity* Oral Rat: Inhalation Rat: ALD > 17,000 mg/kg; LD50 > 25,000 mg/kg 4 hr: ALC = 57 mg/m3 Skin Irritation: Not a skin irritant Eye Irritation: Minimal irritant Sensitization: Not an irritant or sensitizer 25 Nov. 2002 Aquatic Toxicity* Rainbow Trout : 96Hr. LC50 > 1,000 mg/L Daphnia Magna : 48Hr. EC50 >1,000 mg/L Algae : 1Q2003 Biodegradability* : OECD 301 70% Chemical Solutions Enterprise Company Sanitized. Does not contain TSCA CBI. * studies conducted on 35% active test material containing isopropanol AR-226 21 Surfactant : Telomer Phosphate Repeated-Dose Toxicology (Rat) : Summary (35% a.i.; with isopropanol) 90 Day Subchronic Oral : Dose Levels : 10, 60, 300 mg/kg/day Inhalation (Two Week) : Dose Levels : 0.2, 2.0, 20 mg/m3 Dermal (28 Day) : Dose Levels : 10, 100, 1000 mg/kg/day (IPA containing, 35% a.i.) Female NOEL = 60 mg/kg/day Male : NOEL < 10 mg/kg/day Pathology peer review in progress Study Started 29 Oct. 2002 25 Nov. 2002 (20% a.i.; no isopropanol) Reproductive Toxicity : Dose Levels : 75, 500, 3500 mg/kg/day Report in Progress Developmental Toxicity : Report in Progress Dose Levels : 625, 1250, 2500 mg/kg/day Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 22 Surfactant : Telomer Phosphate* 90 Day Oral Study Results Study Conclusion: Female (F) : NOEL = 60 mg/kg/day 25 Nov. 2002 Male (M) : NOEL < 10 mg/kg/day 300 mg/kg/day (35% active, with isopropanol) - low body weight, food parameters (M) - decreased red cell mass (M) - liver: elevated enzymes, increased weights, necrosis (M&F) - kidney: increased weights, hypertrophy (M) - thyroid: hypertrophy (M&F) 60 mg/kg/day - liver: elevated enzymes, increased weights, necrosis (M) - kidney: increased weights, hypertrophy (M) - thyroid: hypertrophy (M) 10 mg/kg/day - liver: elevated enzymes, necrosis (M) * study conducted on 35% active test material containing isopropanol NOTE: Minimally elevated Beta Oxidation at 60 and 300 mg/kg/day Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 23 25 Nov. 2002 Surfactant : Telomer Phosphate Reproduction Study Results Study Conclusion: Report in Progress (20% a.i., no isopropanol) Study Design Doses : 75, 500, 3500 mg/kg/day P1 Pathology - the same target organs identified from 90-Day Subchronic Study with isopropanol-containing test material will be evaluated In-life Parameters - observed body weight effects (M & F) only at the high dose Study Report Complete: January 2003 Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 24 Surfactant : Telomer Phosphate Developmental Study Results Study Conclusion : Report in progress (20% a.i., no isopropanol) Study Design Doses : 625, 1250, 2500 mg/kg/day Study Report Complete: December 2002 25 Nov. 2002 Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 25 Surfactant : Telomer Phosphate Two-Week Inhalation Study Study Status: Report in preparation 25 Nov. 2002 Concentrations: 0.2, 2, and 20 mg/m3 Exposures: 6 hrs/day x 9 days, 2-week recovery Animals: 10 male rats/group Additional Blood Analysis : total fluorine In-life: observed reduced body weight only at high dose Necropsy: No increased organ weights at any dose Microscopic findings: respiratory tract appears to be the most sensitive target Study Report Complete : 1Q 2003 Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 26 Surfactant : Telomer Phosphate 28 Day Dermal Study Study Status: Study started 29 October 2002 25 Nov. 2002 Doses: 10, 100, 1000 mg/kg/day Application: 6 hrs/day for 28 days Animals: 10 male rats/group Tissues: Skin and target tissues identified from oral study Additional Blood Analysis : total fluorine Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 27 25 Nov. 2002 Fluorotelomer Products Repeated-Dose Study Observations Common across all DuPont Telomer Product Studies : - liver and thyroid hypertrophy : physiological response - in the rat : males more sensitive than females Target endpoints are unique to each test