Document DMBKpV0jrYbXovebNOZaEgYvB

AMG - iiH-7 DuPont Fluorotelomer Product Stewardship Update 25 Nov. 2002 Presented to The United States Environmental Protection Agency November 25, 2002 z? T. S. Bingman, R. C. Buck, S. H. Korzeniowski, J. C. Stadler Chemical Solutions Enterprise Company Sanitized. Does not contain TSCA CBI. AR-226 Company Sanitized 1 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 Environmental Fate & Effects Physical / chemical properties Environmental compartments Fate (abiotic & biotic) Effects : aquatic, terrestrial 14C Labeled Material DuPont CCER E nvironm en tal Risk Assessment input Exposure Product Trails Mass Balance Human & Environmental Exposure Assessment Risk Characterization DuPont CRG Chemical Solutions Enterprise Company Sanitized. Does not contain TSCA CBI. AR-226 3 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 DUPONT \ y e a r s Chemical Solutions Enterprise Company Sanitized. Does not contain TSCA CBI. AR-226 4 25 Nov. 2002 DuPont Fluorotelomer Product Groups: Intermediates, Surfactants, Polymers 1) Intermediates CF2=CF2 (TFE) Sales Products F(CF2CF2)nI (Telom er A) n = 2-8 F(CF2CF2)nCH2CH2I (Telom er B) 2) Surfactants / "Molecules" Anionic - Phosphate, Carboxylate, Sulfonate Nonionic - Ethoxvlate Betaine F(CF2CF2)nCH2CH2OH (Telomer BA) Straight Chain Alkyl F(CF2CF2)nCH2CH2OC(O)C(R)=CH2 Zonyl TM (r=ch3) ; Zonyl T A N (r=h) 3) Polymers Acrylic Ester Amide Urethane Urea 5 Test Compounds Represent Large Per Cent of Product Line Chemical Solutions Enterprise Company Sanitized. Does not contain TSCA 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 Company Sanitized. Does not contain TSCA CBI. AR-226 6 DuPont Toxicology Studies Timeline* 25 Nov. 2002 DUPONT years Test Material Telomer Urethane Polymer Telomer BA Intermediate Telomer Ethoxylate Surfactant Telomer Phosphate Surfactant Telomer Acrylate Polymer Work 90 Day Oral Repeat Dose, 1Gen Repro (Rat) Developmental Study (Rat) Dermal Permeation (Rat) 90-Day Follow-Up 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) 90 Day Range Finding 90 Day Oral Repeat Dose,1Gen Repro (Rat) Developmental Study Rangefinder Developmental Study (Rat) 90 Day Range Finding 90 Day Oral Repeat Dose (Rat) 1Gen Reproduction Study (Rat) Developmental Range Finder Developmental Study (Rat) 28 Day Dermal Repeat Dose (Rat) 14-Day Inhalation Repeat Dose (Rat) 90-Day Range Finding 90 Day Oral Repeat Dose,1Gen Repro (Rat) Developmental Study Rangefinder Developmental Study (Rat) Work Complete Work Underway Projected Timing Chemical Solutions Enterprise * This is a proposed timeline and subject to change. Company Sanitized. Does not contain TSCA CBI. AR-226 7 DuPont Toxicity Studies : Rat Model Multiple Routes of Exposure 25 Nov. 2002 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 Company Sanitized. Does not contain TSCA CBI. AR-226 8 Intermediate : Telomer BA Study Summary & Timeline 25 Nov. 2002 F ( C F 2 C F 2) nC H 2C H 2 O H 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 113Q 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 9 Polymer: Telomer Urethane Study Summary & Timeline 25 Nov. 2002 F ( C F 2C F 2) nC H 2C H 2O H ( T e l o m e r B A ) n = 3 _6 Straight Chain Alkyl ^ Telomer Urethane Polymer Aqueous Dispersion with surfactant Test Material Telomer Urethane Polymer Work 90 Day Oral Repeat Dose + 1Gen Repro (Rat) Developmental Study (Rat) Dermal Permeation (Rat) Nasal Lesion - Follow-Up Study 2003 Q2Q3Q4Q1Q2Q3Q4Q 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 Company Sanitized. Does not contain TSCA 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 Company Sanitized. Does not contain TSCA 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 Company Sanitized. Does not contain TSCA CBI. AR-226 12 25 Nov. 2002 Static Diffusion Cell : In Vitro Dermal Permeation Saline receptor fluid Chemical Solutions Enterprise Company Sanitized. Does not