Fluorotelomer Sulfonic Acid Research Articles

Novel and legacy per- and polyfluoroalkyl substances in bald eagle eggs from the Great Lakes region

Decades of large-scale production of per- and polyfluoroalkyl substances (PFASs) have resulted in their ubiquitous presence in the environment worldwide. Similarly to other persistent and bioaccumulative organic contaminants, some PFASs, particularly the long-chain congeners, can be biomagnified via food webs, making top predators vulnerable to elevated PFAS exposure. In this study, we measured seven classes of PFASs in bald eagle (Haliaeetus leucocephalus) eggs for the first time. The eggs (n = 22) were collected from the North American Great Lakes in 2000–2012. The ranges of total concentrations of perfluoroalkyl sulfonic acids (∑PFSAs) and perfluoroalkyl carboxylic acids (∑PFCAs) were 30.5–1650 and 5.4–216 ng/g wet weight (ww), respectively. In addition to these traditional PFAS compounds, 6:2 fluorotelomer sulfonic acid (6:2 FTS; median: 15.7 ng/g ww), perfluoro-4-ethylcyclohexanesulfonic acid (PFECHS; 0.22 ng/g ww), and 8-chloro-perfluorooctanesulfonic acid (Cl-PFOS, detected in wildlife for the first time; 0.53 ng/g ww) were also frequently detected. Bald eagle eggs from breeding areas located less than 8 km from a Great Lake shoreline or tributary had significantly greater total PFAS concentrations (∑PFASs) than those from breeding areas located further than 8 km (p < 0.05). In these samples, ∑PFASs rivalled the total concentration of brominated flame retardants, and were significantly greater than those of several other organic contaminants, such as dechlorane-related compounds, organophosphate esters, and flame retardant metabolites.

Aerobic biotransformation of 6:2 fluorotelomer sulfonic acid in soil

Per- and polyfluoroalkyl substances (PFASs) have been widely used in numerous industrial and household products due to its hydrophobic and lipophobic nature. As the main active ingredient, PFASs have been widely used in aqueous film forming foam (AFFF) used to fight liquid-fueled fires. As the electrochemical fluorination (ECF)-based PFASs were gradually phased out by major PFAS manufacturers worldwide, fluorotelomer-based PFASs, such as 6:2 fluorotelomer sulfonic acid (6:2 FTSA, [F(CF2)6CH2CH2SO3H]) and its precursors, have been widely detected in soil and groundwater effected by firefighting training activities. A few precursors (e.g., 6:2 fluorotelomer alcohol, 6:2 FTOH, [F(CF2)6CH2CH2OH]) have been well studied, but there are still leaving major gaps in understanding of 6:2 FTSA fate and aerobic biotransformation in soil. Soil collected from forest area was dosed with 6:2 FTSA to investigate its biotransformation rate and to identify major transformation products in a flow-through soil incubation system over 90 d. The overall mass balance at day 90 in sterile and live treatments averaged 97.4% and 76.8%, respectively, suggesting that there may be soil-bound residues and conjugates between fluorinated transformation products and dissolved soil components only in live test system not in the sterile soil. The 6:2 FTSA biotransformation was relatively low with a half-life more than 56 d, and 33% of initial 6:2 FTSA remained at day 90. According to the transformation products and the results in 6:2 FTSA biodegradation, the pathways of 6:2 FTSA aerobic biodegradation in the soil were proposed. The volatile 5:2 secondary alcohol (5:2 sFTOH, [F(CF2)5CH(OH)CH3]) and 5:2 fluorotelomer ketone (5:2 FT ketone, [F(CF2)5COCH3]) were the most abundant intermediate transformation products at the beginning, and reached highest at day 7 and 14, respectively. Perfluoropentanoic acid (PFPeA, [F(CF2)4COOH]) and perfluorohexanoic acid (PFHxA, [F(CF2)5COOH]) were produced as end products by 6:2 FTSA through desulfonation, oxidation and other reactions. In another minor pathway, 5:3 polyfluorinated acid (5:3 acid, [F(CF2)5CH2CH2COOH]) and perfluorobutanoic acid (PFBA, [F(CF2)3COOH]) were also formed. The concentrations of these end products, including PFBA, PFPeA, PFHxA, and 5:3 acid, increased in all experiment period. At day 90, the generations of PFPeA, PFHxA, 5:3 acid, and PFBA at a yield of 20.4 mol%, 6.5 mol%, 9.5 mol%, and 1.0 mol% were observed. Perfluoroheptanoic acid (PFHpA, [F(CF2)6COOH]) was not detected in the soil, suggesting that there was no α-oxidation in the process of 6:2 FTSA biotransformation in live soil. NaOH-acetonitrile extraction plus ENVI-Carb™ clean up could breakdown the binding between 5:3 acid and organic matter of the soil, and an enhancement factor up to 18 could be achieved for 5:3 acid by this cleanup method. The sorption of 6:2 FTSA to soil could low the biotransformation. The enzymatic desulfonation step may limit 6:2 FTSA biotransformation in aerobic soil. This study indicates that 6:2 FTSA may be persistent in aerobic soil, and a potential source of short chain perfluorocarboxylic acids (PFCAs) in soil. More studies need to be done to understanding the fate of AFFF-related polyfluoroalkyl precursors in soil environment in the future work.