material Plasma and Urine Fluoride values indicate that test materials are processed differently - functionality appears to drive the observed unique endpoints Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 28 25 Nov. 2002 Hazard Assessment Example - "Reference Dose" This translates the animal data to a proposed "safe" human exposure level Animal Model Toxicity Testing 10A: Animals to Humans Unce rtain ty Fa ctors 10S: Chronic vs. Subchronic LOEL* = 50 mg/kg/day Telomer Urethane * expect NOEL to be near this value 10 1000 fold** 10 **Using the highest value of uncertainty factor range (1-10) 10 10H: Human Variability Human Criterion "Reference Dose" = 0.05 mg/kg/day Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 29 Risk Assessment Framework Characterize Fate & Transport Properties Release Estimate Characterize Distribution in the Environment 25 Nov. 2002 Human Health Population Exposure Direct Use / Release Exposure Measure Predict Estimated Human Toxicity Hazard Assessment Chemical Solutions Enterprise Exposure Assessment RISK ASSESSMENT Human Health Ecological Risk Management Decisions Company Sanitized. Does not contain TSCA CBI. Non-Human Population Exposure Measure Predict Estimated EcoToxicity Hazard Assessment AR-226 30 25 Nov. 2002 How Did We Approach the Analysis? What types of products do we sell? Who buys our products? What consumer products contain our products? How do our customers use our products? In what form? How do consumers come in contact with our products? What is the magnitude of potential consumer exposure? How much? How often? How does exposure compare to what we know about potential hazard? Risk Characterization Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 31 Exposure Assessment Overview Potentially Exposed Subpopulation Consumer Food Wrap Paper * Ingestion Carpets * Dermal * Indirect Ingestion Apparel * Dermal 25 Nov. 2002 Potentially Exposed Subpopulation Occupational Medical Worker Garment Worker Painter Custodial Worker Medical Fabric Paints * Dermal * Dermal * Dermal * Inhalation Cleaning Products * Dermal Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 32 CBI Information has been redacted 25 Nov. 2002 CBI Information has been redacted Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 33 CBI Information has been redacted 25 Nov. 2002 CBI Information has been redacted Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 34 Critical Exposure Variables CBI Information has been redacted 25 Nov. 2002 Developed point estimates for all necessary variables: - (1) Concentration of telomer urethane - (2) Loss of polymer over time - (3) Exposure period - (4) Skin surface area - (5) Dermal transfer coefficient - (6) Body weight - (7) Food surface area - (8) Bioavailability of the telomer urethane Also developed probabilistic inputs for key parameters in the analysis: Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 35 CBI Information has been redacted 25 Nov. 2002 CBI Information has been redacted Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 36 CBI Information has been redacted 25 Nov. 2002 CBI Information has been redacted Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 37 CBI Information has been redacted 25 Nov. 2002 CBI Information has been redacted Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 38 CBI Information has been redacted 25 Nov. 2002 CBI Information has been redacted Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 39 CBI Information has been redacted 25 Nov. 2002 CBI Information has been redacted Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 40 CBI Information has been redacted 25 Nov. 2002 CBI Information has been redacted Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 41 CBI Information has been redacted 25 Nov. 2002 CBI Information has been redacted Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 42 25 Nov. 2002 Exposure Assessment Summary