Short-chain Perfluorocarboxylic Acids Research Articles

Persistent organic pollutants in the Antarctic marine environment: The influence impacts of human activity, regulations, and climate change

This study investigates the presence, distribution, and potential impacts of perfluoroalkyl substances (PFASs) and hexabromocyclododecanes (HBCDs) on the Antarctic marine environment. The analysis results from the King Sejong Station, the Jang Bogo Station, and Cape Evans revealed the highest concentrations of both PFASs and HBCDs at King Sejong Station, indicating the significant influence of human activity. Short-chain perfluorocarboxylic acids (PFCAs) dominated the seawater samples, with PFPeA at the highest concentration (0.076 ng/L) at King Sejong Station, whereas perfluorosulfonic acids (PFSAs) were prevalent in the sediments, with PFHxS reaching 0.985 ng/g. Total PFASs in benthos ranged from N.D. to 2.40 ng/g ww across all stations. This indicated the effects of long-range transport and glacial meltwater. α-HBCD was the most common diastereomer in benthos samples, detected in 58.3% of samples, suggesting its selective persistency. Although risk quotient analysis revealed low immediate risks to lower-trophic organisms, potential risks remain owing to their persistence and bioaccumulation potential. Contaminant patterns changed after regulations: perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) levels decreased, unregulated PFASs increased, HBCD stereoisomer ratios shifted towards α-HBCD dominance, and overall HBCD concentrations declined. Widespread persistence of regulated substances was observed in Antarctic environments, highlighting the need for comprehensive and long-term monitoring strategies. This study provides essential baseline data on contaminant distributions across the Southern Ocean, contributing to our understanding of emerging pollutants in Antarctic regions and informing future environmental protection efforts.

Bioelectricity drives transformation of nitrogen and perfluorooctanoic acid in constructed wetlands: Performances and mechanisms

In this study, constructed wetland-microbial fuel cell (CW-MFC) filled with modified basalt fiber (MBF) via iron modification was utilized for treating perfluorooctanoic acid (PFOA) containing sewage. Results showed the significant promotion by bioelectricity on ammonium and total nitrogen by 7.80–8.14 %. Although such enhancement was suppressed by PFOA, higher removal was still observed with closed circuit, and PFOA removal also increased by 9.05 %. Bioelectricity contributed to enrichment of bacteria involved in nitrifying (Nitrospira and Ellin6067), denitrifying (like Thauera and Dechloromonas), iron redox (Geobacter), and sulfate-reducing (Desulfobacter), aligned with up-regulated of functional genes, including amoA, narG , napA, narK, narS, nrfA, sulp and sqr. Enrichment of autohydrogenotrophic and sulfide-oxidizing autotrophic denitrifiers, and nitrate dependent iron oxidation bacteria by bioelectricity all promoted denitrification. Moreover, bioelectricity boosted relative abundance of organic compounds degradation enzymes, such as dehydrogenase, decarboxylase, and dehalogenase, supporting the enhancement on PFOA removal. Generally, PFOA was converted to short-chain perfluorocarboxylic acids (PFCAs) via decarboxylation, hydroxylation, HF elimination, hydrolysis, F- elimination, C-C bond scission, and dehydration in CW-MFC. The final PFCAs-products determined was perfluorobutyric acid. This work estimated feasibility of treating PFOA containing sewage by CM-MFC, and offered new insights on enhancing mechanisms of nitrogen and PFOA conversion.

Enhanced perfluorooctanoic acid (PFOA) degradation by electrochemical activation of peroxydisulfate (PDS) during electrooxidation for water treatment

