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Here, we report a comparative study of different sum parameter analysis methods for the extraction of per- and polyfluoroalkyl substances (PFAS) from manufactured consumer products, which can be measured by combustion ion chromatography (CIC). Therefore, a hydrolysis-based extraction method was further developed, which accounts for the addition of hydrolyzable covalently bound polyfluoroalkylated side-chain polymers (SFPs) to the extractable organic fluorine portion of the mass balance proposed as "hydrolyzable organically bound fluorine" (HOF). To test this hypothesis, the method was applied to 39 different consumer products containing fluoropolymers or monomeric PFAS taken from four different categories: outdoor textiles, paper packaging, carpeting, and permanent baking sheets. We also evaluated the method's efficiency by extracting four synthesized fluorotelomer polyacrylate reference compounds. The total fluorine (TF) and extractable organically bound fluorine (EOF) values were measured through CIC using established protocols. The TF values ranged from sub-ppb to %-levels, depending on the compound class. All samples showed results for hydrolyzed organofluorine (HOF) between 0.03 and 76.3 μg/g, while most EOF values were lower (

Total fluorine was determined in 45 consumer product samples from the Swedish market which were either suspected or known to contain fluorinated polymers. Product categories included cookware (70-550 000 ppm F), textiles (10-1600 ppm F), electronics (20-2100 ppm F), and personal care products (10-630 000 ppm F). To confirm that the fluorine was organic in nature, and deduce structure, a qualitative pyrolysis-gas chromatography-mass spectrometry (pyr-GC/MS) method was validated using a suite of reference materials. When applied to samples with unknown PFAS content, the method was successful at identifying polytetrafluoroethylene (PTFE) in cookware, dental products, and electronics at concentrations as low as 0.1-0.2 wt%. It was also possible to distinguish between 3 different side-chain fluorinated polymers in textiles. Several products appeared to contain high levels of inorganic fluorine. This is one of the few studies to quantify fluorine in a wide range of consumer plastics and provides important data on the concentration of fluorine in materials which may be intended for recycling, along with insights into the application of pyr-GC/MS for structural elucidation of fluorinated polymers in consumer products.

Per- and polyfluoroalkyl substances (PFAS) are widely used for durable water-repellent finishing of different fabrics and textiles such as outdoor clothing, carpets, medical textiles and more. Existing PFAS extraction techniques followed by target analysis are often insufficient for detecting widely used side-chain fluorinated polymers (SFPs) that are barely or non-extractable. SFPs are typically copolymers consisting of a non-fluorinated backbone with perfluoroalkyl side-chains to obtain desired properties. We compared the accessible analytical information and performance of complementary techniques based on oxidation (dTOP and PhotoTOP assays), hydrolysis (THP assay), standard extraction, extractable organic fluorine (EOF), and total fluorine (TF) with five functional textiles and characterized 7 further textiles only by PhotoTOP oxidation. The results show that when applied directly to textile samples, dTOP and PhotoTOP oxidation and also hydrolysis (THP) are able to capture large fractions of TF in the form of perfluoroalkyl side-chains present in the textiles while methods relying on extracts (EOF, target and non-target analysis) yield much lower fractions of TF ( e.g. , factor ∼25-50 lower). The conversion of large fractions of the measured TF into PFCAs or FTOHs from fluorinated side chains is in contrast to previous studies. Concentrations ranged from -1 after oxidation/hydrolysis and -1 for TF, while EOF and target PFAS in extracts were detected at much lower concentrations (up to ∼60 mg F kg -1 ) (amount of fluorine is in the order: extraction ≪ EOF ≪ oxidation/hydrolysis ≤ TF). Perfluoroalkyl carboxylic acids (PFCAs) and fluorotelomer alcohols (FTOHs) from THP hydrolysis and PhotoTOP oxidation both represented chain-length distribution in the textiles showing that long-chain SFPs are still used in current textiles. Further advantages and disadvantages of the applied methods are discussed.