Losses of poly- and perfluoroalkyl substances to syringe filter materials

Syringe filters are used to separate solids from liquids prior to analysis of poly- and perfluoroalkyl substances (PFASs). This is a critical step in sample preparation, as losses of PFASs to the filter material can be significant and lead to underestimation. This study evaluated losses of 21 PFASs in three different matrices (methanol, MilliQ water, and water containing 10 mg L−1 dissolved organic carbon (DOC)) to six different types of syringe filter (0.45 and 0.22 μm). Regarding sample matrix, the lowest average ∑21PFAS losses were observed in methanol (13%), followed by DOC water (19%) and MilliQ water (26%). Regarding syringe filter material, the lowest average losses of ∑21PFAS in DOC water and MilliQ water were observed for a recycled cellulose filter (average losses 16% and 21%, respectively), while a polypropylene filter had the lowest ∑21PFAS losses in methanol (9%). A smaller polyethersulfone (PES) filter (0.22 μm, 17 mm Ø) showed significantly (p < 0.05) lower ∑21PFAS losses in DOC water (on average 7.3%) than a larger PES filter (0.45 μm, 37 mm Ø) (23%). In DOC water, losses to the filter increased by 3.8%, 5.1%, and 8.4% per CF2-moiety for C3-C11 perfluoroalkyl carboxylates (PFCAs), perfluoroalkyl sulfonates (PFSAs), and fluorotelomer sulfonic acids (FTSAs), respectively. Comparing different functional groups of PFASs, losses increased as follows: PFCAs < PFSAs < FTSAs < perfluorooctanesulfonamides (FOSAs). Thus, care is needed when including filtration in PFAS analysis, since losses can be significant (up to 100%) depending on the type of syringe filter, target PFAS, and matrix.

Fate of 6:2 fluorotelomer sulfonic acid in pumpkin (Cucurbita maxima L.) based on hydroponic culture: Uptake, translocation and biotransformation

6:2 fluorotelomer sulfonic acid (6:2 FTSA) is currently used as an alternative to perfluorooctanesulfonate (PFOS) and is widely detected in the environment. The uptake, translocation and biotransformation of 6:2 FTSA in pumpkin (Cucurbita maxima L.) were investigated by hydroponic exposure for the first time. The root concentration factor (RCF) of 6:2 FTSA was 2.6–24.2 times as high as those of perfluoroalkyl acids (PFAAs) of the same or much shorter carbon chain length, demonstrating much higher bioaccumulative ability of 6:2 FTSA in pumpkin roots. The translocation capability of 6:2 FTSA from root to shoot depended on its hydrophobicity. Six terminal perfluorocarboxylic acid (PFCA) metabolites, including perfluoroheptanoic acid (PFHpA), perfluorohexanoic acid (PFHxA), perfluoropentanoic acid (PFPeA), perfluorobutanoic acid (PFBA), perfluoropropionic acid (PFPrA) and trifluoroacetic acid (TFA) were found in pumpkin roots and shoots. PFHpA was the primary metabolite in roots, while PFBA was the major product in shoots. 1-aminobenzotriazole (ABT), a cytochromes P450 (CYPs) suicide inhibitor, could decrease the concentrations of PFCA products with dose-dependent relationships in pumpkin tissues, implying the role of CYP enzymes involved in plant biotransformation of 6:2 FTSA. This study indicated that the application of 6:2 FTSA can lead to the occurrence of PFCAs (C2–C7) in plants.