Improved treatment of per- and polyfluoroalkyl substances (PFAS) in water is critically important in light of the proposed United States Environmental Protection Agency (USEPA) drinking water regulations at ng L−1 levels. The addition of peroxymonosulfate (PMS) during electrooxidation (EO) can remove and destroy PFAS, but ng L−1 levels have not been tested, and PMS itself can be toxic. The objective of this research was to test peroxydisulfate (PDS, an alternative to PMS) activation by boron-doped diamond (BDD) electrodes for perfluorooctanoic acid (PFOA) degradation. The influence of PDS concentration, temperature, and environmental water matrix effects, and PFOA concentration on PDS-EO performance were systematically examined. Batch reactor experiments revealed that 99 % of PFOA was degraded and 69 % defluorination was achieved, confirming PFOA mineralization. Scavenging experiments implied that sulfate radicals (SO4–) and hydroxyl radicals (HO) played a more important role for PFOA degradation than 1O2 or electrons (e−). Further identification of PFOA degradation and transformation products by liquid chromatography-mass spectrometry (LC-MS) analysis established plausible PFOA degradation pathways. The analysis corroborates that direct electron transfers at the electrode initiate PFOA oxidation and SO4– improves overall treatment by cleaving the CC bond between the C7F15 and COOH moieties in PFOA, leading to possible products such as C7F15 and F−. The perfluoroalkyl radicals can be oxidized by SO4– and HO, resulting in the formation of shorter chain perfluorocarboxylic acids (e.g., perfluorobutanoic acid [PFBA]), with eventual mineralization to CO2 and F−. At an environmentally relevant low initial concentration of 100 ng L−1 PFOA, 99 % degradation was achieved. The degradation of PFOA was slightly affected by the water matrix as less removal was observed in an environmental river water sample (91 %) compared to tests conducted in Milli-Q water (99 %). Overall, EO with PDS provided a destructive approach for the elimination of PFOA.

Investigating the sources and fate of per- and polyfluoroalkyl substances (PFAS) in food waste compost

Composting municipal food waste is a key strategy for beneficially reusing methane-producing waste that would otherwise occupy landfill space. However, land-applied compost can cycle per- and polyfluoroalkyl substances (PFAS) back into the food supply and the environment. We partnered with a pilot-scale windrow composting facility to investigate the sources and fate of 40 PFAS in food waste compost. A comparison of feedstock materials yielded concentrations of ∑PFAS under 1 ng g−1 in mulch and food waste and at 1380 ng g−1 in leachate from used compostable food contact materials. Concentrations of targeted ∑PFAS increased with compost maturity along the windrow (1.85–23.1 ng g−1) and in mature stockpiles of increasing curing age (12.6–84.3 ng g−1). Among 15 PFAS quantified in compost, short-chain perfluorocarboxylic acids (PFCAs) – C5 and C6 PFCAs in particular – led the increasing trend, suggesting biotransformation of precursor PFAS into these terminal PFAS through aerobic decomposition. Several precursor PFAS were also measured, including fluorotelomer carboxylic acids (FTCAs) and polyfluorinated phosphate diesters (PAPs). However, since most targeted analytical methods and proposed regulations prioritize terminal PFAS, testing fully matured compost would provide the most relevant snapshot of PFAS that could be land applied. In addition, removing co-disposed food contact materials from the FW feedstock onsite yielded only a 37 % reduction of PFAS loads in subsequent compost, likely due to PFAS leaching during co-disposal. Source-separation of food contact materials is currently the best management practice for meaningful reduction of PFAS in food waste composts intended for land application.

Combined adsorption and electrochemical oxidation of perfluorooctanoic acid (PFOA) using graphite intercalated compound

Perfluorooctanoic acid (PFOA) is a bioaccumulative synthetic chemical containing strong C–F bonds and is one of the most common per- and polyfluoroalkyl substances (PFAS) detected in the environment. Graphite intercalated compound (GIC) flakes were used to adsorb and degrade PFOA through electrochemical oxidation. The adsorption followed the Langmuir model with a loading capacity of 2.6 µg PFOA g−1 GIC and a second-order kinetics (3.354 g µg−1 min−1). 99.4% of PFOA was removed by the process with a half-life of 15 min. When PFOA molecules broke down, they released various by-products, such as short-chain perfluoro carboxylic acids like PFHpA, PFHxA, and PFBA. This breakdown indicates the cleavage of the perfluorocarbon chain and the release of CF2 units, suggesting a transformation or degradation of the original compound into these smaller acids. Shorter-chain perfluorinated compounds had slower degradation rates compared to longer-chain ones. Combining these two methods (adsorption and in situ electrochemical oxidation) was found to be advantageous because adsorption can initially concentrate the PFOA molecules, making it easier for the electrochemical process to target and degrade them. The electrochemical process can potentially break down or transform the PFAS compounds into less harmful substances through oxidation or other reactions.

