Short-chain PFCAs Research Articles

Mobility and persistence of pesticides and emerging contaminants in age-dated and redox-classified groundwater under a range of land use types

Understanding groundwater contamination patterns is hampered by the heterogeneous groundwater age and redox status over the depth range typically sampled for identifying pesticides and emerging contaminants threats. This study explores depth patterns of groundwater age and redox status across various land use types, unraveling spatial and temporal trends of pesticides and emerging contaminants using data from groundwater quality monitoring in the south of the Netherlands. The Netherlands is an ideal testing ground due to its high population density and widespread groundwater contamination from multiple sources. 146 multi-level observation wells were age-dated using 3H/3He, and contaminant concentrations were analyzed based on recharge year, land use type, and redox conditions, mitigating uncertainties from spatial and depth-dependent variations in both groundwater age and redox status. Redox-recharge year diagrams were developed to visually evaluate contaminant patterns in relation to these factors and to assess concentration patterns in relation to contamination history. Most detections of pesticides, metabolites, and emerging contaminants occurred in the youngest recharge periods (2000–2010 and 2010–2020) and in agricultural areas. However, certain contaminants, including BAM, desphenyl-chloridazon, short-chain PFCAs, PFOA, and EDTA, were consistently found in older water and Fe- or SO4-reduced conditions, indicating their mobility and persistence in the regional groundwater system. Comparing the presence of contaminants in specific redox classes and recharge periods with known application or leaching history provides insights into retardation (e.g., PFOS) and degradation (e.g., 2-hydroxy-atrazine, benzotriazole), explaining lower detection frequencies in earlier recharge periods. Identifying recharge years from age-dated groundwater helps relate contaminants to farmland application or river water recharge periods, revealing leaching history and contamination origins. The presented framework has the potential to enhance the interpretation of large groundwater datasets from dedicated, short-screened observation wells, such as those from the Danish GRUMO network, the Dutch monitoring networks, and parts of the US National Water Quality Program.

PFAS in municipal landfill leachate: Occurrence, transformation, and sources

To understand sources and processes affecting per- and polyfluoroalkyl substances (PFAS), 32 PFAS were measured in landfill leachate from 17 landfills across Washington State in both pre-and post-total oxidizable precursor (TOP) assay samples, using an analytical method that was the precursor to EPA Draft Method 1633. As in other studies, 5:3FTCA was the dominant PFAS in the leachate, suggesting that carpets, textiles, and food packaging were the main sources of PFAS. Total PFAS concentrations (Σ32PFAS) ranged from 61 to 172,976 ng/L and 580–36,122 ng/L in pre-TOP and post-TOP samples, respectively, suggesting that little or no uncharacterized precursors remained in landfill leachate. Furthermore, due to chain-shortening reactions, the TOP assay often resulted in a loss of overall PFAS mass. Positive matrix factorization (PMF) analysis of the combined pre- and post-TOP samples produced five factors that represent sources and processes. Factor 1 consisted primarily of 5:3FTCA (intermediate of 6:2 fluorotelomer degradation and characteristic of landfill leachate), while factor 2 was dominated by PFBS (degradant of C-4 sulfonamide chemistry) and, to a lesser extent, by several PFCAs and 5:3FTCA. Factor 3 consisted primarily of both short-chain PFCAs (end-products of 6:2 fluorotelomer degradation) and PFHxS (derived from C-6 sulfonamide chemistry), while the main component of factor 4 was PFOS (dominant in many environmental media but minor in landfill leachate, perhaps reflecting a production shift from longer to shorter chain PFAS). Factor 5, highly loaded with PFCAs, was dominant in post-TOP samples and therefore represented the oxidation of precursors. Overall, PMF analysis suggests that the TOP assay approximates some redox processes which occur in landfills, including chain-shortening reactions which yield biodegradable products.

