Evaluation of the Transformation and Leaching Behavior of Two Polyfluoroalkyl Phosphate Diesters in a Field Lysimeter Study.

In this study, 6:2 and 8:2 polyfluoroalkyl phosphate diester (diPAP) were individually investigated in lysimeters under near-natural conditions. Leachate was sampled for 2 years, as was the soil after the experiment. In the leachate of the diPAP-spiked soils, perfluorocarboxylic acids (PFCAs) of different chain lengths were detected [23.2% (6:2 diPAP variant) and 20.8% (8:2 diPAP variant) of the initially applied molar amount]. After 2 years, the soils still contained 36-37% 6:2 diPAP and 41-45% 8:2 diPAP, respectively, in addition to smaller amounts of PFCAs (1.5 and 10.6%, respectively). Amounts of PFCAs found in the grass were low (<0.1% in both variants). The recovery rate of both 6:2 diPAP and 8:2 diPAP did not reach 100% (63.9 and 83.2%, respectively). The transformation of immobile diPAPs into persistent mobile PFCAs and their transport into the groundwater shows a pathway for human exposure to hazardous PFCAs through drinking water and irrigation of crops.

Degradation and Plant Transfer Rates of Seven Fluorotelomer Precursors to Perfluoroalkyl Acids and F-53B in a Soil-Plant System with Maize (Zea mays L.).

Fluorotelomer precursors in soil constitute a reservoir for perfluoroalkyl acids (PFAAs) in the environment. In the present study, precursor degradation and transfer rates of seven fluorotelomer precursors and F-53B (chlorinated polyfluoroalkyl ether sulfonates) were investigated in pot experiments with maize plants (Zea mays L.). The degradation of fluorotelomer precursors to perfluoroalkyl carboxylic acids (PFCAs) and their uptake spectra corresponded to those of fluorotelomer alcohol (FTOH) in terms of the number of perfluorinated carbon atoms. Short-chain PFCAs were translocated into the shoots (in descending order perfluoropentanoic, perfluorobutanoic, and perfluorohexanoic acid), whereas long-chain PFCAs mainly remained in the soil. In particular, fluorotelomer phosphate diesters (diPAPs) were retained in the soil and showed the highest degradation potential including evidence of α-oxidative processes. F-53B did not degrade to PFAAs and its constituents were mainly detected in the roots with minor uptake into the shoots. The results demonstrate the important role of precursors as an entry pathway for PFCAs into the food chain.

Leaching and Transformation of Perfluoroalkyl Acids and Polyfluoroalkyl Phosphate Diesters in Unsaturated Soil Column Studies.

Per- and polyfluoroalkyl substances (PFAS) are environmentally ubiquitous, anthropogenic substances with adverse effects on organisms, which shows the need to study their environmental fate and leaching behavior. In the present soil columns study, the leaching behavior and fate of nontransformable and transformable (precursors) were investigated. Ten nontransformable PFAS in two different soils, two precursors and two field soils, which were already contaminated with a mixture of PFAS, and two uncontaminated controls, were set up for a time span of 2 years. At the end of the study, the molecular balance could not be closed for nontransformable PFAS. This effect was positively correlated to the fluorinated carbon chain length. The precursors, which were both polyfluoroalkyl phosphate diesters (diPAP), had different transformation products and transformation rates, with a higher rate for 6:2 diPAP than 8:2 diPAP. After 2 years, amounts of diPAP were still found in the soil with no significant vertical movement, showing high adsorption to soils. Transformation products were estimated to be simultaneously formed. They were predominantly found in the percolation water; the amounts left in soil were negligible. Up to half of the initial precursor amounts could not be balanced and were considered missing amounts. The results of contaminated field soil experiments showed the challenge to estimate PFAS leaching without knowing all occurring precursors and complex transformation dynamics. For this purpose, it was shown that a broad examination of contaminated soil with different analytical methods can help with qualitative estimations of leaching risks. For a better quantitative estimation, analytical determination of more PFAS and a quantification of the missing amounts are needed. Environ Toxicol Chem 2022;41:2065-2077. © 2022 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

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.