Comparing the removal and fate of long and short chain per- and polyfluoroalkyl substances (PFAS) during surface water treatment via specialty adsorbents

The oleophobic and hydrophobic properties of per- and polyfluoroalkyl substances (PFAS) favoring their industrial applications have resulted in the persistence, transport, transformation, and accumulation of PFAS in environmental matrices around the globe. Specialty adsorbents comprise specialty ingredients that have wide availability tailored for scalable applications in any landscape. This study investigated 2 specialty adsorbents, Zero-Valent-Iron and Perlite-based Green Environmental Media (ZIPGEM) and Clay-Perlite and Sand sorption media (CPS) in removing long-chain and short-chain PFAS via a fixed-bed column study. The adsorption of perfluorooctane sulfonic acid (PFOS) by ZIPGEM was best explained by pseudo-second-order kinetics. The intraparticle diffusion model was a better fit for adsorption of perfluorooctanoic acid (PFOA) by both CPS and ZIPGEM. CPS exhibited a higher initial removal of PFOA (approximately 91 %) compared to that by ZIPGEM (approximately 84 %). During the initial 2-h run, the removals of perfluoropentanoic acid (PFPeA), perfluorobutanesulfonic acid (PFBS), and perfluorobutanoic acid (PFBA) by CPS were approximately 82 %, 72 %, and 54 %, respectively. The removals of PFPeA, PFBS, and PFBA by ZIPGEM were approximately 42 %, 90 %, and 36 %, respectively. In general, the order of adsorption by CPS and ZIPGEM was PFOS > PFOA > PFHxS > PFHpA > PFHxA > PFPeA > PFBS > PFBA. The preference of adsorption generally follows the media affinity initially by adsorbing larger molecules with higher molecular weights, followed by short-chain perfluorocarboxylic acids and perfluorosulfonic acids. Overall, adsorption was the dominant PFAS removal mechanism with some possible transformation of long-chain PFAS to short-chain PFAS when using CPS and ZIPGEM.

Combustion of high-calorific industrial waste in conventional brick kilns: An emerging source of PFAS emissions to agricultural soils

The brick kilns in the South Asian region are widely documented to partially combust high-calorific waste components of synthetic-industrial origin, which contain hazardous constituents, including per- and polyfluoroalkyl substances (PFAS). Correspondingly, these establishments are necessarily built on agricultural land to easily acquire clay by excavating soil horizons, thus making cultivation soils vulnerable to PFAS contaminations. In this pioneering study, the occurrence, distribution profile, traceability and human health risk exposure to forty-four legacy and novel PFAS homologues, including two ultrashort-chain (C2-C3) PFAS, were investigated in agricultural soils around thirty-two conventional brick kilns across three districts of Pakistan. ⅀44PFAS concentrations ranged from 14.3 to 465 ng/g (median: 28.2 ng/g), which were 2 to 70 folds higher than those in background soils, and slightly higher than those reported in agricultural soils in the global literature. The highest occurrence was observed for PFAS alternatives, i.e., 6:2 fluorotelomer sulfonate (6:2 FTSA) (40 %) and 6:2 chlorinated polyfluorinated ether sulfonate (6:2 Cl-PFESA) (4.5 %). A significant positive correlation (p < 0.01) was observed among the concentrations of short-chain perfluoroalkyl acids (C4-C7) and novel PFOS substitutes, implying their origin from common sources. Furthermore, ultrashort-chain and short-chain perfluorocarboxylic acids (PFCA) (89 %) and perfluorosulfonic acids (PFSA) (63 %) dominated over long-chain's PFCA (11 %) and PFSA (37 %), respectively. The estimated daily intake to children exposed in surrounding inhabited communities, at 95th percentile concentrations was found to be approaching the European tolerable daily intake limit of 0.63 ng/kg bw/day. Therefore, the brick manufacturing industry is identified as a novel source of PFAS in the adjacent environment and for residents. This suggests the need for further investigations to elucidate the origin of emerging contaminants in the waste streams of the region to safeguard ecological integrity.

