Exposure Assessment And Risk Characterization
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Exposure Assessment And Risk Characterization






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Exposure Assessment And Risk Characterization Exposure Assessment And Risk Characterization Presentation Transcript

  • Exposure Assessment and Risk Characterization of Certain Fluoroorganic Chemicals Used in Food Packaging Stephen Korzeniowski , Robert C. Buck, Hsu-nan Huang, and Mary Kaiser 3rd International Symposium on Food Packaging Ensuring the Safety, Quality and Traceability of Foods 17-19 November 2004 Barcelona, Spain
  • Poster Abstract
    • The results of an exposure assessment and risk characterization study are reported for consumer paper food packaging articles manufactured with DuPont products. The goal was to develop a more in depth understanding of the magnitude of potential exposure to certain fluoroorganics that may occur through consumer use of commercial paper packaging.
    • An additional goal was to develop a risk characterization based on Margins of Exposure (MOE's) approach. Results from a variety of tested articles will be presented showing MOE's of all > 30,000. Paper packaging was one of the articles tested in this study.
    • Extraction studies were performed on paper packaging using a variety of solvents including water and ethanol and various cooking oils. Results from these studies as well as a review of the analytical challenges and significant method development efforts will be provided.
    • The implications of this body of work and path forward will also be discussed.
  • DuPont Fluorotelomer Product Groups: Intermediates, Surfactants, Polymers CF 2 =CF 2 (TFE) F(CF 2 CF 2 ) n I (Telomer A) F(CF 2 CF 2 ) n CH 2 CH 2 I (Telomer B) F(CF 2 CF 2 ) n CH 2 CH 2 OH ( Telomer BA ) Straight Chain Alkyl Sales Products F(CF 2 CF 2 ) n CH 2 CH 2 OC(O)C(R)=CH 2 Zonyl ® TM (R=CH 3 ) ; Zonyl ® TAN (R=H) n = 2-8
    • Surfactants
    • Anionic - Phosphate , Carboxylate, Sulfonate
    • Nonionic - Ethoxylate
    • Betaine
    • Polymers
    • Acrylic
    • Ester
    • Amide
    • Urethane
    • Urea
    Raw Materials 5 Test Compounds Represent Majority Product Line
  • How do they Work ?
    • The fluorotelomer functionality is attached to a functional backbone which adheres to the substrate surface.
    • The fluorocarbon chain orients perpendicular to the surface, at the air interface.
    • CF 3 Groups give very low surface tension
    • Oil, grease and water repellent surface
    CF 3 | (CF 2 ) n | (CH 2 ) 2 | Paper Substrate CF 3 | (CF 2 ) n | (CH 2 ) 2 | CF 3 | (CF 2 ) n | (CH 2 ) 2 | CF 3 | (CF 2 ) n | (CH 2 ) 2 | Backbone bulk paper properties are unaffected
  • Risk Characterization
    • Risk is a function of Hazard and Exposure
    • Hazard Assessment
      • Determine potential hazard(s) from toxicity testing linked to routes of exposure
    • Exposure Assessment
      • Routes of Exposure : Oral, Dermal, Inhalation
      • Determine how people come in contact with our products, how much & how often
    Risk = f (Exposure, Hazard)
  • Science-Based Product Stewardship Approach
    • Environmental Fate & Effects
    • Physical / chemical properties
    • Environmental compartments
    • Fate (abiotic & biotic)
    • Effects : aquatic, terrestrial
    • Exposure
    • Product Trails, Mass Balance
    • Human & Environmental
    • Exposure Assessment
    • Risk Characterization
    • Toxicology
    • Acute & Chronic Studies
    • Oral, Dermal, Inhalation
    • Pharmacokinetics
    Human Health Risk Assessment Environmental Risk Assessment
    • Analytical
    • Product & Substrate Analysis
    • Method Development and Validation
    • Chemical “Standards”
    • External Labs
    Academic Collaboration
    • Communication
    • Publications
    • Presentations
    • Manufacturing Technology
    • Process Improvements
    • Facilities Re-engineering
    • Emissions Reduction
    DuPont Chemical Solutions Enterprise d Product Stewardship Business Process
  • Product Stewardship Through the Entire “Life-Cycle” DuPont Manufacturing Industrial Processing Professional Use/Installation Consumer Use Disposal
  • Scope of the Exposure Assessment and Risk Characterization: Consumer Article Study DuPont Manufacturing Industrial Processing Professional Use/Installation Consumer Use Disposal
    • Focus of the Assessment:
    • Direct use of the article;
    • Home fabrication using the article;
    • Incidental exposure to the article;
    • Care and maintenance of the article; and,
    • Foreseeable misuse of the article.