During thermal processes utilized in affixing fluoropolymer coatings dispersion to fibers and fabrics, coating components are vaporized. It is suspected that per- and polyfluoroalkyl substances (PFAS) from the dispersions may undergo chemical transformations at the temperatures used, leading to additional emitted PFAS thermal byproducts. It is important to characterize these emissions to support evaluation of the resulting environmental and health impacts. In this study, a bench-scale system was built to simulate this industrial process via thermal application of dispersions to fiberglass utilizing relevant temperatures and residence times in sequential drying, baking, and sintering steps. Experiments were performed with two commercially available dispersions and a simple model mixture containing a single PFAS (6:2 fluorotelomer alcohol [6:2 FTOH]). Vapor-phase emissions were sampled and characterized by several off-line and real-time mass spectrometry techniques for targeted and nontargeted PFAS. Results indicate that multiple PFAS thermal transformation products and multiple nonhalogenated organic species were emitted from the exit of the high temperature third (sintering) furnace when 6:2 FTOH was the only PFAS present in the aqueous mixture. This finding supports the hypothesis that temperatures typical of these industrial furnaces may also induce chemical transformations within the fluorinated air emissions. Experiments using the two commercial fluoropolymer dispersions indicate air emissions of part-per-million by volume (ppmv) concentrations of heptafluoropropyl-1,2,2,2-tetrafluoroethyl ether (Fluoroether E1), as well as other PFAS at operationally relevant temperatures. We suspect that E1 is a direct thermal decomposition product (via decarboxylation) of 2,3,3,3-tetrafluoro-2-(heptafluoropropoxy)propanoic acid (commonly referred to as HFPO-DA) present in the dispersions. Other thermal decomposition products, including the monomer, tetrafluoroethene, may originate from the PFAS used to stabilize the dispersion or from the polymer particles in suspension. This study represents the first researcher-built coating application simulator to report nontargeted PFAS emission characterization, real-time analyses, and the quantification of 30 volatile target PFAS. Implications : Thermal processes used to affix fluoropolymers to fabrics are believed to be a source of PFAS air emissions. These coating operations are used by many large and small manufacturers and typically do not currently require any air emissions control. This research designed and constructed a bench-scale system that simulates these processes and used several off-line and advanced real-time mass spectroscopy techniques to characterize PFAS air emissions from two commercial fluoropolymer dispersions. Further, as the compositions of commercial dispersions are largely unknown, a model three-component solution containing a single PFAS was used to characterize emissions of multiple PFAS thermal transformation products at operationally relevant conditions. This research shows that fluoropolymer fabric coating facilities can be sources of complex mixtures of PFAS air emissions that include volatile and semivolatile PFAS present in the dispersions, as well as PFAS byproducts formed by the thermal transformation of fluorocarbon and hydrocarbon species present in these dispersions.

Objectives: Perfluoroalkyl acid surfactants are used in the chemical industry for the synthesis of perfluoroalkyl polymers. In one Italian fluoropolymer plant and in the research and innovation center, two major perfluoroalkyl surfactants have been historically used: PFOA and ADV and a third, cC6O4 substituted PFOA from mid-2013. This work is summarizing occupational exposure to these chemicals in the period 2004-2021, assessed by biological monitoring. Moreover, taking advantage of the phasing out of PFOA, the elimination kinetics of PFOA in humans is investigated., Methods: Workers exposed to PFOA (from beginning of the sixties to 2013), ADV (since 1996), and/or cC6O4 (since 2012) in the production of fluoropolymers, in the synthesis, research, and analysis, were periodically surveyed from 2004, measuring the concentration of perfluoroalkyl acid surfactants in serum. Workers of the same plants, not directly exposed, were surveyed as well. Applying the first-order kinetics model, the half-life of PFOA was calculated., Results: 809 Workers were investigated with measurements of PFOA (n = 3692), ADV (n = 4288) and cC6O4 (n = 2272) in serum. In the production plant, median PFOA ranged from 1900 to 14 µg/l from 2004 to 2021; median ADV ranged from 434 to 86 µg/l from 2011 to 2021. For cC6O4 the detection percentage ranged from 9 to 47%; in detected samples median cC6O4 ranged from 3 to 16 µg/l in the period 2013-2021. Adopted mitigation measurements included: the phasing out of PFOA, the improvement of the plastomer and elastomer post-treatments; the reinforcement of the staff involved in prevention. Decreasing trends were observed for all chemicals along years (P value for linear trend of means < 0.01). For PFOA, a half-life of 3.16 (95% CI 2.98-3.37) years was calculated., Conclusions: In the study plants, several initiatives to reduce exposure and the risk associated with perfluoroalkyl surfactants were undertaken; results of biomonitoring show that they were effective, with a 5- to 136-fold reduction in the concentration of perfluoroalkyl compounds in the serum of workers., (© The Author(s) 2023. Published by Oxford University Press on behalf of the British Occupational Hygiene Society.)