Efficient defluorination of perfluorooctanoic acid enabled by single-atom Cu/reduced graphene oxide electrocatalytic anode and peroxymonosulfate activation

In this study, an electrocatalytic system using reduced graphene oxide supported single-atom copper (SA-Cu/rGO) anode was constructed for perfluorooctanoic acid (PFOA) defluorination. The successful doping of SA-Cu elevated the oxygen evolution potential and electrochemical active surface area of the anode and provided high electrocatalytic properties. Under optimum initial conditions with a peroxymonosulfate (PMS) concentration of 10 mM, a current density of 15 mA·cm−2, and an unadjusted pH of 7.75, the SA-Cu/rGO system achieved 98.8% removal ratio, 92.5% defluorination, and 94.4% mineralization of 20 mg·L-1 PFOA in 120 min. Kinetic studies indicate PFOA degradation following a pseudo-first-order model, with a rate constant of 4.7 × 10−2 min−1. The presence of PMS in the electrocatalytic system significantly improved the degradation rate and defluorination ratio. Radical trapping and quenching experiments confirmed that both ·OH and ·SO4- radicals contributed to PFOA degradation, with ·SO4- playing a more important role in defluorination. The system show high flexibility in initial PFOA concentrations (0.2–20 mg·L−1) and environmental pH values (3.0–10.0), as well as good durability. The electrocatalytic degradation mechanism of PFOA was proposed through determination of intermediates and density functional theory (DFT) calculation. The total short-chain perfluorocarboxylic acids (PFCAs) intermediates generated throughout the degradation were far from sufficient recovery of the PFOA loss, indicating that apart from the ·OH mediated decarboxylation-hydroxylation-elimination-hydrolysis (DHEH) pathway, the ·SO4- mediated decarboxylation-hydroxylation-oxidation-decarbonyl fluoride (DHOD) pathway may play a significant role in the near-complete defluorination and mineralization of PFOA. Moreover, DFT calculations suggest that the DHOD pathway is energetically favorable over DHEH. This study provides a further understanding of the defluorination mechanism of PFOA in electrocatalytic systems and demonstrates that electrochemical degradation with single-atom copper catalyst is an promising method for PFOA remediation in aqueous environment.

Enhanced removal of perfluorooctanoic acid with sequential photocatalysis and fungal treatment

In this paper, we report the degradation of perfluorooctanoic acid (PFOA), which is a persistent contaminant in the environment that can severely impact human health, by exposing it to a photocatalyst, bismuth oxyiodide (BiOI), containing both Bi4O5I2 and Bi5O7I phases and a fungal biocatalyst (Cunninghamella elegans). Individually, the photocatalyst (after 3 h) and biocatalyst (after 48 h) degraded 35–40% of 100 ppm PFOA with 20–30% defluorination. There was a marked improvement in the degree of degradation (90%) and defluorination (60%) when PFOA was first photocatalytically treated, then exposed to the fungus. GC- and LC–MS analysis identified the products formed by the different treatments. Photocatalytic degradation of PFOA yielded short-chain perfluorocarboxylic acids, whereas fungal degradation yielded mainly 5:3 fluorotelomer carboxylic acid, which is a known inhibitor of cytochrome P450-catalysed degradation of PFAS in C. elegans. The combined treatment likely resulted in greater degradation because photocatalysis reduced the PFOA concentration without generating the inhibitory 5:3 fluorotelomer carboxylic acid, enabling the fungus to remove most of the remaining substrate. In addition, new fluorometabolites were identified that shed light on the initial catabolic steps involved in PFOA biodegradation.

Degradation and Defluorination of Per- and Polyfluoroalkyl Substances by Direct Photolysis at 222 nm.

The susceptibility of 19 representative per- and polyfluoroalkyl substances (PFAS) to direct photolysis and defluorination under far-UVC 222 nm irradiation was investigated. Enhanced photolysis occurred for perfluorocarboxylic acids (PFCAs), fluorotelomer unsaturated carboxylic acids (FTUCAs), and GenX, compared to that at conventional 254 nm irradiation on a similar fluence basis, while other PFAS showed minimal decay. For degradable PFAS, up to 81% of parent compound decay (photolysis rate constant (k222nm) = 8.19-34.76 L·Einstein-1; quantum yield (Φ222nm) = 0.031-0.158) and up to 31% of defluorination were achieved within 4 h, and the major transformation products were shorter-chain PFCAs. Solution pH, dissolved oxygen, carbonate, phosphate, chloride, and humic acids had mild impacts, while nitrate significantly affected PFAS photolysis/defluorination at 222 nm. Decarboxylation is a crucial step of photolytic decay. The slower degradation of short-chain PFCAs than long-chain ones is related to molar absorptivity and may also be influenced by chain-length dependent structural factors, such as differences in pKa, conformation, and perfluoroalkyl radical stability. Meanwhile, theoretical calculations indicated that the widely proposed HF elimination from the alcohol intermediate (CnF2n+1OH) of PFCA is an unlikely degradation pathway due to high activation barriers. These new findings are useful for further development of far-UVC technology for PFAS in water treatment.