  • Exposure Assessment and Risk Characterization Work Process Conceptualize Exposure Quantify Exposure Develop Risk Characterization Conduct Peer Review Issue Final Report Develop Hazard Assessment Analytical Data
  • Articles Included in the Assessment
    • Quantitative Evaluation of:
    • Medical garments
    • Carpeting
    • Carpet care products
    • Textiles (Apparel)
    • Thread sealant tape
    • Cookware
    • Membranes (Apparel)
    • Food Contact Paper
    • Quantitative Evaluation (Ingredients-basis) of:
    • Stone, tile and wood sealants
    • Industrial floor waxes and wax removers
    • Latex paint
    • Home and office cleaning products
    • Textiles (Upholstery)
    • Textiles (Home)
    • Textiles (Technical)
  • Food-Contact Paper Types
    • Linerboards
    • Folding Cartons
    • Bags
    • Flexible Packaging
    • Support Cards
  • Food-Contact Paper : Conceptual Exposures
    • Exposure Pathways Quantified
      • Dermal Contact
      • Ingestion via Hand-to-Mouth
      • Ingestion of Food
    • Exposure Pathway dealt with as Uncertainty
      • Paper Mouthing
  • Food Exposure Factors: Examples
    • Dermal
    • Mass Available for transfer ng/cm 2
    • Fraction Transferred
    • Skin Surface Area
    • Dermal Absorption Coefficient
    • Exposure Time to Perspiration
    • Exposure Frequency (events/day)
    • Hand-to-Mouth
    • Mass Available for transfer ng/cm 2
    • Fraction Transferred
    • # Contact Events
    • Saliva Transfer Factor
    • Oral Absorption factor
    • Ingestion of Food
    • Mass Available for Transfer
    • Fraction Transferred
    • Contact Area: Paper-Food
    • Food Consumption Rate
    • Fraction of Consumed Food in Contact with paper
    • Exposure Frequency/Duration
    • Oral Absorption Factor
    • Vapor Inhalation
    • Various Rates and Exposure Factors - Time, Frequency, Duration
  • Risk Characterization Margins of Exposure
    • Ratios of estimated human exposure levels to relevant health benchmarks
    • Calculated separately for each article, each endpoint, and each receptor
    • Aggregate MOE calculated to consider multiple-article exposure
    Applicable Health Benchmark Estimated Human Exposure MOE =
  • Overall Results and Conclusions
    • Based on the exposure assessment and risk characterization:
      • Margins of exposure (MOEs, or “safety ratio) for all articles tested ranged from 30,000 to 9 billion for R easonable M aximum E xposure scenarios (highly conservative)
      • DuPont paper and packaging products had MOEs all >100,000
    • The study reaffirms that our products are safe for their intended uses
  • Analytical Development and Characterization of Fluoroorganic Species in Food Packaging
    • Develop a representative recovery analytical procedure for perfluorooctanoic acid (PFOA) in various oil matrixes
      • goal to develop method suitable primarily for microwave packaging testing
    • Construct a sensitive, specific and rugged analytical method for quantifying PFOA or its methyl ester (PFOME)
    • Perform recovery analyses of PFOA/PFOME in fractionated coconut oil (MIGLYOL), silicone oils, corn oil, and olive oil
      • at room temperature and at 232 o C for 5 minutes
  • Recovery Analytical Procedure
    • Spike a 1g oil sample with known concentrations of PFOA in acetone
    • For room temperature recovery skip to next step, for 232 o C recovery heat sample vials in an oven to temperature for 5 minutes
    • Add 1mL of methanolic HCl to esterify PFOA to PFOME. Heat to 60 o C for 30 minutes
    • Extract organic layer and analyze via GC/MS.
  • Analytical Detection Procedure
    • Quantify the extracted PFOME by gas chromatography / mass spectrometry (GC/MS) technique
    • Acquire heightened sensitivity through the use of chemical ionization, negative mode (NCI)
    • Selectivity is produced by the selected ion monitoring (SIM) option
    • Quantify analyte with external standard calibration
    • Draft analytical method has a demonstrated limit of detection (LOD) of 1 ppb and a limit of quantitation of 5 ppb
  • Equipment and Supplies: Oil Studies Agilent GC 6890N US10206015 Agilent MSD 5973Network US10482241 Agilent Autosampler/Injector 7683 US20414158 CN14523138 Edwards vacuum pump G1099-80023 Agilent Enhanced ChemStation Version D.00.00.38 DB-1ms 30m X 0.25mm X 0.25µm capillary column Ultra High Purity helium carrier gas MG Industries Ultra High Purity methane reagent gas MG Industries Mettler AE 163 analytical balance 86796 Acetone EM Science HR-GC AX0110-1 Hydrogen Chloride, Methanol Reagent 10 TCI America X0041 Methyl perfluorooctanoate, Oakwood Products, Inc. (98%) 002278 lot # T19L Acetonitrile, EMD Chromo. grade AX0142-1 Hexanes, EM Science Chromo. grade HX0298-6 MILLI-Q water
  • Representative External Standard Calibration Curve PFOME Standards range from 1.2 ppb to 120 ppb .