Per- and polyfluoroalkyl substances (PFASs) in precipitation from mainland China: Contributions of unknown precursors and short-chain (C2[sbnd]C3) perfluoroalkyl carboxylic acids

A nationwide survey was conducted on per- and polyfluoroalkyl substances (PFASs) in precipitation across mainland China. Twenty-two PFASs, including precursors to perfluoroalkyl acids (pre-PFAAs), were investigated in thirty-nine precipitation samples collected from twenty-eight cities. Trifluoroacetate (TFA), perfluorooctanoic acid, and perfluorooctane sulfonic acid (PFOS) were ubiquitous in precipitation. TFA displayed the highest concentrations (8.8–1.8 × 103 ng/L), which were particularly elevated in coastal cities. 6:2 chlorinated polyfluorinated ether sulfonic acid, an alternative to PFOS, was detected for the first time in precipitation at a frequency of 43%. Polyfluoroalkyl phosphoric acid diesters and 6:2 fluorotelomer sulfonic acid were also occasionally detected. PFAS fluxes in the northeastern area (C4C12; 2.0 × 102–3.4 × 103 ng/m2/d) with major PFAS manufacturing facilities were higher than those in the southwestern area (63–1.7 × 103 ng/m2/d). Using total oxidizable precursor (TOP) assay, the occurrence of unknown pre-PFAAs was for the first time uncovered in precipitation with maximum estimated fluxes of C6 and C8 pre-PFAAs at 3.1 × 103 and 4.3 × 103 ng/m2/d, respectively. The relative contribution of ultrashort-chain PFCAs (C2C3) ranged from 22% to 91% of ∑PFASs, while unknown pre-PFAAs accounted for 6%–56% of the total molar concentrations of PFASs. This bears critical concerns on underestimation of PFAS mass load from precipitation to surface environment ascribed to monitoring data solely on known PFASs. Unknown precursors of PFAAs in the atmosphere are yet to be identified for their chemical structures and relevant environmental risks as well.

Deep seepage of per- and polyfluoroalkyl substances through the soil of a firefighter training site and subsequent groundwater contamination

Per- and polyfluoroalkyl substances (PFASs) are utilized in specific firefighting foams. The objectives of this study were i) to map PFAS distribution in the soil and groundwater of a firefighter training site active for more than 3 decades, ii) to locate the main points of entry of PFASs into the aquifer and iii) to identify which PFASs seeped most deeply into the soil. A total of 44 soil cores and 17 groundwater samples were collected. Perfluorooctane sulfonate (PFOS), 6:2 fluorotelomer sulfonic acid (6:2 FTSA) and 6:2 Fluorotelomer sulfonamide alkylbetaine (6:2 FTAB) were the most predominant PFASs in surface soil. The highest total PFAS concentrations (up to 357 μg/g) were measured in two areas. Both areas were considered as potential points of entry of PFASs into the aquifer since PFASs were detected in soil 15 m below the surface, despite the presence of clay layers. The highest total PFAS concentrations were recorded in the monitoring wells located in the perimeter of the firefighter training site and in the spring located downgradient in the direction of groundwater flow. They ranged from 300 to 8300 ng/L. The fluorotelomer 6:2 FTAB was quantified in 6 monitoring wells, suggesting that this FT can reach a water table 20 m below the ground's surface.

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.