Emission of Per- and Polyfluoroalkyl Substances from a Waste-to-Energy Plant─Occurrence in Ashes, Treated Process Water, and First Observation in Flue Gas.

Per- and polyfluoroalkyl substances (PFASs) are a large group of compounds commonly used as industrial chemicals and constituents of consumer products, e.g., as surfactants and surface protectors. When products containing PFASs reach their end of life, some end up in waste streams sent to waste-to-energy (WtE) plants. However, the fate of PFASs in WtE processes is largely unknown, as is their potential to enter the environment via ash, gypsum, treated process water, and flue gas. This study forms part of a comprehensive investigation of the occurrence and distribution of PFASs in WtE residues. Sampling was performed during incineration of two different waste mixes: normal municipal solid waste incineration (MSWI) and incineration of a waste mix with 5-8 wt % sewage sludge added to the MSWI (referred to as Sludge:MSWI). PFASs were identified in all examined residues, with short-chain (C4-C7) perfluorocarboxylic acids being the most abundant. Total levels of extractable PFASs were higher during Sludge:MSWI than during MSWI, with the total annual release estimated to be 47 and 13 g, respectively. Furthermore, PFASs were detected in flue gas for the first time (4.0-5.6 ng m-3). Our results demonstrate that some PFASs are not fully degraded by the high temperatures during WtE conversion and can be emitted from the plant via ash, gypsum, treated process water, and flue gas.

Fluorescence Turn-On/Off Responses of In (III)-MOF to Short-Chain Perfluorocarboxylic Acids

AbstractShort-chain perfluorocarboxylic acids (PFCAs) are a class of persistent organic pollutants that are widely used as substitutes for long-chain PFCAs. However, they also pose a non-negligible risk to ecosystems. In this study, we demonstrated that a fluorescent metal–organic framework (MOF) (named V-101) constructed from In3+ and an aromatic-rich tetratopic carboxylate ligand 5-[2,6-bis (4-carboxyphenyl) pyridin-4-yl] isophthalic acid (H4BCPIA) exhibited highly efficient turn-off and turn-on fluorescence responses toward five short-chain PFCAs in water and methanol, respectively. The limits of detection of V-101 toward five short-chain PFCAs are down to μg/L level, and it showed good anti-interference abilities toward short-chain PFCAs in the presence of common metal ions. The major mechanisms associated with fluorescence responses were molecular collisions and interactions between V-101 and short-chain PFCAs. This work demonstrates that the structure variety of MOFs imparts them with the potential of MOFs in the detection of short-chain PFCAs for pollution control.

Photocatalytic Degradation of Perfluorooctanoic Acid on Pb-doped TiO2 Coated with Reduced Graphene Oxide.

Poor reactivity of extraordinarily strong per- and polyfluoroalkyl substances (PFAS) with TiO2 makes it necessary to advance photocatalytic materials. In this present work, lead (Pb)-doped TiO2 coated with reduced graphene oxide (TiO2 -Pb/rGO) was prepared using hydrothermal method and then its photocatalytic activity with various PFAS in water, especially perfluorooctanoic acid (PFOA), was investigated. PFAS decomposition kinetics by TiO2 -Pb/rGO was compared to neat TiO2 , Pb-doped TiO2 (TiO2 -Pb) and rGO-coated TiO2 (TiO2 /rGO). TiO2 -Pb/rGO (0.33 g/L) under UV showed superior removal of PFOA (10 mg/L) at 98% after 24 hr, following TiO2 -Pb/UV at 80%, TiO2 /rGO/UV at 70%, TiO2 /UV at <10%, and UV at <10%. Doping of TiO2 with Pb and introduction of rGO to TiO2 greatly changed the physicochemical properties of TiO2 and the subsequent charge transfer mechanism. Radical scavenger experiments indicated that holes, superoxide radical anion, and singlet oxygen were responsible for the observed PFOA decomposition. Decomposition of PFOA by TiO2 -Pb/rGO under UV led to formation of short-chain perfluorocarboxylic acids (PFCAs) as reaction intermediates through step-by-step removal of CF2 units. Polyfluoroalkyl substance (6:2 fluorotelomer sulfonate (6:2FTS)) and long-chain PFCAs such as PFOA were significantly removed and defluorinated by TiO2 -Pb/rGO while it was ineffective towards perfluorosulfonic acids and short-chain PFCAs. Removal kinetics decreased in order of 6:2FTS > PFOA >> PFOS > PFHpA ≈ PFHxS ≈ PFBA ≈ PFBS. Pb doping to TiO2 /rGO showed better performance than Fe doping. Overall, this study implied that proper designing of TiO2 photocatalytic materials enables to expedite decomposition of persistent organic pollutants in water, in particular highly challenging fluorinated chemicals.