contain TSCA CBI. AR-226 13 Polymer: Telomer Urethane In-vitro Dermal Permeation 25 Nov. 2002 Methods - 20 pl product solution was applied to rat epidermal membrane - Total of 1234 pg 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 Company Sanitized. Does not contain TSCA CBI. AR-226 14 25 Nov. 2002 Aqueous emulsion polymerization of monomer composition : - F(CF2CF2)nCH2CH2OC(O)CH=CH2 n = 4 - 6 CBI Information has been redacted - 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 Company Sanitized. Does not contain TSCA 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 Company Sanitized. Does not contain TSCA 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 Company Sanitized. Does not contain TSCA CBI. AR-226 17 Polymer: Telomer Acrylate Study Summary & Timeline 25 Nov. 2002 Test Material Telom er Acrylate Polymer Work 90-Day Range Finding 90 Day Oral Repeat Dose,1Gen Repro (Rat) Developmental Study Rangefinder Developmental Study (Rat) Work Complete 4Q Work Underway 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 Company Sanitized. Does not contain TSCA CBI. AR-226 18 Surfactant : Telomer Phosphate _______ Chemistry_______ 25 Nov. 2002 F(CF2CF2)nCH2CH2OH (Telomer BA) n = 3 - 6 P2O5, H2O, isopropanol, NR3 [F(CF2 CF2 )n CH2 CH2 O]x P(O)(ONR3 H)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 19 25 Nov. 2002 Test Material Telomer Phosphate Surfactant Surfactant : Telomer Phosphate Timeline 2000 2001 2002 2003 Work 3Q 4Q 1Q2Q 3Q4Q 1Q2Q3Q4C 1Q2Q3Q4Q 90-Day Range Finding 90 Day Oral Chronic Repeat Dose (Rat) 1Gen Reproduction Study (Rat) Developm ental Range Finder Developmental Study 28 Day Dermal Repeat Dose (Rat) 14 Day Inhalation Repeat Dose (Rat) 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 Company Sanitized. Does not contain TSCA CBI. AR-226 20 Surfactant : Telomer Phosphate Toxicology Information Acute Toxicity* Oral Rat: Inhalation Rat: Skin Irritation: Eye Irritation: Sensitization: ALD > 17,000 mg/kg; LD50> 25,000 mg/kg 4 hr: ALC = 57 mg/m3 Not a skin irritant Minimal irritant 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% * studies conducted on 35% active test material containing isopropanol Chemical Solutions Enterprise Company Sanitized. Does not contain TSCA CBI. AR-226 21 25 Nov. 2002 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 (20% a.i.; no isopropanol) Reproductive Toxicity : Report in Progress Dose Levels : 75, 500, 3500 mg/kg/day Developmental Toxicity : Report in Progress Dose Levels : 625, 1250, 2500 mg/kg/day Chemical Solutions Enterprise Company Sanitized. Does not contain TSCA CBI. AR-226 22 Surfactant : Telomer Phosphate * 25 Nov. 2002 90 Day Oral Study Results Study Conclusion: Female (F) : NOEL = 60 mg/kg/day 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) * material containing isopropanol NOTE: Minimally elevated Beta Oxidation at 60 and 300 mg/kg/day Chemical Solutions Enterprise Company Sanitized. Does not contain TSCA 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 Company Sanitized. Does not contain TSCA 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 Company Sanitized. Does not contain TSCA 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 Company Sanitized. Does not contain TSCA 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 Company Sanitized. Does not contain TSCA CBI. AR-226 27 Fluorotelomer Products Repeated-Dose Study Observations 25 Nov. 2002 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 Company Sanitized. Does not contain TSCA CBI. AR-226 28 25 Nov. 2002 Hazard Assessment Example - "Reference Dose This translates the animal data to a proposed "safe" human exposure level 10A: Animals to Humans Animal Model Toxicity Testing 10S: Chronic vs. Subchronic LOEL* = 50 mg/kg/day Telomer Urethane * expect NOEL to be near this value **Using the highest value o f uncertainty factor range (1-10) DUPONT y e a r s Chemical Solutions Enterprise // V * 10H: Human Variability Human Criterion `Reference Dose" = 0.05 mg/kg/day Company Sanitized. Does not contain TSCA CBI. AR-226 29 25 Nov. 2002 Risk Assessment Framework Characterize Fate & Transport Properties Release Estimate Characterize Distribution in the Environment fHuman Health Population Exposure i Exposure Assessment 1 Non -Hum an Population Exposure Direct Use / Release Exposure Measure Predict Estimated Human Toxicity i Hazard Assessment DUPONT y e a r s Chemical Solutions Enterprise RISK ASSESSMENT Human Health Ecological Measure Predict Estimated EcoToxicity Risk Management Decisions Company Sanitized. Does not contain TSCA CBI. azard 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? O Risk Characterization Chemical Solutions Enterprise Company Sanitized. Does not contain TSCA CBI. AR-226 31 Exposure Assessment Overview 25 Nov. 2002 P o te n tia lly Exposed S u b p o p u la tio n C onsum er Food W rap Paper * Ingestion C a rp e ts * D erm al * Indirect In g e s tio n Apparel * D erm al P o te n tia lly Exposed S u b p o p u la tio n O c c u p a tio n a l M edical W o rk e r G arm ent W orker P a in te r C ustodial W o rke r Chemical Solutions Enterprise M e d ic a l Fabric P a in ts C le a n in g Products * D erm al * D erm al * D erm al * Inhalation * D erm al Company Sanitized. Does not contain TSCA CBI. AR-226 32 CBI Information has been redacted 25 Nov. 2002 CBI Information has been redacted Chemical Solutions Enterprise Company Sanitized. Does not contain TSCA CBI. AR-226 33 CBI Information has been redacted 25 Nov. 2002 CBI Information has been redacted Chemical Solutions Enterprise Company Sanitized. Does not contain TSCA CBI. AR-226 34 Critical Exposure Variables CBI Information has been redacted 25 Nov. 2002 Developed point estimates for all necessary variables: - (1) C o n cen tratio n o f telo m er u reth an e - (2) L oss o f p o ly m er o v er tim e - (3) E x p o su re p erio d - (4) S kin su rface area - (5) D erm al tran sfer co efficien t - (6) B o d y w eig h t - (7) F o o d surface area - (8) B io av ailab ility o f the telo m er u reth an e Also developed probabilistic inputs for key parameters in the analysis: Chemical Solutions Enterprise Company Sanitized. Does not contain TSCA CBI. AR-226 35 CBI Information has been redacted 25 Nov. 2002 CBI Information has been redacted Chemical Solutions Enterprise Company Sanitized. Does not contain TSCA CBI. AR-226 36 CBI Information has been redacted 25 Nov. 2002 CBI Information has been redacted Chemical Solutions Enterprise Company Sanitized. Does not contain TSCA CBI. AR-226 37 CBI Information has been redacted 25 Nov. 2002 CBI Information has been redacted Chemical Solutions Enterprise Company Sanitized. Does not contain TSCA CBI. AR-226 38 CBI Information has been redacted 25 Nov. 2002 CBI Information has been redacted Chemical Solutions Enterprise Company Sanitized. Does not contain TSCA CBI. AR-226 39 CBI Information has been redacted 25 Nov. 2002 CBI Information has been redacted Chemical Solutions Enterprise Company Sanitized. Does not contain TSCA CBI. AR-226 40 CBI Information has been redacted 25 Nov. 2002 CBI Information has been redacted Chemical Solutions Enterprise Company Sanitized. Does not contain TSCA CBI. AR-226 41 CBI Information has been redacted 25 Nov. 2002 CBI Information has been redacted Chemical Solutions Enterprise Company Sanitized. Does not contain TSCA CBI. AR-226 42 Exposure Assessment Summary 25 Nov. 2002 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 Company Sanitized. Does not contain TSCA 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 : A cu te D ata, B C F S creen , C h ro m ic F ish E L S - Environmental Fate In term ed iate S u rfactan ts P o ly m ers Chemical Solutions Enterprise Company Sanitized. Does not contain TSCA CBI. AR-226 44 25 Nov. 2002 Physical - Chemical Properties : Water Solubility 6-2, 8-2 Telomer B