Electrochemical oxidation of 6:2 fluorotelomer sulfonic acid (6:2 FTSA) on BDD: electrode characterization and mechanistic investigation

6:2 Fluorotelomer sulfonic acid (6:2 FTSA) is used as surfactant and foam stabilizer in the formulation of air firefighting foams (AFFFs). 6:2 FTSA is produced as an alternative to persistent and bioaccumulative long-chain perfluoroalkyl compounds. This study investigates the electrochemical degradation of 6:2 FTSA on a boron-doped diamond (BDD) anode. First, the BDD anode was characterized by cyclic voltammetry, revealing that the direct oxidation of 6:2 FTSA occurred at an anodic potential of 2.72 V versus Ag/AgCl (saturated KCl) electrode. Increasing the scan rate resulted in an increased current intensity of the direct oxidation peak, and this relationship was analyzed using the Randles–Sevcik equation to calculate the diffusion coefficient of 6:2 FTSA in aqueous media (D = 4.16 × 10−6 cm2 s−1 at room temperature). This value is in close agreement to the predicted value obtained by the Wilke–Chang correlation. In electrolysis experiments under potentiostatic control, increasing the anode potential over 2.72 V greatly enhanced the 6:2 FTSA removal, and the simultaneous formation of short-chain perfluorocarboxylic acids (perfluorohexanoic acid, perfluorpentanoic acid and perfluorobutanoic acid) and fluoride release were observed. Based on these observations, the 6:2 FTSA degradation pathway was predicted to start by the attack of hydroxyl radicals to the non-fluorinated carbons to form a perfluorocarboxylate, followed by a single electron transfer to the anode to yield a reactive radical C6F13COO‧. The latter species decarboxylated and finally combined with hydroxyl radicals to allow defluorination to form shorter-chain perfluorocarboxylic acids.

Editor's perspective – Per‐ and polyfluorinated substances pose substantial challenges to remediation practitioners

Editor's perspective – Per‐ and polyfluorinated substances pose substantial challenges to remediation practitioners

Cytotoxicity of novel fluorinated alternatives to long-chain perfluoroalkyl substances to human liver cell line and their binding capacity to human liver fatty acid binding protein.

Although shorter chain homologues and other types of fluorinated chemicals are currently used as alternatives to long-chain perfluoroalkyl substances (PFASs), their safety information remains unclear and urgently needed. Here, the cytotoxicity of several fluorinated alternatives (i.e., 6:2 fluorotelomer carboxylic acid (6:2 FTCA), 6:2 fluorotelomer sulfonic acid (6:2 FTSA), 6:2 chlorinated polyfluorinated ether sulfonate (6:2 Cl-PFESA), and hexafluoropropylene oxide (HFPO) homologues) to human liver HL-7702 cell line were measured and compared with perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS). Their binding mode and affinity to human liver fatty acid binding protein (hL-FABP) were also determined. Compared with PFOA and PFOS, 6:2 Cl-PFESA, HFPO trimer acid (HFPO-TA), HFPO tetramer acid (HFPO-TeA), and 6:2 FTSA showed greater toxic effects on cell viabilities. At low exposure doses, these alternatives induced cell proliferation with similar mechanism which was different from that of PFOA and PFOS. Furthermore, binding affinity to hL-FABP decreased in the order of 6:2 FTCA<6:2 FTSA<HFPO dimer acid (HFPO-DA)<PFOA<PFOS/6:2 Cl-PFESA/HFPO-TA. Due to their distinctive structure, 6:2 Cl-PFESA and HFPO homologues were bound to the hL-FABP inner pocket with unique binding modes and higher binding energy compared with PFOA and PFOS. This research enhances our understanding of the toxicity of PFAS alternatives during usage and provides useful evidence for the development of new alternatives.

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.

Contribution of precursor compounds to the release of per- and polyfluoroalkyl substances (PFASs) from waste water treatment plants (WWTPs)