Adsorption of PFOS onto graphite intercalated compound and analysis of degradation by-products during electro-chemical oxidation

Perfluorooctane sulfonate (PFOS) is a highly recalcitrant perfluoro chemical belonging to the family of per- and polyfluoroalkyl substances (PFAS). Its adsorption and degradation was demonstrated in a novel PFAS remediation process involving the adsorption onto graphite intercalated compounds (GIC) and the electrochemical oxidation. The Langmuir type of adsorption was characterized by a loading capacity of 53.9 μg PFOS g−1 GIC and a second order kinetics (0.021 g μg−1 min−1). Up to 99% of PFOS was degraded in the process with a half-life of 15 min. The breakdown by-products included short chain perfluoroalkane sulfonates such as Perfluoroheptanesulfonate (PFHpS), Perfluorohexanesulfonate (PFHxS), Perfluoropentanesulfonate (PFPeS) and Perfluorobutanesulfonate (PFBS), but also short chain perfluoro carboxylic acids such as perfluorooctanoic acid (PFOA), perfluorohexanoic acid (PFHxA) and perfluorobutanoic acid (PFBA) indicating different degradation pathways. These by-products could also be broken down but the shorter the chain the slower the degradation rate. This novel combined adsorption and electrochemical process offers an alternative treatment for PFAS contaminated waters.

The influence of environmental and ecological factors on the accumulation and distribution of short- and long-chain perfluoroalkyl acids in a mid-trophic avian insectivore

Perfluoroalkyl acids (PFAAs) include perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA), perfluorohexane sulfonic acid (PFHxS), and perfluorodecane sulfonic acid (PFDS), as well as increasingly used alternative short-chain perfluorosulfonic acids (PFSAs) and short- and long-chain (≥C9) perfluorocarboxylic acids (PFCAs). In the present study, tissues of tree swallows (Tachycineta bicolor) from two sites in southern Ontario, Canada, were analyzed for 17 individual PFAAs and showed egg and nestling tissue (liver, carcass) profiles dominated by PFOS (57–66%). The remaining PFAAs contributed ≤7% each, although collectively the long-chain PFCAs comprised 21–29% of the PFAAs. The short-chain PFSAs and PFCAs were among the lowest concentrations, suggesting that despite increased production and use of these alternative PFAAs, they are not accumulated to the same extent as the long-chain PFSAs and PFCAs. PFOS, PFDS, and some long-chain PFCAs were significantly higher in eggs than in livers and carcasses, whereas PFOA and the two short-chain PFCAs were significantly higher in nestling tissues than in eggs. For the two short-chain PFSAs, concentrations were similar among tissues. Tree swallow tissues at the site near a wastewater treatment plant (WWTP) outfall showed higher concentrations of PFOS, PFDS, PFHxS, and some long-chain PFCAs than tree swallows sampled at the nearby reference site; however, the influence of the WWTP was more equivocal for PFOA, other long-chain PFCAs, and short-chain PFSAs and PFCAs. Carbon stable isotopes (δ13C) and fatty acid signatures indicated that the diets of the WWTP swallows were more terrestrial than the reference swallows. Nonetheless, models considering environmental and ecological variables indicated that site was often the primary driver of PFAA variation among the swallows, with less or no influence of dietary patterns, or sex or body condition, revealing that of WWTP effluent can be an important environmental source of the major PFAAs in tree swallows.