Agricultural activities impact on soil and sediment fluorine and perfluorinated compounds in an endemic fluorosis area

Perfluorinated compounds (PFCs) are organo-fluorine compounds which have been identified at significant levels in soils due to their widespread usage in industrial and commercial applications. However, few studies are available regarding the occurrence of PFCs in the environment of endemic fluorosis areas. To address the issue, soils collected from an endemic fluorosis area of southwestern China were analyzed for the distribution of fluorine and 21 kinds of PFCs. The average water-soluble fluorine concentration in cultivated soil (4.87 mg kg−1) was significantly higher than that in uncultivated soil (3.15 mg kg−1), which mainly ascribed to the utilization of fluorine-enriched fertilizers during agricultural practices. Concentrations of ΣPFCs in all soils ranged from 0.508 to 6.83 ng g−1, with an average of 2.81 ng g−1, dominated by perfluorononanoic acid (PFNA) and perfluorooctanoic acid (PFOA). Highest ΣPFCs was found in the soil samples collected from cropland with intensive agricultural activities. Long-chain PFCs, including four perfluoroalkylcarboxylic acids (PFCAs, C ≥ 8) and one perfluoroalkylsulfonic acids (PFSAs) (perfluorooctane sulfonate (PFOS), C8), exhibited high levels in soils, probably due to their higher hydrophobicity and lower water-solubility than short-chain PFCs. While in sediments, short-chain PFCAs were the dominant compounds. Based on correlation analysis, the relationship between total fluorine and PFCs was insignificant, and soil organic matter was a relevant factor affecting PFCs distribution in soils. This study is expected to present a more comprehensive information about fluorine contamination under the influence of agricultural activities in an endemic fluorosis area.

Evaluation of perfluoroalkyl substances in field-cultivated vegetables

Perfluoroalkyl substances (PFASs) were investigated in three types of vegetables (fruit, leafy, and root vegetables) that were cultivated and harvested from 2014 to 2017. The cultivated soil was mainly affected by perfluoroalkyl carboxylic acid (PFCAs; 91.8% detection rate) rather than perfluoroalkyl sulfonic acids (PFSAs; 8.2%). The cultivated soil (i.e., a volcanic cohesive soil) had a high total organic carbon (TOC = 3.4%) and therefore showed strong adsorption of long-chain PFASs. Short-chain PFCAs (i.e., under C9) were mainly detected in vegetables; specifically, PFBA showed high concentration in tomato shoots. Principal component analysis (PCA) plots clearly showed that PFASs in vegetables were different from those of cultivated soil, air, and rainwater. Interestingly, the whole potato (i.e., including peel) was in the same group as soil, indicating that the whole potato can easily be affected by the cultivated soil. Energy Dispersive X-ray Spectrometry-Scanning Electron Microscope (EDS-SEM) results showed that presence of unremovable micron-sized cultivated soil particles on the potato surface. Comparing the regional differences between the cultivated area of Tsukuba city (East Japan) and Osaka city (West Japan), PFASs patterns were similar in cucumber but differed in green perilla and potato.

BDD anodic treatment of 6:2 fluorotelomer sulfonate (6:2 FTSA). Evaluation of operating variables and by-product formation

The concerns about the undesired impacts on human health and the environment of long chain perfluorinated alkyl substances (PFASs) have driven industrial initiatives to replace PFASs by shorter chain fluorinated homologues. 6:2 fluorotelomer sulfonic acid (6:2 FTSA) is applied as alternative to PFOS in metal plating and fluoropolymer manufacture. This study reports the electrochemical treatment of aqueous 6:2 FTSA solutions on microcrystalline BDD anodes. Bench scale batch experiments were performed, focused on assessing the effect of the electrolyte and the applied current density (5–600 A m−2) on the removal of 6:2 FTSA, the reduction of total organic carbon (TOC) and the fluoride release. Results showed that at the low range of applied current density (J = 50 A m−2), using NaCl, Na2SO4 and NaClO4, the electrolyte exerted a minimal effect on removal rates. The formation of toxic inorganic chlorine species such as ClO4− was not observed. When using Na2SO4 electrolyte, increasing the applied current density to 350–600 A m−2 promoted a notable enhancement of the 6:2 FTSA removal and defluorination rates, pointing to the positive contribution of electrogenerated secondary oxidants to the overall removal rate. 6:2 FTSA was transformed into shorter-chain PFCAs, and eventually into CO2 and fluoride, as TOC reduction was >90%. Finally, it was demonstrated that diffusion in the liquid phase was controlling the overall kinetic rate, although with moderate improvements due to secondary oxidants at very high current densities.