Per- and polyfluoroalkyl substances (PFASs) are ubiquitous in sludge and water from waste water treatment plants, as a result of their incorporation in everyday products and industrial processes. In this study, we measured several classes of persistent PFASs, precursors, transformation intermediates, and newly identified PFASs in influent and effluent sewage water and sludge from three municipal waste water treatment plants in Sweden, sampled in 2015. For sludge, samples from 2012 and 2014 were analyzed as well. Levels of precursors in sludge exceeded those of perfluoroalkyl acids and sulfonic acids (PFCAs and PFSAs), in 2015 the sum of polyfluoroalkyl phosphoric acid esters (PAPs) were 15–20ng/g dry weight, the sum of fluorotelomer sulfonic acids (FTSAs) was 0.8–1.3ng/g, and the sum of perfluorooctane sulfonamides and ethanols ranged from non-detected to 3.2ng/g. Persistent PFSAs and PFCAs were detected at 1.9–3.9ng/g and 2.4–7.3ng/g dry weight, respectively. The influence of precursor compounds was further demonstrated by an observed substantial increase for a majority of the persistent PFCAs and PFSAs in water after waste water treatment. Perfluorohexanoic acid (PFHxA), perfluorooctanoic acid (PFOA), perfluorohexane sulfonic acid (PFHxS), and perfluorooctane sulfonic acid (PFOS) had a net mass increase in all WWTPs, with mean values of 83%, 28%, 37% and 58%, respectively. The load of precursors and intermediates in influent water and sludge combined with net mass increase support the hypothesis that degradation of precursor compounds is a significant contributor to PFAS contamination in the environment.

Characterization of occurrence, sources and sinks of perfluoroalkyl and polyfluoroalkyl substances (PFASs) in a tropical urban catchment

Understanding the sources, occurrence and sinks of perfluoroalkyl and polyfluoroalkyl substances (PFASs) in the urban water cycle is important to protect and utilize local water resources. Concentrations of 22 target PFASs and general water quality parameters were determined monthly for a year in filtered water samples from five tributaries and three sampling stations of an urban water body. Of the 22 target PFASs, 17 PFASs were detected with a frequency >93% including PFCAs: C4-C12 perfluoroalkyl carboxylates, C4, C6, C8, and C10 perfluoroalkane sulfonates, perfluorooctane sulfonamides and perfluorooctane sulfonamide substances (FOSAMs), C10 perfluoroalkyl phosphonic acid (C10 PFPA), 6:2 fluorotelomer sulfonic acid (6:2 FTSA) and C8/C8 perfluoroalkyl phosphinic acid (C8/C8-PFPIA). The most abundant PFASs in water were PFBS (1.4–55 ng/L), PFBA (1.0–23 ng/L), PFOS (1.5–24 ng/L) and PFOA (2.0–21 ng/L). In the tributaries, PFNA concentrations ranged from 1.2 to 87.1 ng/L except in the May 2013 samples of two tributaries, which reached 520 and 260 ng/L. Total PFAS concentrations in the sediment samples ranged from 1.6 to 15 ng/g d.w. with EtFOSAA, PFDoA, PFOS and PFDA being the dominant species. Based on water and sediment data, two types of sources were inferred: one-time or intermittent point sources and continuous non-point sources. FOSAMs and PFOS released continually from non-point sources, C8/C8 PFPIA, PFDoA and PFUnA was released from point sources. The highly water soluble short-chain PFASs including PFBA, PFPeA and PFBS remained predominantly in the water column. The factors governing solution phase concentrations appear to be compound hydrophobicity and sorption to suspended particles. Correlation of the dissolved phase concentrations with precipitation data suggested stormwater was a significant source of PFBA, PFBS, PFUnA and PFDoA. Negative correlations with precipitation indicated sources feeding FOSAA and FOSA directly into the tributaries.

Temporal trends of PFSAs, PFCAs and selected precursors in Australian serum from 2002 to 2013

