<>EPA www.epa.gov Evaluating Per- and Polyfluoroalkyl Substances (PFAS) by In Vitro Toxicokinetic Data Generation with In Vitro-ln Vivo Extrapolation (IVIVE) Smeltz, M.a, Crizer, D. b, McMillan, L.a, Patlewicz, G.a, DeVito, M.a, Wetmore, B.A.a f ' a United States Environmental Protection Agency, Office of Research and Development, Research Triangle Park, North Carolina; b Division of the National Toxicology Program, National Institute of Environmental Health Sciences, Research Triangle Park, North Carolina Background New approach methodologies (NAMs) make use of in vitro high-throughput screening (HTS) data and in silico approaches to inform chemical safety assessment through the translation of bioactive in vitro assay concentrations to administered dose equivalents. This approach utilizes in vitro point of departure information from HTS studies where in vitro toxicokinetic (TK) data is applied to assigned administered dose equivalents, and to compare exposure estimates to define ad hoc margin of exposure. in vitro TK data and modeling -¥ in vivo concentrations ad hoc MOE Per- and polyfluoroalkyl substances (PFAS) have become chemicals of concern for human health as more is learned about their widespread presence and persistence in the environment. Given the inclusion of 1,220 PFAS on the Toxic Substances Control Act (TSCA) inventory, the availability of in vivo toxicologic data and exposure information on only a subset is inadequate to provide an understanding of the potential exposures, TK, and toxicities across this structurally diverse domain. To address this deficiency, we are applying NAMs to a panel of PFAS, containing carboxylic acid, sulfonate, and ether functionalities, for use in IVIVE models to predict systemic concentrations and eventual application in read-across approaches. In Vitro Toxicokinetic Assays • Human plasma (10-donor pool, mixed sex) centrifuged at 850,000xg to separate aqueous fraction from albumin, lipoproteins, and fatty acids • Analyte quantitation (multiple reaction monitoring, MRM) for aqueous fraction performed on Waters Xevo TQ-S (ultra-high- performance liquid chromatography-tandem mass spectrometry, UPLC-MS/MS) FU=AF/(T5) • Substrate depletion approach using primary human hepatocytes (50-donor pool, mixed sex) at 1 jjM PFAS concentration • Time course: 0, 15, 30, 60, 90, 120, and 240 min with non-linear regression fit to determine half-life (T1/2) • Single Ion Monitoring mode on Thermo * Vanquish with Q Exactive Plus / U.S. Environmental Protection Agency Office of Research and Development Determining Fraction Unbound by LC-MS/MS Fraction unbound (Fu) was determined by measuring PFAS concentration in aqueous fraction and plasma by Waters Xevo TQ-S micro (UPLC-MS/MS) in 6.5 min run with low ppb (pg/pL) sensitivity DTXSID3031864 PFOS DTXSID7027831 NMeFOSE Category-based Grouping and Distribution Analyses of PFAS Plasma Protein Binding Data cO.001 0.005 0.01 0.05 0.10 0.15 Fu Distribution Marci Smeltz I smelt2.marci@epa.gov I 919-541-1064 IVIVE Modeling Results IVIVE modeling was performed using collected in vitro Clhepatic and Fu data for a representative set of PFAS to predict steady-state blood concentrations (Css) for an adult population: Compound Name Fu Clrenal (L/hr) Clhepatic (L/hr) Css (nM) Potassium perfluorohexanesulfonate 0.0011 0.0075 3.82E-07 894.5132 Ammonium perfluorooctanoate 0.0014 0.0094 1.16E-04 713.7360 Perfluorononanoic acid 0.0013 0.0088 8.33E-03 368.6974 Perfluorohexanoic acid 0.0076 0.0507 2.33E-04 183.6569 Potassium perfluorobutanesulfonate 0.0087 0.0581 2.75E-02 101.5252 Perfluorooctanesulfonic acid 0.0073 0.0490 5.38E-02 57.1902 Perfluoro(4-methoxybutanoic) acid 0.0142 0.0950 2.97E-01 26.7545 Perfluorobutanoic acid 0.1032 0.6927 1.68E-05 19.8299 2H,2H,3H,3H-Perfluorooctanoic acid 0.0072 0.0483 5.15E-01 15.2577 Perfluoro-3,6,9-trioxatridecanoic acid 0.0026 0.0176 6.38E-01 7.9748 4:2 Fluorotelomer sulfonic acid 0.0142 0.0951 5.55E+00 1.5874 N-Ethylperfluorooctanesulfonamide 0.0464 0.3110 5.57E+00 0.9485 N-Methylperfluorooctanesulfonamide 0.0113 0.0757 7.43E+00 0.7633 Perfluorooctanesulfonamide 0.0229 0.1536 3.60E+01 0.1630 Assumptions: 1 pg/kg/day exposure, linear kinetics, 100% bioavailability, and nonmetabolic renal clearance only Summary .) are being measured on over 100 PFAS for Experimental in vitro toxicokinetic data (Fu and Clhe use in IVIVE modeling. Plasma protein binding data on 49 PFAS measured to date using UPLC-MS indicate high binding rates, with 75% exhibiting Fu values from 0.001 - 0.05. Preliminary category-based analyses of Fu values show perfluoroalkyl carboxylates have the greatest range, while other functional groups exhibit tighter distributions. Assuming an external exposure of 1 pg/kg/day, Css predictions ranged from 0.16-895 pM, with a median value of 23.29 pM. Half-life (T!4) estimates tracked similarly, with 50% of tested PFAS having T1/4 s < 100 hr and ~20% with VA values exceeding 1000 hr. Data generation across additional PFAS and toxicokinetic assays for bioavailability and renal reuptake are currently underway. Disclaimer: The views expressed in this poster are those of the authors and do not necessarily represent the views or policies of the U.S. Environmental Protection Agency. ------- |