  • PFOME Recovery Results: Oil Matrices
  • PFOA Oil Recovery Result Summary
    • MIGLYOL room temperature experiment produced acceptable recoveries between 70% to 120%
    • MIGLYOL at 232 o C for 5 minutes experiment produced significantly lower recoveries between 0% to 49%
    • Both Silicone Oils tested at room temperature and elevated temperature produced negligible recoveries
    • Corn oil at room temperature yield 3-5% recoveries and at 232 o C yield even lower (0.5-1%) recoveries
    • Olive oil at room temperature yield 8-12% recoveries and 0-40% recoveries at elevated temperature
    • Conclusion
    • Use of the oils tested to conduct paper and packaging extraction analyses for PFOA is unlikely to provide a meaningful result due to unacceptably low recoveries
      • It appears that the PFOA is reacting with the subject oils and therefore preventing appropriate recovery
  • Food Simulant Extraction Studies
    • Ethanol solutions explored as food simulants for paper extraction studies to determine potential PFOA levels in paper and packaging
    • Tested both 10% and 50% Ethanol solutions
    • Although not as desirable, determine if these simulants can be used as a surrogate for oil extractants/simulants
    • Other analytes were also considered in this study
  • PFOA Analyses in Paper: Ethanol Simulants
    • LC/MS/MS for sensitivity and selectivity
    • Require 5x signal to background at LOQ
      • Minimize sample contact with fluoropolymers
        • HPLC parts and tubing
        • Autosampler vial caps
    • 13 C-PFOA dual isotopic internal standard corrects for matrix effects
  • Shaker Sample Preparation Paper Sample Subsample #1 1 gram Subsample #2 1 gram Extract 2 Hrs Centrifuge Vial #1 Vial #2 Spike Extract 2 Hrs Centrifuge Vial #1 Vial #2 Spike
  • Experimental Conditions
    • Sciex API 4000 (Multiple Reaction Monitoring Mode)
      • PFOA (413 to 369 m/z)
      • Dual 13 C PFOA IS (415 to 370 m/z)
    • HPLC Agilent 1100
      • Genesis C8 Column (2.1 mm x 50 mm, 4 um particle 120 Angstom)
      • Mobile Phase A: 2 mMolar ammonium acetate in nanopure H2O
      • Mobile Phase B: Methanol
      • 10 uL Injection Volume
      • Isocratic at 65% solvent B
      • PFOA Peak Elution 1.0 minute
  • PFOA Calibration Curve 50% EtOH PFOA Standard Concentration (ng/mL) 13 - C - PFOA Internal Standard Concentration (ng/mL) Average PFOA Area Response (413 > 369 transition) Average 13 C - PFOA Internal Standard Area Response (415 > 370 transition ) 0.1 5.00 75093. 2781000. 0.5 5.00 322430. 2745900. 1.0 5.00 629740. 2794800. 5.0 5.00 2854000. 2707400. 20.0 5.00 5366700. 2545000.
  • Example Chromatogram (LLOQ Standard) 0.1 ng/mL PFOA 5.0 ng/mL 13 C-PFOA IS
  • PFOA Method Validation in Paper Simulants Three treated paper samples fortified in triplicate at each level
  • Food Simulant Extraction Studies
    • Ethanol solutions explored as food simulants for paper extraction studies
    • Tested both 10% and 50% Ethanol solutions
    • Conclusion
    • Methods have been developed to readily use ethanol/water mixtures as food simulants for the determination of PFOA in food packaging
    • An LOQ of 100 ppt and an LOD of 10 ppt were established in these matrices
  • Environmental Compartments Under Study Sources Sewer Air wwtp Agric. Soil Surface Water Freshwater Sediment Sea Estuary & Marine Sediment Natur. Soil Grassland Landfill Incineration Focus Areas
  • E-Fate Studies Approach Studies are underway. Biotic results are expected during the 1Q-4Q 2005 time period
  • Acknowledgments
    • Mike Mawn
    • Miguel Botelho
    • Barbara Larsen
    • Rhea Holtzman