Per- and polyfluoroalkyl substances (PFASs) are a family of compounds that includes numerous compound classes. To date, only a subset of these PFASs have been studied thoroughly in the general population. In this study, pooled serum samples from Australia collected in 2002–2013 were analyzed for PFASs according to gender and age (age categories of 0–4 years, 5–15 years, 16–30 years, 31–45 years, 46–60 years, and >60 years), in total 54 pooled samples and 4920 individuals. Compound classes included were perfluorocarboxylic acids (PFCAs), perfluorosulfonic acids (PFSAs), and two groups of PFCA precursor compounds; polyfluoroalkyl phosphate diesters (diPAPs), and fluorotelomer sulfonic acids (FTSAs). Several PFASs that were not reported in previous studies of Australian serum samples were found in this sample set including; diPAPs, FTSAs, perfluoropentane sulfonic acid (PFPeS), perfluoroheptane sulfonic acid (PFHpS), perfluoroheptane carboxylic acid (PFHpA), perfluoroundecanoic acid (PFUnDA), perfluorododecanoic acid (PFDoDA), and perfluorotridecanoic acid (PFTrDA). Various temporal trends were observed with a significant reduction (p < 0.05) between 2002 and 2013 for 8:2 FTSA, perflurohexane sulfonic acid (PFHxS), PFHpS, PFOS, and perflurooctanoic acid (PFOA). Levels of longer-chained PFDA and PFUnDA started to decrease more recently, between 2006 and 2013, while PFDoDA increased during the same time period. Higher levels in younger age groups (0–4 and 5–15 years) compared to adults (>15 years) were found for 8:2 FTSA and PFHpA, while levels of PFHpS, PFOS, PFUnDA, PFDoDA and PFTrDA were higher in adult age groups compared to younger age groups. Gender-specific patterns were seen for PFOA, PFHxS, PFHpS and PFOS, where levels were lower in women. Changes in manufacturing processes were reflected in the temporal time trends, and differences in bioaccumulation potential between homologues could be associated with age trends. Our results emphasize the importance of including emerging classes of PFASs in biomonitoring studies.

An alternative treatment method for fluorosurfactant-containing wastewater by aerosol-mediated separation

The treatment of fluorosurfactant-containing wastewater is still challenging nowadays. Here, a method is presented to remove fluorosurfactants from water, amongst others from electroplating wastewater. This elimination technique is based on the generation of gas bubbles in solution, enrichment and scavenging of fluorosurfactants by transport of the gas bubbles to the water surface. Finally the bubbles collapse and release an aerosol which is enriched with fluorosurfactants. By sampling of the released aerosols a mass balance was established for 6:2 fluorotelomer sulfonic acid (6:2 FTSA). Thereby 99.8% of the initial amount was revocered in the collected aerosols. Fluorosurfactant concentration in solution decreased exponentially with half-lives ranging from 2 to 6 min for 6:2 FTSA as well as perfluorooctane carboxylate (PFOA) and perfluorooctane sulfonate (PFOS). Elimination rate in defined matrix (0.2 M H2SO4) within 60 min was 99.6, 99.9 and 99.8% for 6:2 FTSA, PFOA and PFOS, respectively. The removal rate of 6:2 FTSA increased in solutions with higher ionic strength. Different wastewater from an electroplating industry containing 6:2 FTSA was treated with the described method without any sample pre-treatment and elimination of 6:2 FTSA took place with the same effectiveness as in synthetic matrices.

Potential exposure routes and accumulation kinetics for poly- and perfluorinated alkyl compounds for a freshwater amphipod: Gammarus spp. (Crustacea)

Gammarids were exposed to sediments from a deposition site located on the Rhône River (France) downstream of a fluoropolymer manufacturing plant. Gammarids accumulated to various extents four long-chain perfluoroalkyl carboxylic acids (PFCAs) from C9 to C13, one sulfonate, perfluorooctane sulfonate (PFOS) and three of its precursors (the perflurooctane sulfonamide (FOSA), the N-methyl perfluorooctane sulfonamidoacetic acid (MeFOSAA), the N-ethyl perfluorooctane sulfonamidoacetic acid (EtFOSAA) and the 6:2 fluorotelomer sulfonic acid (6:2 FTSA). Whatever the compound, the steady state was not achieved after a 3-week exposure; elimination was almost complete after a 3-week depuration period for perfluorononanoic acid (PFNA), PFOS, the three precursors and the 6:2FTSA. However, this was not the case for long-chain PFCAs, whose elimination rates decreased with increasing chain length. PFAS accumulation in gammarids occurred via the trophic and respiratory pathways, in proportions varying with the carbon chain length and the terminal moiety.

Microbial toxicity and biodegradability of perfluorooctane sulfonate (PFOS) and shorter chain perfluoroalkyl and polyfluoroalkyl substances (PFASs).