Boron doped diamond electrooxidation of 6:2 fluorotelomers and perfluorocarboxylic acids. Application to industrial wastewaters treatment

The aim of this study was to determine the viability of electrochemical oxidation to degrade and mineralize poly- and perfluoroalkyl substances (PFASs) in wastewaters from an industrial facility dedicated to the production of side-chain-fluorinated polymers and fluorotelomer-based products for fire-fighting foams. 6:2 fluorotelomer sulfonamide alkylbetaine (6:2 FTAB, 1111μg/L), 6:2 fluorotelomer sulfonic acid (6:2 FTSA, 242.5μg/L) and 6:2 fluorotelomer sulfonamide propyl N,N dimethylamine (M4, 34.4μg/L) were the most abundant PFASs in the industrial wastewater, that also contained perfluorocarboxylic acids (ΣPFCAs, 12.2μg/L), high TOC and chloride as main anion. 2L samples were treated in bench scale experiments performed at a current density of 50mA/cm2, in a commercial cell equipped with a boron doped diamond (BDD) anode (70cm2). 97.1% of the initial PFASs content was removed after 8h of electrochemical treatment. Furthermore, the TOC removal (82.5%) and the fluoride release confirmed the PFASs mineralization. Based on the evolution of the different PFASs, electrochemical degradation pathways were proposed. Fluorotelomers sulfonamides 6:2 FTAB and M4 would be degraded into 6:2 FTSA, which conversely would give rise to PFHpA and preferentially PFHxA. The latter PFCAs were transformed into shorter-chain PFCAs, and eventually into CO2 and fluoride. The reported results support the technical viability of BDD electrooxidation for the treatment of PFASs in industrial wastewater.

Photochemical decomposition of 1H,1H,2H,2H-perfluorooctane sulfonate (6:2FTS) induced by ferric ions

Perfluorooctane sulfonate (PFOS) had wide applications, such as in the electroplating industry, but its use was restricted in 2009 by the Stockholm Convention, due to its environmental persistence and potential hazards. As the most common PFOS alternative, 1H,1H,2H,2H-perfluorooctane sulfonic acid (6:2FTS) and its salts have been increasingly used. However, little is known about its photochemical decomposition. This paper reports the ferric ion-induced efficient decomposition and defluorination of 6:2FTS under 254nm ultraviolet (UV) irradiation; the underlying mechanisms were also investigated. In the presence of 100μmol/L ferric ion and at pH3.0, the first-order decomposition rate constant of 6:2FTS (10mg/L) was 1.59/hr, which was 6 times higher than for direct UV photolysis. The effects of the ferric ion concentration and the solution pH on the 6:2FTS photodecomposition were investigated and the optimal reaction conditions were determined. In addition to fluoride and sulfate ions, shorter-chain PFCAs (C2–C7) were detected as major intermediates. The addition of hydrogen peroxide or oxalic acid accelerated the decomposition of 6:2FTS under UV irradiation, but not its defluorination, indicating that hydroxyl radicals can directly react with 6:2FTS but not with the shorter-chain PFCAs. Accordingly, a mechanism for 6:2FTS photochemical decomposition in the presence of ferric ion was proposed, which comprises two reaction pathways. First, hydroxyl radicals can directly attack 6:2FTS, leading to CC bond cleavage. Alternatively, 6:2FTS coordinates with ferric ion to form Fe(III)-6:2FTS complexes, which can undergo ligand-to-metal charge transfer under UV irradiation, causing CS bond cleavage.

Reprint of: Temporal trends of polyfluoroalkyl compounds (PFCs) in liver tissue of grey seals ( Halichoerus grypus) from the Baltic Sea, 1974–2008

Temporal trends of polyfluoroalkyl compounds (PFCs) were examined in grey seal ( Halichoerus grypus) liver from the Baltic Sea over a period of 35 years (1974–2008). In total, 17 of 43 PFCs were found, including the perfluoroalkyl sulfonates (C 4–C 10 PFSAs), perfluorooctanesulfinate (PFOSi), long chain perfluoroalkyl carboxylates (C 7–C 14 PFCAs), and perfluoroalkyl sulfonamides (i.e., perfluorooctane sulfonamide (FOSA) and N-ethyl perfluorooctane sulfonamide (EtFOSA)), whereas saturated and unsaturated fluorotelomer carboxylates, shorter chain PFCAs and perfluoroalkyl phosphonic acids were not detected. Perfluorooctane sulfonate (PFOS) was the predominant compound (9.57–1444 ng g −1 wet weight (ww)), followed by perfluorononanoate (PFNA, 0.47–109 ng g −1 ww). C 6–C 8 PFSAs, PFOSi and C 7–C 13 PFCAs showed statistically significant increasing concentrations between 1974 and 1997, with a peak in 1997 and then decreased or levelled off (except for C 12 and C 13 PFCAs). FOSA had a different temporal trend with a maximum in 1989 followed by significant decreasing concentrations until 2008. Toxicological implications for grey seals are limited, but the maximal PFOS concentration found in this study was about 40 times lower than the predicted lowest observed effect concentrations (LOEC). The statistically significant decreasing concentrations or levelling off for several PFCs in the relative closed marine ecosystem of the Baltic Sea indicate a rapidly responding to reduced emissions to the marine environment. However, the high concentrations of PFOS and continuing increasing concentrations of the longer chain PFCAs (C 12–C 14) shows that further work on the reduction of environmental emissions of PFCs are necessary.