Comparative investigation of PFAS adsorption onto activated carbon and anion exchange resins during long-term operation of a pilot treatment plant

Widespread contamination of groundwater with per- and polyfluoroalkyl substances (PFAS) has required drinking water producers to quickly adopt practical and efficacious treatments to limit human exposure and deleterious health outcomes. This pilot-scale study comparatively investigated PFAS adsorption behaviors in granular activated carbon (GAC) and two strong-base gel anion exchange resin (AER) columns operated in parallel over a 441-day period to treat contaminated groundwater dominated by short-chain perfluorocarboxylic acids (PFCA). Highly-resolved breakthrough profiles of homologous series of 2–8 CF2 PFCA and perfluorosulfonic acids (PFSA), including ultrashort-chain compounds and branched isomers, were measured to elucidate adsorption trends. Sample ports at intermediate bed depths could predict 50% breakthrough of compounds on an accelerated basis, but lower empty bed contact times led to conservative estimates of initial breakthrough. Homologous PFAS series displayed linear (GAC) and log-linear (AER) relationships between chain-length and breakthrough, independent of initial concentration. AERs generally outperformed GAC on a normalized bed volume basis, and this advantage widened with increasing PFAS chain-length. As designed, all treatments would have short full-scale service times (≤142 days for GAC; ≤61 days for AERs) before initial breakthrough of short-chain (2–4 CF2) PFCA. However, AER displayed far longer breakthrough times for PFSA compared to GAC (>3× treatment time), and breakthrough was not observed for PFSA with >4 CF2 in AERs. GAC had a finite molar adsorption capacity for total PFAS, leading to a stoichiometric replacement of short-chain PFCA by PFSA and longer-chain PFCA over time. AERs quickly reached a finite adsorption capacity for PFCA, but they showed substantially greater selectivity for PFSA whose capacity was not reached within the duration of the pilot. Breakthrough characteristics of keto- and unsaturated-PFSA, identified in the groundwater by suspect screening, were also evaluated in absence of reference standards. Modified PFAS structures (branched, keto-, unsaturated-) broke through faster than linear and unmodified perfluorinated structures with equal degrees of fluorination, and the effects were more pronounced in GAC compared to AERs. The results highlight that the design of robust PFAS treatment systems should consider facets beyond current PFAS targets including operational complexities and impacts of unregulated and unmonitored co-contaminants.

Exposure of a single wild boar population in North Rhine-Westphalia (Germany) to perfluoroalkyl acids

Perfluoroalkyl acids (PFAA) are among the leading chemical pollutants in the twenty-first century. Of these, perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) have been widely detected in a large number of animal and environmental samples. Wild boars accumulate PFAA in their livers, but it has not yet been clarified to what extent wild boars of the same population accumulate different PFAA in their livers or whether any conclusions can be drawn from any differences found in regard to environmental contamination. In this study, liver samples from wild boars killed during driven hunts in 2019 and 2020 from a defined forest area in North Rhine-Westfalia, Germany were analyzed for 13 different PFAA. A mean load of 493 µg/kg (± 168 µg/kg) PFAA was measured in 2020. Perfluorosulfonic acids accounted for 87% of the total load in both years, with PFOS dominating this group. These results were similar to those of 14 liver samples collected from other regions of Germany for comparison. In addition, the livers of hunted pregnant sows and fetuses were examined. The load of short-chain perfluorocarboxylic acids (< C8) in the fetus liver was as high as that of the sows, whereas the concentrations of long-chain perfluorocarboxylic acids (≥ C8) were lower than in the dams. This result shows for the first time that fetuses take up PFAA from their mothers in utero. Our study shows that PFAA content in wild boar livers is comparably high in all animals in a local population and indicates a need for further research regarding a nationwide background exposure to PFAA in wild boars and their surrounding environment.

Per- and polyfluoroalkyl substance (PFAS) retention by colloidal activated carbon (CAC) using dynamic column experiments

