Search

The toxicokinetics of 6:2 fluorotelomer alcohol (6:2 FTOH) and its terminal perfluorinated and polyfluorinated metabolites (PFBA, PFHxA, PFHpA and 5:3 Acid) have been calculated from laboratory studies of rats and from a biomonitoring study of humans. In vitro studies with mouse, rat and human hepatocytes indicate qualitatively similar metabolic pathways of 6:2 FTOH. In a one-day inhalation study of 6:2 FTOH in rats, PFBA, PFHxA, PFHpA and 5:3 Acid were determined to be the major metabolites in plasma with calculated elimination half-lives of 1.3–15.4 h and metabolic yields up to 2.7 mol%. In five-day and 23-day inhalation studies and a 90-day oral study of 6:2 FTOH, the plasma or serum concentration profile of 5:3 Acid was several-fold higher than concentrations observed in the single day study, resulting in an estimated elimination half-life of 20–30 d. In contrast, the concentrations of PFBA, PFHxA and PFHpA showed little or no concentration increase with repeated exposure. Elimination half-lives of PFHxA, PFHpA and 5:3 Acid in humans were estimated from a study of professional ski wax technicians who were occupationally exposed to aerosolized and volatilized components of fluorinated glide wax. The resulting human elimination half-life values of PFHxA, PFHpA and 5:3 Acid were 32, 70 and 43 d, respectively. Based on a one compartment toxicokinetic model, current environmental air concentrations of 6:2 FTOH are estimated to result in plasma concentrations of PFHxA, PFHpA and 5:3 Acid that are less than or equal to typical LOQ values, in agreement with extant biomonitoring results. [ABSTRACT FROM AUTHOR]

Highlights: [•] Elimination half-life of PFHxA determined from blood of ski wax technicians. [•] Geomean human elimination half-life of PFHxA is 32d (range 14–49d). [•] Elimination half-life of PFHxA in mammalian species is proportional to body weight. [•] Rate of PFHxA elimination from mammals is useful for subsequent risk assessment. [ABSTRACT FROM AUTHOR]

A next-generation mobile automobile air-conditioning (MAC) refrigerant, HFO-1234yf (CF3CF = CH2), is being developed with improved environmental characteristics. In the atmosphere, it ultimately forms trifluoroacetic acid (TFA(A); CF3COOH), which is subsequently scavenged by precipitation and deposited on land and water as trifluoroacetate (TFA; CF3COO-). Trifluoroacetate is environmentally stable and has the potential to accumulate in terminal water bodies, that is, aquatic systems receiving inflow but with little or no outflow and with high rates of evaporation. Previous studies have estimated the emission rates of HFO-1234yf and have modeled the deposition concentrations and rates of TFA across North America. The present study uses multimedia modeling and geographic information system (GIS)-based modeling to assess the potential concentrations of TFA in terminal water bodies over extended periods. After 10 years of emissions, predicted concentrations of TFA in terminal water bodies across North America are estimated to range between current background levels (i.e., 0.01-0.22 µg/L) and 1 to 6 µg/L. After 50 years of continuous emissions, aquatic concentrations of 1 to 15 µg/L are predicted, with extreme concentrations of up to 50 to 200 µg/L in settings such as the Sonoran Desert along the California/Arizona (USA) border. Based on the relative insensitivity of aquatic organisms to TFA, predicted concentrations of TFA in terminal water bodies are not expected to impair aquatic systems, even considering potential emissions over extended periods. Environ. Toxicol. Chem. 2012; 31: 1957-1965. © 2012 SETAC [ABSTRACT FROM AUTHOR]

Abstract: This study is the first to evaluate the rate of formation of perfluorooctanoate (PFO) from the aerobic biodegradation of a fluorotelomer-based urethane polymer and to use this information to assess the global environmental significance of this source. A fluorotelomer-based urethane polymer product test substance was studied in four aerobic soils over two years to determine the rate at which the fluorotelomer side-chains covalently bonded to the polymer backbone were cleaved and subsequently transformed to form the anions of perfluorocarboxylic acids including PFO. Over the two year duration of the experimental study, a polymer biodegradation half-life of 102 years (range: 28–241) was calculated for the urethane polymer based on regression analysis of the rate of PFO formation in four test soils. When this half-life was applied to the estimated total historic production, use and disposal of fluorotelomer-based urethane polymer, the annual potential global generation of PFO was estimated to be less than one tonne per year. [Copyright &y& Elsevier]