Alcohols & Iodides 12C Solubility 25C 37C 60C C 6 F 13C H 2C H 2OH 12 ppm 17 ppm C8F17CH2CH2OH 130 + 30 ppb 140 + 50 ppb 318 + 176 ppb 225 + 50 ppb C 6 F 13C H 2C H 2 I 9 ppb C 8 F 17C H 2C H 2 I < 10 ppb (LOQ) p H 3, 7, 9 ; T = 12, 25, 37, 6 0 C in d eio n ized w a ter see n o d ifferen ces in so lu b ility v ersu s p H T elo m e r Io d id e w a ter so lu b ility v ery low ; h av e d ecid ed n o t to p u rsu e fu rth er testin g and fo cu s on p ro d u cts Chemical Solutions Enterprise Company Sanitized. Does not contain TSCA CBI. AR-226 45 Release, Fate and Effects Compartments Release to Air Volatilization ? Sources wwtp Sludge Amendment Deposition Natur. Soil Grassland Agric. Soil Volatilization ? 25 Nov. 2002 Release to Water ----------------------- Landfill Direct Discharge a Surface Water _ J ___ Freshwater Sediment Incineration Sea _____ * _____ Estuary & Marine Sediment DUPONT y e a r s Chemical Solutions Enterprise Company Sanitized. Does not contain TSCA CBI. AR-226 46 Potential Environmental Routes of Entry 25 Nov. 2002 A ir Soil Interm ediates Particle adsorbed or vapor phase? Surfactants Fugitive em issions from W W TP? P o lym ers Air Deposition Soil - Landfill Land applied sludge Landfill Land applied sludge Landfill Land applied sludge Sedim ent WWTP Air Deposition direct discharge WWTP direct discharge Direct discharge - point source W ater W W TP & Septic direct discharge surface presence? W W TP & Septic direct discharge surface presence? W W TP & Septic Chemical Solutions Enterprise Company Sanitized. Does not contain TSCA CBI. AR-226 47 25 Nov. 2002 DuPont : Acute Environmental Effects Data Summary Telo m er A lcohol Interm ediate Telom er Phosphate S u rfa c ta n t T elo m er E thoxylate S u rfa c ta n t Telom er U rethane* Polym er T elo m er A crylate* Polym er A cute Fish mg/L 96H r LC 50 = 316 fathead minnow 96H r LC 50 > 1,000 rainbow trout 96H r TL50 = 100-140 rainbow trout 96H r LC 50 > 4,000 fathead minnow 96H r LC 50 = 181 fathead minnow A cute D aphnid mg/L 48H r E C 50 = 965 A cute A lgae mg/L 72H r E C 50 = 1,000 48H r E C 50 > 1,000 1Q2003 48H r E C 50 = 72 1Q2003 48H r E C 50 = 500-5,000 72H r EC 50 = 870 48Hr EC50 = 234 72Hr EC50 = 36.2 * tested as sales product including hydrocarbon surfactants Chemical Solutions Enterprise Company Sanitized. Does not contain TSCA CBI. AR-226 48 25 Nov. 2002 O bjective: To conduct screening studies evaluating the bioconcentration potential fluorotelomer-based products in fish M ethods: Juvenile fathead minnows, flow-through design Test Substances (consistent F concentration) - N eg ativ e C o n tro l - P o sitiv e co n tro l : P F O S - S u rfactan ts : T elo m er P h o sp h ate; T elo m er E th o x y late - In term ed iate : T elo m er A lco h o l - P o ly m er : T elo m er U reth an e Stock concentrations and tissue residues analysis - (total Fluorine) - U p tak e phase - days 0, 2, 5, 7, 9, 12, 14 - D ep u ratio n 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 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 Company Sanitized. Does not contain TSCA CBI. AR-226 50 DuPont Fluorotelomer-based Products Environmental Effects Studies Timeline* 25 Nov. 2002 Test Materials 8-2& 6-2 B, BA Multiple Compounds Intermediate, Surfactant and Polymer Phosphate Surfactant Ethoxylate Surfactant Acrylate Polym er W ork Physical Properties Bioconcentration Factor (BCF) S creen (Fathead Minnow) I I2002 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 - 1 Work Planned * This is a proposed timeline and subject to change. Chemical Solutions Enterprise Company Sanitized. Does not contain TSCA 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 Company Sanitized. Does not contain TSCA 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 non biological 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 -p H 1.2 @ 37C Four replicates at 0 and 5 Days Chemical Solutions Enterprise Company