We have a great deal of confidence in this assessment and the process we are using. We believe that this information supports our belief that our products are safe for their intended uses. We are working to develop information with regard to community, ecological and integrated exposure We are using this process to identify data needs and to focus our research efforts We welcome your feedback on our initial efforts and your support in helping us to move forward Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 43 25 Nov. 2002 DuPont Environmental Fate & Effects Work Plan We began with Physical-Chemical Property characterization for Telomer B and Telomer B Alcohol Intermediates Methods development progress now enables us to begin fate work on products Environmental Fate & Effects Study Plans : Product Focus - Physical- Chemical Properties - Environmental Effects : Acute Data, BCF Screen , Chromic Fish ELS - Environmental Fate Intermediate Surfactants Polymers Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 44 25 Nov. 2002 Physical - Chemical Properties : Water Solubility 6-2, 8-2 Telomer B Alcohols & Iodides Solubility 12C 25C 37C 60C C6F13CH2CH2OH 12 ppm 17 ppm C8F17CH2CH2OH 130 + 30 ppb 140 + 50 ppb 318 + 176 ppb 225 + 50 ppb C6F13CH2CH2I 9 ppb C8F17CH2CH2I < 10 ppb (LOQ) pH 3, 7, 9 ; T = 12, 25, 37, 60C in deionized water see no differences in solubility versus pH Telomer Iodide water solubility very low; have decided not to pursue further testing and focus on products Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 45 Release, Fate and Effects Compartments Release to Air Air Volatilization ? Sources wwtp Sludge Amendment Deposition Natur. Soil Grassland Agric. Soil Volatilization ? 25 Nov. 2002 Release to Water Sewer Direct Discharge Landfill Surface Water Freshwater Sediment Incineration Sea Estuary & Marine Sediment Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 46 Potential Environmental Routes of Entry 25 Nov.2002 Intermediates Surfactants Polymers Air Particle adsorbed or Fugitive emissions vapor phase? from WWTP? Soil Air Deposition Landfill Landfill Soil - Landfill Land applied sludge Land applied sludge Land applied sludge Sediment WWTP Air Deposition direct discharge WWTP direct discharge Direct discharge - point source Water WWTP & Septic direct discharge surface presence? WWTP & Septic direct discharge surface presence? WWTP & Septic Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 47 25 Nov. 2002 DuPont : Acute Environmental Effects Data Summary Telomer Alcohol Intermediate Telomer Phosphate Surfactant Telomer Ethoxylate Surfactant Telomer Urethane* Polymer Telomer Acrylate* Polymer Acute Fish mg/L 96Hr LC50 = 316 fathead minnow 96Hr LC50 > 1,000 rainbow trout 96Hr TL50 = 100-140 rainbow trout 96Hr LC50 > 4,000 fathead minnow 96Hr LC50 = 181 fathead minnow Acute Daphnid mg/L 48Hr EC50 = 965 Acute Algae mg/L 72Hr EC50 = 1,000 48Hr EC50 > 1,000 1Q2003 48Hr EC50 = 72 1Q2003 48Hr EC50 = 500-5,000 72Hr EC50 = 870 48Hr EC50 = 234 72Hr EC50 = 36.2 * tested as sales product including hydrocarbon surfactants Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 48 Aquatic Bioconcentration Screening Study Objective: To conduct screening studies evaluating the bioconcentration potential fluorotelomer-based products in fish Methods: Juvenile fathead minnows, flow-through design Test Substances (consistent F concentration) - Negative Control - Positive control : PFOS - Surfactants : Telomer Phosphate; Telomer Ethoxylate - Intermediate : Telomer Alcohol - Polymer : Telomer Urethane Stock concentrations and tissue residues analysis - (total Fluorine) - Uptake phase - days 0, 2, 5, 7, 9, 12, 14 - Depuration phase - days 16, 19, 21, 23, 26 28 In-life complete, data evaluation on-going (complete 1Q2003) Chemical Solutions Enterprise Company Sanitized. Does not contain TSCA CBI. AR-226 25 Nov. 2002 49 Telomer Phosphate Aquatic