Temporal trends of polyfluoroalkyl compounds (PFCs) in liver tissue of grey seals (Halichoerus grypus) from the Baltic Sea, 1974–2008

Temporal trends of polyfluoroalkyl compounds (PFCs) were examined in grey seal (Halichoerus grypus) liver from the Baltic Sea over a period of 35years (1974–2008). In total, 17 of 43 PFCs were found, including the perfluoroalkyl sulfonates (C4–C10 PFSAs), perfluorooctanesulfinate (PFOSi), long chain perfluoroalkyl carboxylates (C7–C14 PFCAs), and perfluoroalkyl sulfonamides (i.e., perfluorooctane sulfonamide (FOSA) and N-ethyl perfluorooctane sulfonamide (EtFOSA)), whereas saturated and unsaturated fluorotelomer carboxylates, shorter chain PFCAs and perfluoroalkyl phosphonic acids were not detected. Perfluorooctane sulfonate (PFOS) was the predominant compound (9.57–1444ng g−1 wet weight (ww)), followed by perfluorononanoate (PFNA, 0.47–109ng g−1 ww). C6–C8 PFSAs, PFOSi and C7–C13 PFCAs showed statistically significant increasing concentrations between 1974 and 1997, with a peak in 1997 and then decreased or levelled off (except for C12 and C13 PFCAs). FOSA had a different temporal trend with a maximum in 1989 followed by significant decreasing concentrations until 2008. Toxicological implications for grey seals are limited, but the maximal PFOS concentration found in this study was about 40times lower than the predicted lowest observed effect concentrations (LOEC). The statistically significant decreasing concentrations or levelling off for several PFCs in the relative closed marine ecosystem of the Baltic Sea indicate a rapidly responding to reduced emissions to the marine environment. However, the high concentrations of PFOS and continuing increasing concentrations of the longer chain PFCAs (C12–C14) shows that further work on the reduction of environmental emissions of PFCs are necessary.

Quantitative characterization of short- and long-chain perfluorinated acids in solid matrices in Shanghai, China

Perfluorinated acids (PFAs) have been recognized as emerging environmental pollutants because of their widespread occurrences, persistence, and bioaccumulative and toxicological effects. PFAs have been detected in aquatic environment and biota in China, but the occurrences of these chemicals have not been reported in solid matrices in China. In the present study, short- and long-chain PFAs (C2–C14) have been quantitatively determined in solid matrices including sediments, soils and sludge collected in Shanghai, China. The results indicate that sludge contains more PFAs than sediments and soils, and the total PFAs concentrations in sediments, soil and sludge are 62.5–276 ng g − 1 , 141–237 ng g − 1 and 413–755 ng g − 1 , respectively. In most cases, trifluoroacetic acid was the major PFA and accounted for 22–90% of the total PFAs. Although the levels of perfluorooctanoate (PFOA) and perfluorooctanesulfonate (PFOS) were not only lower than trifluoroacetic acid, but also lower than some short-chain PFCAs (<C8) in some individual cases, PFOA and PFOS were still the major pollution compounds in most cases and they constituted 2–34% and 1–9% of the total PFAs, respectively. Meanwhile, unlike previous studies, PFOS levels were not always higher than PFOA in solids collected in Shanghai, China. Given that some short-chain PFAs such as trifluoroacetic acid are mildly phytotoxic and their higher levels in solid matrices were collected in Shanghai, China, these chemicals should be included in future environmental monitoring efforts.