Biodegradation of fluorinated polymers is of interest to assess them as a potential source of perfluorocarboxylates (PFCAs) in the environment A fluoroacrylate polymer product test substance was studied in four aerobic soils over two years to assess whether the fluorotelomer alcohol (FTOH) side chains covalently bonded to the polymer backbone may be transformed to form PFCAs. The test substance itself was not directly measured; instead, nine analytes were determined to evaluate biodegradation. Terminal biotransformation products measured included periluorooctanoate (PFO), perfluorononanoate (PFN), perfluorodecanoate (PFD), pertluoroundecanoate (PFU), and pentadecafluorodecanoate (7-3 acid). The molar concentration of 8-2 fluorotelomer alcohol (8-2 FTOH) in the test substance, fluoroacrylate polymer and residual unreacted raw materials and impurities ("residuals") were compared with the molar concentrations of the terminal biotransformation products for mass balance and kinetic assessments. Over the two year time frame of the experimental study, the fluoroacrylate polymer showed a slight extent of potential biodegradation under the experimental conditions of the study. A biodegradation half-life of 1200-1700 years was calculated for the fluoroacrylate polymer based on the rate of formation of PFO in aerobic soils. When the degradation rates of the fluoroacrylate polymer and residuals were applied to estimated total historic fluoroacrylate polymer production, use and disposal,the biodegradation of fluoroacrylate polymer and residuals is calculated to contribute less than 5 tonnes of PFO per year globally to PFCAs present in the environment. [ABSTRACT FROM AUTHOR]

Compares predictions of the pesticide root zone model (PRZM) 3.12 with measured data collected in nine different field leaching studies. Predictions of soil pore-water concentrations for pesticides for simulations based on the best choices for input parameters; Sensitivity of leaching to degradation rate.

Computer based simulation models are being used increasingly to predict the environmental fate of crop protection chemicals. Some considerations that should be given in selecting appropriate models for regulatory purposes include: model applicability, validation, capability, ease of use and documentation. Current applications of regulatory modeling include the rationalization of field data, evaluation of the leaching potential of pesticides and estimation of the probability of leaching. Problems commonly encountered in modeling include: limited accuracy, lack of defined objectives and standard modeling practices, and misuse of models and results. Models will continue to play an important role in the regulation of crop protection chemicals. It is important that regulators and industry agree on appropriate models and practices, and that regulatory decisions are not based solely on model results but take into account all available data. [ABSTRACT FROM PUBLISHER]

This work assessed the usefulness of a current air quality model (American Meteorological Society/Environmental Protection Agency Regulatory Model [AERMOD]) for predicting air concentrations and deposition of perfluorooctanoate (PFO) near a manufacturing facility. Air quality models play an important role in providing information for verifying permitting conditions and for exposure assessment purposes. It is important to ensure traditional modeling approaches are applicable to perfluorinated compounds, which are known to have unusual properties. Measured field data were compared with modeling predictions to show that AERMOD adequately located the maximum air concentration in the study area, provided representative or conservative air concentration estimates, and demonstrated bias and scatter not significantly different than that reported for other compounds. Surface soil/grass concentrations resulting from modeled deposition flux also showed acceptable bias and scatter compared with measured concentrations of PFO in soil/ grass samples. Errors in predictions of air concentrations or deposition may be best explained by meteorological input uncertainty and conservatism in the PRIME algorithm used to account for building downwash. In general, AERMOD was found to be a useful screening tool for modeling the dispersion and deposition of PFO in air near a manufacturing facility. [ABSTRACT FROM AUTHOR]