Chronic Fish (ELS) Toxicity Test 25 Nov. 2002 Objective: To determine a chronic LOEC (lowest observed effect concentration) and a chronic NOEC (no observed effect concentration). Methods: OECD TG 210, OPPTS 850.1400, (90-d trout ELS) Dose response - dilution water and solvent (IPA) controls, 0.63, 1.25, 2.5, 5, and 10 mg/L Telomer Phosphate (a complex mixture) Analytical confirmation of test concentrations Analysis by LC/MS Start Date : 8 November 2002 Est. Completion Date (in-life): 8 February 2003 Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 50 25 Nov. 2002 DuPont Fluorotelomer-based Products Environmental Effects Studies Timeline* Test Materials 8-2& 6-2 B, BA Multiple Compounds Intermediate, Surfactant and Polymer Phosphate Surfactant Ethoxylate Surfactant Acrylate Polymer Work Physical Properties Bioconcentration Factor (BCF) Screen (Fathead Minnow) I 2002 2003 1Q 2Q 3Q 4Q 1Q 2Q 3Q 4Q 90 Day Fish ELS (GLP) 72Hr Algae (GLP) 90 Day Fish ELS (GLP) 72Hr Algae (GLP) Acute Aquatic Study Set Work Complete Work Underway Work Planned * This is a proposed timeline and subject to change. Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 51 E-Fate Studies Approach 25 Nov. 2002 Intermediates Surfactants Abiotic Photolysis - Air Hydrolytic Stability Photolysis - Water Adsorption-Desorption Hydrolysis Aging / Sequestration Adsorption-Desorption (Kd) Aging / Sequestration Biotic Aerobic : Ready, Inherent Respiration Inhibition Anaerobic Aerobic : Ready, Inherent Polymers Hydrolytic Stability Respiration Inhibition Aerobic : Ready, Inherent Anaerobic ? Telomer Research Program 8-2 Telomer B Alcohol DuPont Focus on Products Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 52 25 Nov. 2002 Telomer-Based Surfactants & Polymers Abiotic Transformation : Hydrolytic Stability Surfactants Phosphate, Ethoxylate Polymers Urethane, Acrylate Reactions in water are one of the most common means of nonbiological degradation of substances in the environment. Aqueous stability tests should be performed at environmentally and biologically relevant pH's and temperatures. - pH 4, 7, 9 @ 50C - pH 1.2 @ 37C Four replicates at 0 and 5 Days Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 53 25 Nov. 2002 8-2 Telomer B Alcohol Biodegradation Studies "Ready" Biodegradability Screening "Inherent" Accelerated Biodegradability Screening "Cold" Study material Qualitative Identification & Analysis Enable method development Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 54 CATABOL Biodegradation Prediction C8F17CH2CH2OH 25 Nov. 2002 0.0% C8F17CH2CH2OH 75% C8F17CH2COOH 6.8% C7F15CF=CHCOOH 13.7% C7F15CF=CH2 1.2% C7F15C(O)COOH 3.3% C7F15COOH The sum of the % values = 100 The model predicts this will be the distribution of transformation products Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 55 25 Nov. 2002 Accelerated Biodegradation Screening Acclimated Municipal Sludge : C8F17CH2CH2OH (8-2TBA) Growth Medium: E2-BSMYE buffer and minerals plus 20 g/L yeast extract as organic nutrient. Incubated at room temperature (21-25C) Inoculum source: Municipal POTW (Incubated for 3 days) Conclusion Test material is transformed with adapted sludge 8-2 Telomer B Alcohol (ppb) Study Period : 3 Days 160 140 120 Control 100 Control 80 60 40 20 0 Medium + 8-2 TBA Medium + 8-2 TBA + o 4 C-Stored Sludge Medium + 8-2 TBA + Adapted Sludge Culture Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 56 25 Nov. 2002 Modified "Ready" Aerobic Biodegradation Screening with Non-acclimated Municipal Sludge : C8F17CH2CH2OH Growth medium: OECD 301D mineral medium + 4 mg/L yeast extract as organic nutrient Inoculum source: Municipal POTW, fresh sludge; non-acclimated (Incubated for 0 - 28 days) Conclusion Test material decreases No significant fluoride concentration increase ppb Study Period : 28 Days Fluoride 800 8-2 TBA 600 400 200 0 0 5 10 15 20 25 30 Days After the