Developing effective remediation methods for per- and polyfluoroalkyl substance (PFAS)-contaminated soils is a substantial step towards counteracting their widespread occurrence and protecting our ecosystems and drinking water sources. Stabilisation of PFAS in the subsurface using colloidal activated carbon (CAC) is an innovative, yet promising technique, requiring better understanding. In this study, dynamic soil column tests were used to assess the retardation of 10 classical perfluoroalkyl acids (PFAAs) (C5–C11 perfluoroalkyl carboxylic acids (PFCAs) and C4, C6, C8 perfluoroalkane sulfonates (PFSAs)) as well as two alternative PFAS (6:2 and 8:2 fluorotelomer sulfonates) using CAC at 0.03% w/w, to investigate the fate and transport of PFAS under CAC treatment applications. Results showed high retardation rates for long-chain PFAS and eight times higher retardation for the CAC-treated soil compared to the non-treated reference soil for the ∑PFAS. Replacement of shorter chain perfluorocarboxylic acids (PFCAs), such as perfluoropentanoic acid (PFPeA), by longer chained PFAS was observed, indicating competition effects. Partitioning coefficients (Kd values) were calculated for the CAC fraction at ∼103–105 L kg−1 for individual PFAS, while there was a significant positive correlation (p < 0.05) between perfluorocarbon chain length and Kd. Mass balance calculations showed 37% retention of ∑PFAS in treated soil columns after completion of the experiments and 99.7% higher retention rates than the reference soil. Redistribution and elution of CAC were noticed and quantified through organic carbon analysis, which showed a 23% loss of carbon during the experiments. These findings are a step towards better understanding the extent of CAC's potential for remediation of PFAS-contaminated soil and groundwater and the limitations of its applications.

Degradation of perfluoroalkyl substances using UV/Fe0 system with and without the presence of oxygen

ABSTRACT The wide presence of per- and poly-fluoroalkyl substances (PFAS) in the environment is a global concern, thus their degradation is an imminent task. In this study, oxidative and/or reductive degradation of three representative PFAS – perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), and perfluorooctane sulfonate (PFOS) was achieved using nanoscale zero-valent iron (Fe0 NPs) under ultraviolet (UV) light, both with and without the presence of oxygen. Higher degradation and defluorination rates were obtained for a longer chain PFNA compared to PFOA, and a higher removal of PFAS was achieved without the presence of O2 compared to that with O2. The degradation followed first-order reaction kinetics, and obtained the highest rates of 97.6, >99.9, and 98.5% without the presence of O2 for PFOA, PFNA, and PFOS, respectively. The degradation rates increased with an increase in the nanoparticle concentrations in the range of 1–100 mg/L. In addition to fluoride ions, shorter chain perfluorocarboxylic acids (PFCAs) were detected as the main intermediates during PFAS degradation; PFHpS and 6:2 FTS were also detected during PFOS degradation. Hydroxyl radicals (·OH) and superoxide radicals (·O2 −) were not involved in the degradation of PFOA, but likely involved in the degradation of PFOS. Emerging contaminants PFAS degradation using the UV/Fe0 system is a cost-effective technology owing to the low cost and recyclability of Fe0 nanomaterials, low energy consumption in the system, and its capability to degrade PFAS both with and without the presence of oxygen. This technology can be potentially applied to treat PFAS-contaminated waters in the environment.

Dependency of the photocatalytic and photochemical decomposition of per- and polyfluoroalkyl substances (PFAS) on their chain lengths, functional groups, and structural properties.

This study reports the removal of per- and polyfluoroalkyl substances (PFAS) in water using various photocatalytic and photochemical processes. PFAS were chosen, based on chain lengths, functional groups, and structural properties: four perfluorocarboxylic acids (PFCAs), including perfluorooctanoic acid (PFOA), three perfluorosulfonic acids (PFSAs), including perfluorooctanesulfonic acid (PFOS), hexafluoropropylene oxide dimer (GenX), and 6:2 fluorotelomer sulfonate (6:2 FTS), and dependency of the photocatalytic decomposition of PFAS on their properties was investigated. Oxidants and reductants were introduced to study the photochemical decomposition of PFAS, and reactive species and reaction byproducts were identified to elucidate the decomposition mechanism of PFAS. Some notable findings include: long chain PFCAs (95% in 48 h) and 6:2 FTS (100%) were removed via chemical decomposition in TiO2/UVC while GenX (37%), long chain PFSAs (60%), short chain PFSAs (0-10%) and short chain PFCAs (5-18%) were removed via physical adsorption. Sulfate radicals generated with persulfate (PS) played an important role in decomposing PFCAs (60-90%). Sulfite activated by UVC worked for defluorination of PFOA (75%) and PFOS (80%). PFOA was removed faster by UVC/sulfite > UVC/TiO2/sulfite ≈ UVC/TiO2/PS ≥ UVC/PS > UVC/TiO2 while PFOS was removed faster by UVC/sulfite ≫ UVC/TiO2/sulfite ≈ UVC/TiO2/PS ≈ UVC/TiO2 ≫ UVC/PS. Susceptibility of PFAS to the chemical reactions could be explained by their properties and the reactive species produced in each system.