The environment contains various direct and indirect sources of perfluorooctanoic acid (PFOA). The present study uses a dynamic multispecies environmental fate model to analyze the potential formation of perfluorooctanoate (PFO), the anion of PFOA, in the environment from fluorotelomer acrylate polymer (FTacrylate) emitted to landfills and wastewater, residual fluorotelomer alcohol (8:2 FTOH) in FTacrylate, and residual PFOA in FTacrylate. A multispecies version of the SimpleBox model, which is capable of determining the fate of a chemical and its degradation products, was developed for this purpose. An uncertainty analysis on the chemical-specific input parameters was performed to examine for uncertainty in modeled concentrations. In 2005, residual 8:2 FTOH made up 80% of the total contribution of FTacrylate use to PFO concentrations in global oceans, and residual PFOA in FTacrylate contributed 15% to PFO concentrations from FTacrylate use in global oceans. After hundreds of years, however, the main source of PFO from total historical FTacrylate production is predicted to be FTacrylate degrading in soil following land application of sludge from sewage treatment plants, followed by FTacrylate still present in landfills. Uncertainty in modeled PFO concentrations was up to a factor of 3.3. Current FTacrylate use contributes less than 1% of the PFO in seawater, but because direct PFOA emission sources are reduced and PFOA continues to be formed from FTacrylate in soil and in landfills, this fraction grows over time. [ABSTRACT FROM AUTHOR]

This study reports on an investigation of the presence of polyfluorinated chemicals in a spatially and temporally integrated set of biological samples representing an Arctic food web. Zooplankton, Arctic cod, and seal tissues from the western Canadian Arctic were analyzed for perfluoroalkyl sulfonates [PFAS], perfluorocarboxylates [PFCAs], and other polyfluorinated acids. Perfluorooctane sulfonate [PFOS] was found in all samples [0.20–34ng/g] and in the highest concentrations. PFCAs from nine to 12 carbons were quantified in most of the samples [0.28–6.9ng/g]. PFCAs with carbon chain lengths of eight or less were not detected. Likewise, 8-2 fluorotelomer acid [8-2 FTA] and 8-2 fluorotelomer unsaturated acid [8-2 FTUA], products of fluorotelomer environmental transformation, were not detected. 2H,2H,3H,3H, heptadecafluoro decanoic acid [7-3 Acid], an additional metabolite from fluorotelomer biological transformation, was detected only in seal liver tissue [0.5–2.5ng/g]. The ratios of branched to linear PFOS isomers in fish and seal tissue were not similar and did not match that of technical PFOS as manufactured. No branched PFCA isomers were detected in any samples. It is concluded that differing pharmacokinetics complicate the use of branched to linear ratios of PFCAs in attributing their presence to a specific manufacturing process. A statistical analysis of the data revealed significant correlations between PFOS and the PFCAs detected as well as among the PFCAs themselves. The 7-3 Acid was not correlated with either PFCAs or PFAS, which suggests that it may have a different exposure pathway. [Copyright &y& Elsevier]

Abstract: 8:2 fluorotelomer alcohol (8:2 FTOH) inhalation exposure was investigated to (1) compare plasma metabolites to oral data, (2) conduct a route-to-route extrapolation (oral to inhalation), (3) develop a human equivalent air concentration (HEC) from a 90-day oral sub-chronic study in rats using BMD analysis, and (4) calculate a margin of exposure (MOE) between the HEC and measured air concentrations. Male and female rats were exposed nose-only for 6h at 3 or 30mg/m3. Blood was collected at 1, 3 and 6h during exposure and 6 and 18h post exposure. Alcohol, perfluorocarboxylic acid and polyfluorinated acid metabolites were determined in plasma by LC–MS/MS. 8:2 FTOH was