Initiation Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 57 25 Nov. 2002 Accelerated Aerobic/Anaerobic Biodegradation Screening Acclimated Industrial Sludge : C8F17CH2CH2OH 8-2 Telomer B alcohol (ppb) 8-2 TBA + Fresh Sludge 1200 CONTROL : 8-2 TBA, Sludge,2 mM NaCN 1000 Growth Medium: 800 E2-BSMYE (1 g/L yeast extract 600 as organic nutrient) 400 Inoculum source: 200 Industrial WWTP; acclimated 0 70 (28 days) 60 Extraction Efficiency (%): 50 115.8 11.0 40 (ppb) F- Conclusion Test material is readily transformed Significant fluoride formation 30 20 10 0 0 5 10 15 20 25 30 Days after the initiation Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 58 25 Nov. 2002 8-2 Telomer B Alcohol Biodegradation Screening Studies Summary Under modified "ready biodegradability" conditions, little defluorination occurred and C8F17CH2COOH appears to be the primary metabolite. Under modified accelerated conditions, transformation is rapid - Primary transformation products observed are : C8F17CH2COOH C7F15CF=CHCOOH Mass balance <50%; Other products/losses? On-going studies to understand controls, incomplete recoveries, and other transformation products Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 59 Telomer-based Surfactants & Polymers Biodegradation Studies Respiration Inhibition Test 25 Nov. 2002 Ready Biodegradation Screening Studies Ethoxylate and Phosphate Surfactants (OECD 301B, 28 days) Ready Biodegradation Screening Studies Acrylate and Urethane polymers (OECD 301B, 28 days) Yes No further Test Needed Chemical Solutions Enterprise Assess Ready Biodegradability No Modified Inherent Biodegradation (Modified OECD 302; 28-56 days) DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 60 Telomer-based Surfactants & Polymers Aerobic "Ready" Biodegradation 25 Nov. 2002 Measured End Points: Time course of CO2 evolution rate Time course of [F-] increase Total fluorine at the beginning and the end of the experiment Dissolved Organic Carbon (DOC) at zero (0) and 28 days Prework: - Total Organic Carbon (TOC) determination on test substance Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 61 25 Nov. 2002 DuPont Fluorotelomer-based Products Environmental Fate Studies Timeline* 2002 2003 Test Materials Work 1Q 2Q 3Q 4Q 1Q 2Q 3Q 4Q C8F17CH2CH2OH Respiration Inhibition "Ready" Biodegradation Screening "Inherent" Biodegradation Screening Telomer Hydrolytic Stability Phosphate Surfactant Respiration Inhibition Biodegradation Screening Telomer Hydrolytic Stability Ethoxylate Surfactant Respiration Inhibition Biodegradation Screening Telomer Urethane Hydrolytic Stability Polymer Respiration Inhibition Biodegradation Screening Telomer Acrylate Hydrolytic Stability Polymer Respiration Inhibition Biodegradation Screening Work Complete * This is a proposed timeline and subject to change. Work Underway Work Planned Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 62 Chemical Standards 25 Nov. 2002 To achieve quantitative precision in transformation studies Isotopically - Labeled Standards - M+5 : C7F1513CF2CD2CD2OH (internal standard) - M+2 : C6F1313CF213COOH "Cold" Standards - C8F17CH2COOH - C7F15CF=CHCOOH Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 63 25 Nov. 2002 DuPont Fluorotelomer-Based Products Product Stewardship Summary We have been proactive and diligent in meeting our commitments to better understand toxicity, environmental fate & effects and exposure. We are taking a comprehensive approach to understanding exposure. We are confident that our products are safe for their intended uses. We have programs in place to learn more about our products: Toxicology, Environmental Fate & Effect, Exposure We will continue to have an open & frequent dialogue with Regulators, Customers, and Employees Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 64 25 Nov. 2002 Reflections, Discussion, Questions Chemical Solutions Enterprise DoesConmotpcaonnytaSiannTitSizCeAd.CBI. AR-226 65