Sanitized. Does not contain TSCA CBI. AR-226 53 8-2 Telomer B Alcohol Biodegradation Studies "Ready" Biodegradability Screening "Inherent" Accelerated Biodegradability Screening "Cold" Study material Qualitative Identification & Analysis Enable method development 25 Nov. 2002 Chemical Solutions Enterprise Company Sanitized. Does not contain TSCA CBI. AR-226 54 25 Nov. 2002 The sum o f the % values = 100 The m odel predicts this w ill be the distribution o f transform ation products Chemical Solutions Enterprise Company Sanitized. Does not contain TSCA CBI. AR-226 55 25 Nov. 2002 Accelerated Biodegradation Screening A cclim ated M unicipal S ludge : C8F 17C H 2C H 2OH (8-2T B A ) Growth Medium: E 2-B S M Y E buffer and m in erals p lu s 20 g /L y east ex tract as o rg an ic n u trien t. In cu b ated at room tem p eratu re (21-25C ) Inoculum source: M u n icip al P O T W ( I n c u b a t e d f o r 3 d a y s ) * Conclusion Test material is transformed with adapted sludge 0I0 160 IS) 140 Study Period : 3 Days 120 100 03 80 n>o 60 o 40 a 20 a U" 0 Medium + 8-2 TBA Medium + 8-2 TBA + 4 C-Stored Sludge Medium + 8-2 TBA + Adapted Sludge Culture Chemical Solutions Enterprise Company Sanitized. Does not contain TSCA CBI. AR-226 56 25 Nov. 2002 Modified "R eady" Aerobic Biodegradation Screening with N on-acclim ated M unicipal S lu d g e : C8F 17C H 2C H 2OH Growth medium: O E C D 301D m in eral m ed iu m + 4 m g /L y e a st ex tract as o rg an ic n u trien t Inoculum source: M u n icip al P O T W , fresh sludge; n o n -acclim ated (In cu b ated fo r 0 - 28 days) Conclusion Test material decreases No significant fluoride concentration increase - 800 600 _Q Q_ 400 200 0 Study Period : 28 Days I---- 1---- 1---- r- Fluoride o 8-2 TBA 0 5 10 15 20 25 Days After the Initiation 30 DUPONT y e a r s Chemical Solutions Enterprise Company Sanitized. Does not contain TSCA CBI. AR-226 57 25 Nov. 2002 Accelerated Aerobic/Anaerobic Biodegradation Screening A cclim ate d Industrial S ludge : C8F 17C H 2C H 2OH 0 8-2 TBA + Fresh Sludge 0 CONTROL : 8-2 TBA, Sludge,2 mM NaCN 00 Growth Medium: E 2 -B S M Y E (1 g /L y e a s t e x tra c t as o rg an ic n u trien t) Inoculum source: In d u strial W W T P ; acclim ated (28 days) Extraction Efficiency (%): 1 1 5 .8 11.0 Conclusion Test material is readily transformed Significant fluoride formation 0 5 10 15 20 25 Days after the initiation 30 Chemical Solutions Enterprise Company Sanitized. Does not contain TSCA CBI. AR-226 58 25 Nov. 2002 Under modified "ready biodegradability" conditions, little de fluorination occurred and C8F17CH2COOH appears to be the primary metabolite. Under modified accelerated conditions, transformation is rapid -- Primary transformation products observed are : C8F17CH22COOH C7F15CF=CHCOOH Mass balance <50%; Other products/losses? On-going studies to understand controls, incomplete recoveries, and other transformation products Chemical Solutions Enterprise Company Sanitized. Does not contain TSCA CBI. AR-226 59 25 Nov. 2002 Telomer-based Surfactants & Polymers Aerobic "Ready" Biodegradation 25 Nov. 2002 Measured End Points: Time course of CO2evolution 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 Company Sanitized. Does not contain TSCA CBI. AR-226 61 DuPont Fluorotelomer-based Products Environmental Fate Studies Timeline* 25 Nov. 2002 Test Materials C8 F17CH2 CH2 OH Work 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 Work Underway * This is a proposed timeline and subject to change. Work Planned Chemical Solutions Enterprise Company Sanitized. Does not contain TSCA 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 Company Sanitized. Does not contain TSCA 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 Company Sanitized. Does not contain TSCA CBI. AR-226 64 25 Nov. 2002 Reflections, Discussion, Questions Chemical Solutions Enterprise Company Sanitized. Does not contain TSCA CBI. AR-226 65