Perfluorooctane sulfonate (PFOS) and related perfluoroalkyl and polyfluoroalkyl substances (PFASs) are emerging contaminants that have been widely applied in consumer and industrial applications for decades. However, PFOS has raised public concern due to its high bioaccumulative character, environmental persistence, and toxicity. Shorter PFASs such as perfluorobutane sulfonate (PFBS) and polyfluoroalkyl compounds have been proposed as alternatives to PFOS but it is unclear whether these fluorinated substances pose a risk for public health and the environment. The objective of this research was to investigate the microbial toxicity and the susceptibility to microbial degradation of PFOS and several related fluorinated compounds, i.e., short-chain perfluoroalkyl and polyfluoroalkyl sulfonic and carboxylic acids. None of the compounds tested were toxic to the methanogenic activity of anaerobic wastewater sludge even at very high concentrations (up to 500 mg L-1). All PFASs evaluated were highly resistant to microbial degradation. PFOS was not reductively dehalogenated by the anaerobic microbial consortium even after very long periods of incubation (3.4 years). Similarly, the tested short chain perfluoroalkyl substances (i.e., PFBS and trifluoroacetic acid) and a polyfluoroalkyl PFOS analogue, 6 : 2 fluorotelomer sulfonic acid (FTSA) were also resistant to anaerobic biodegradation. Likewise, no conclusive evidence of microbial degradation was observed under aerobic conditions for any of the short-chain perfluoroalkyl and polyfluoroalkyl carboxylic acids tested after 32 weeks of incubation. Collectively, these results indicate that PFOS and its alternatives such as short chain perfluoroalkyl sulfonates and carboxylates and their polyfluorinated homologues are highly resistant to microbial degradation.

World-Wide Indoor Exposure to Polyfluoroalkyl Phosphate Esters (PAPs) and other PFASs in Household Dust.

Human exposure to perfluorooctanoic acid (PFOA) and other per- and polyfluoroalkyl substances (PFASs) is ongoing and in some cases increasing, despite efforts made to reduce emissions. The role of precursor compounds such as polyfluorinated phosphate esters (PAPs) has received increasing attention, but there are knowledge gaps regarding their occurrence and impact on human exposure. In this study, mono-, di-, and triPAPs, perfluorinated alkyl acids (PFAAs), saturated, and unsaturated fluorotelomer carboxylic acids (FTCA/FTUCAs), perfluoroalkane sulfonamides, and sulfonamidethanols (FOSA/FOSEs), and one fluorotelomer sulfonic acid (FTSA)) were compared in household dust samples from Canada, the Faroe Islands, Sweden, Greece, Spain, Nepal, Japan, and Australia. Mono-, di-, and triPAPs, including several diPAP homologues, were frequently detected in dust from all countries, revealing an ubiquitous spread in private households from diverse geographic areas, with significant differences between countries. The median levels of monoPAPs and diPAPs ranged from 3.7 ng/g to 1 023 ng/g and 3.6 ng/g to 692 ng/g, respectively, with the lowest levels found in Nepal and the highest in Japan. The levels of PAPs exceeded those of the other PFAS classes. These findings reveal the importance of PAPs as a source of PFAS exposure worldwide.

Bioaccumulation of perfluoroalkyl compounds in midge (Chironomus riparius) larvae exposed to sediment

Midge larvae (Chironomus riparius) were exposed to sediments from a deposition sampled at a site along the Rhône River (France) downstream of an industrial site releasing various perfluorinated chemicals. This sediment is characterized by high concentrations of perfluoroundecanoic acid (PFUnA) and perfluorotridecanoic acid (PFTrDA) and a low perfluorooctane sulfonate (PFOS) concentration. Concentrations of 23 perfluoroalkyl compounds, including C4–C14 carboxylate acids, C4–C10 sulfonates, and seven precursors, were analyzed in overlying and pore water, sediment, and larvae. Midge larvae accumulated carboxylate acids (C11–C14), PFOS, and two precursors (perfluorooctane sulfonamide: FOSA and 6:2 fluorotelomer sulfonic acid, 6:2 FTSA). These substances accumulated mainly during the fourth instar larvae exponential growth phase. Accumulation of 6:2 FTSA, PFUnA, and PFOS occured via trophic and tegumentary routes. Other compounds mainly accumulated from food. Kinetics followed a partition model, from which uptake and elimination constants were derived.