Extending the knowledge about PFAS bioaccumulation factors for agricultural plants - A review.

A main source of perfluoroalkyl and polyfluoroalkyl substances (PFASs) residues in agricultural plants is their uptake from contaminated soil. Bioaccumulation factors (BAFs) can be an important tool to derive recommendations for cultivation or handling of crops prior consumption. This review compiles >4500 soil-to-plant BAFs for 45 PFASs from 24 studies involving 27 genera of agricultural crops. Grasses (Poaceae) provided most BAFs with the highest number of values for perfluorooctanoic acid and perfluorooctane sulfonic acid. Influencing factors on PFAS transfer like compound-specific properties (hydrophobicity, chain length, functional group, etc.), plant species, compartments, and other boundary conditions are critically discussed. Throughout the literature, BAFs were higher for vegetative plant compartments than for reproductive and storage organs. Decreasing BAFs per additional perfluorinated carbon were clearly apparent for aboveground parts (up to 1.16 in grains) but not always for roots (partly down to zero). Combining all BAFs per single perfluoroalkyl carboxylic acid (C4-C14) and sulfonic acid (C4-C10), median log BAFs decreased by -0.25(±0.029) and -0.24(±0.013) per fluorinated carbon, respectively. For the first time, the plant uptake of ultra-short-chain (≤ C3) perfluoroalkyl acids (PFAAs) was reviewed and showed a ubiquitous occurrence of trifluoroacetic acid in plants independent from the presence of other PFAAs. Based on identified knowledge gaps, it is suggested to focus on the uptake of precursors to PFAAs, PFAAs ≤C3, and additional emerging PFASs such as GenX or fluorinated ethers in future research. Studies regarding the uptake of PFASs by sugar cane, which accounts for about one fifth of the global crop production, are completely lacking and are also recommended. Furthermore, aqueous soil leachates should be tested as an alternative to the solvent extraction of soils as a base for BAF calculations.

Per- and polyfluoroalkyl substances in the German environment - Levels and patterns in different matrices.

Per- and polyfluoroalkyl substances (PFAS) in the environment mostly originate from emissions of previously unregulated PFAS. However, there are also many documented incidents of accidental releases. To track such releases, it is essential to distinguish between typical background contamination and legally relevant incidents. This requires a comprehensive overview of all PFAS present in the environment, which is currently only possible to a limited extent due to the large variety of individual compounds. In the present study, a multimethod for capturing 41 PFAS including perfluoroalkyl acid (PFAA) precursors is introduced. The applicability of the method was tested on terrestrial, freshwater and marine samples from the German Environmental Specimen Bank (ESB), thereby providing a rough overview of PFAS contamination in German environment. Special focus was put on soil samples from ESB sites across Germany in comparison to soil samples from a polluted site in south-west Germany. The method was successfully applied to environmental samples. In total, 31 PFAS were detected, among them PFAA precursors and fluorinated ethers. Substance patterns differed between sites and matrices. In ESB soil samples from 2014 (n = 11), the sum of all captured PFAS ranged between 0.75 and 19.5 µg kg-1 dry weight (dw), while concentrations between 416 µg kg-1 and 3530 µg kg-1 were detected in samples from the incident site (n = 10). In other matrices, total PFAS concentrations were magnitudes lower. Highest concentrations were observed for PFOS in bream livers from the Saale (226 µg kg-1). Given the heterogeneous patterns, it will require further broadly-based monitoring data to allow for a solid estimation of relevant background levels. The data provided here may support the differentiation between background levels and hotspot contaminations.

Short-chain perfluoroalkyl acids: environmental concerns and a regulatory strategy under REACH.

BACKGROUND: Short-chain PFASs (per- and polyfluoroalkyl substances) are widely used as alternatives to long-chain PFASs. Long-chain PFASs become gradually regulated under REACH (EC No. 1907/2006) and other international regulations, due to having persistent, bioaccumulative and toxic properties and/or being toxic for reproduction. The increasingly used short-chain PFASs are assumed to have a lower bioaccumulation potential. Nonetheless, they have other properties of concern and are already widely distributed in the environment, also in remote regions. The REACH Regulation does not directly address these emerging properties of concern, complicating the implementation of regulatory measures. Therefore, this study illustrates these environmental concerns and provides a strategy for a regulation of short-chain PFASs within REACH. RESULTS: Short-chain PFASs have a high mobility in soil and water, and final degradation products are extremely persistent. This results in a fast distribution to water resources, and consequently, also to a contamination of drinking water resources. Once emitted, short-chain PFASs remain in the environment. A lack of appropriate water treatment technologies results in everlasting background concentrations in the environment, and thus, organisms are permanently and poorly reversibly exposed. Considering such permanent exposure, it is very difficult to estimate long-term adverse effects in organisms. Short-chain PFASs enrich in edible parts of plants and the accumulation in food chains is unknown. Regarding these concerns and uncertainties, especially with respect to the precautionary principle, short-chain PFASs are of equivalent concern to PBT substances. Therefore, they should be identified as substances of very high concern (SVHC) under REACH. The SVHC identification should be followed by a restriction under REACH, which is the most efficient way to minimize the environmental and human exposure of short-chain PFASs in the European Union. CONCLUSION: Due to an increasing use of short-chain PFASs, an effective regulation is urgently needed. The concerns of short-chain PFASs do not match the "classical" concerns as defined under REACH, but are not of minor concern. Therefore, it is of advantage to clearly define the concerns of short-chain PFASs. This might facilitate the following restriction process under REACH.

Significance thresholds for the assessment of contaminated groundwater: perfluorinated and polyfluorinated chemicals.

BACKGROUND: Per- and polyfluorinated chemicals (PFC) do not occur naturally in the environment and are, therefore, of anthropogenic origin. As a consequence of their wide range of everyday applications and their extreme persistence in the environment, PFC have become ubiquitous in nature and can, therefore, be detected in groundwater as well as in many other environmental matrices. The German States' Water and Soil Consortia have compiled 'significance thresholds' (GFS) to assess groundwater contaminated with PFC. The GFS serve as criteria for the decision whether actions to remediate polluted groundwater are necessary. Thirteen of these PFC had been detected in groundwater at levels above their limit of quantitation and were assigned first priority. RESULTS: The data regarding human health effects were sufficient to derive guide values according to the criteria of the German Drinking Water Ordinance for 7 of the 13 first-priority PFC. With regard to available ecotoxicological data, predicted no-effect concentration values from official risk assessments existed for 2 of the 13 first-priority PFC. A predicted no-effect concentration for protection of the aquatic biocenosis could be derived for eight more substances. CONCLUSIONS: After evaluation of data from available literature regarding both human health and ecotoxicological effects, significance thresholds ranging from 0.06 to 10.0 µg/L could be derived for 7 of the 13 priority PFC in groundwater. As a practical guide valid solely for human health-based values, a summation rule was proposed for exposures to mixtures of these seven PFC.