Perfluorinated acids, including perfluorinated carboxylates (PFCAs), and periluorinated sulfonates (PFASs), are environmentally persistent and have been detected in a variety of wildlife across the globe. The most commonly detected PFAS, perfluorooctane sulfonate (PFOS), has been classified as a persistent and bioaccumulative substance. Similarities in chemical structure and environmental behavior of PFOS and the PFCAs that have been detected in wildlife have generated concerns about the bioaccumulation potential of PFCAs. Differences between partitioning behavior of pertluorinated acids and persistent lipophilic compounds complicate the understanding of PFCA bioaccumulation and the subsequent classification of the bioaccumulation potential of PFCAs according to existing regulatory criteria. Based on available research on the bioaccumulation of periluorinated acids, five key points are highlighted in this review: (1) bioconcentration and bioaccumulation of periluorinated acids are directly related to the length of each compound's fluorinated carbon chain; (2) PFASs are more bioaccumulative than PFCAs of the same fluorinated carbon chain length; (3) PFCAs with seven fluorinated carbons or less (pertluorooctanoate (PFO) and shorter PFCAs) are not considered bioaccumulative according to the range of promulgated bioaccumulation,"B", regulatory criteria of 1000-5000 L/kg; (4) PFCAs with seven fluorinated carbons or less have low biomagnification potential in food webs, and (5) more research is necessary to fully characterize the bioaccumulation potential of PFCAs with longer fluorinated carbon chains (>7 fluorinated carbons), as PFCAs with longer fluorinated carbon chains may exhibit partitioning behavior similar to or greater than PFOS. The bioaccumulation potential of periluorinated acids with seven fluorinated carbons or less appears to be several orders of magnitude lower than "legacy" persistent lipophilic compounds classified as bioaccumulative. Thus, although many PFCAs are environmentally persistent and can be present at detectable concentrations in wildlife, it is clear that PFCAs with seven fluorinated carbons or less (including PFO) are not bioaccumulative according to regulatory criteria. [ABSTRACT FROM AUTHOR]

A high spatial and temporal resolution atmospheric model is used to evaluate the potential contribution of fluorotelomer alcohol (FTOH) and perfluorocarboxylate (PFCA) emissions associated with the manufacture, use, and disposal of DuPont fluorotelomer-based products in North America to air concentrations of FTOH, perfluorooctanoic acid (PFOA), and perfluorononanoic acid (PFNA) in North America and the Canadian Arctic. A bottom-up emission inventory for PFCAs and FTOHs was developed from sales and product composition data. A detailed FTOH atmospheric degradation mechanism was developed to simulate FTOH degradation to PFCAs and model atmospheric transport of PFCAs and FTOHs. Modeled PFCA yields from FTOH degradation agree with experimental smog-chamber results supporting the degradation mechanism used. Estimated PFCA and FTOH air concentrations and PFCA deposition fluxes are compared to monitoring data and previous global modeling. Predicted FTOH air concentrations are generally in agreement with available monitoring data. Overall emissions from the global fluorotelomer industry are estimated to contribute approximately 1–2% of the PFCAs in North American rainfall, consistent with previous global emissions estimates. Emission calculations and modeling results indicate that atmospheric inputs of PECAs in North America from fluorotelomer-based products will decline by an order of magnitude in the near future as a result of current industry commitments to reduce manufacturing emissions and lower the residual fluorotelomer alcohol raw material and trace PFCA product content. [ABSTRACT FROM AUTHOR]

The long-term (1950–2050) global fate of perfluorooctanoate (PFO) is investigated using the global distribution model, GloboPOP. The model is used to test the hypotheses that direct PFO emissions can account for levels observed in the global oceans and that ocean water transport to the Arctic is an important global distribution pathway. The model emission scenarios are derived from historical and projected PFO emissions solely from direct sources. Modeled ocean water concentrations compare favorably to observed PFO concentrations in the world's oceans and thus ocean inventories can be accounted for by direct sources. The model results support the hypothesis that long-range ocean transport of PFO to the Arctic is important and estimate a net PFO influx of approximately 8–23 tons per year flowing into the model's Northern Polar zone in 2005, an amount at least 1 order of magnitude greater than estimated PFO flux to the Arctic from potential indirect sources such as atmospheric transport and degradation of fluorotelomer alcohols. Modeled doubling times of ocean water concentrations in the Arctic between 1975 and 2005 of approximately 7.5–10 years are in good agreement with doubling times of PFO in Arctic biota estimated from monitoring data. The model is further applied to predict future trends in PFO contamination levels using forecasted (2005–2050) direct emissions, including substantial reductions committed to by industry. Modeled ocean water concentrations in zones near to sources decline markedly after 2005, whereas modeled concentrations in the Arctic are predicted to continue to increase until approximately 2030 and show no significant decrease for the remaining 20 years of the model simulation. Since water is the primary exposure medium for Arctic biota, these model results suggest that concentrations in Arctic biota may continue to rise long after direct emissions have been substantially reduced or eliminated. [ABSTRACT FROM AUTHOR]