A selective catalytic converter has been developed to quantify nitrous acid (HONO), a photochemical precursor to NO and OH radicals that drives the formation of ozone and other pollutants in the troposphere. The converter is made from a sulfonated tetrafluoroethylene-based fluoropolymer-copolymer (Nafion) that was found to convert HONO to NO with unity yield under specific conditions. When coupled to a commercially available NO x (=NO + NO 2 ) chemiluminescence (CL) analyzer, the system measures HONO with a limit of detection as low as 64 parts-per-trillion (ppt) (1 min average) in addition to NO x . The converter is selective for HONO when tested against other common gas-phase reactive nitrogen species, although loss of O 3 on Nafion is a potential interference. The sensitivity and selectivity of this method allow for accurate measurement of atmospherically relevant concentrations of HONO. This was demonstrated by good agreement between HONO measurements made with the Nafion-CL method and those made with chemical ionization mass spectrometry in a simulation chamber and in indoor air. The observed reactivity of HONO on Nafion also has significant implications for the accuracy of CL NO x analyzers that use Nafion to remove water from sampling lines.

Perfluorosulfonic acids (PFSAs) are a recalcitrant subclass of per- and polyfluoroalkyl substances (PFASs) linked to numerous negative health effects in humans. Scalable technologies that effectively destroy PFSAs will greatly reduce the future health and ecological impact of these "forever chemicals". Herein, we show that several PFSAs undergo facile mechanochemical destruction (MCD) in the presence of quartz sand (SiO 2 ). This process operates in the absence of solvent, at ambient temperature and pressure, generating a benign solid byproduct. Quantitative analysis of milled samples revealed high destruction efficiencies of 99.95% to 100% for five different PFSAs subjected to MCD conditions in the presence of SiO 2 only. Extensive nontargeted analysis showed that, during degradation, other PFASs form and are ultimately destroyed upon extended mechanochemical treatment. Direct polarization (DP) and cross-polarization (CP) solid-state nuclear magnetic resonance (SSNMR) spectroscopy showed abundant silicon-fluorine (Si-F) bond formation post-MCD, indicating that fluorine was secured in a stable reservoir. Collectively, these results identified the degradation profile for an environmentally sound and effective PFSA degradation process that is amenable to scale-up.

Large fluoropolymer manufacturing facilities are major known sources of per- and polyfluoroalkyl substances (PFAS), many of which accumulate in groundwater, surface water, crops, wildlife, and people. Prior studies have measured high PFAS concentrations in groundwater, drinking water, soil, as well as dry and wet deposition near fluoropolymer facilities; however, much less is known about near-source PFAS air concentrations. We measured airborne PFAS on PM 2.5 filters in close proximity to a major fluoropolymer manufacturing facility (Chemours' Fayetteville Works) located near Fayetteville, North Carolina, USA. Weekly PM 2.5 filter samples collected over a six-month field campaign using high-volume air samplers at locations 3.7 km apart, north-northeast and south-southwest of the facility were analyzed for thirty-four targeted ionic PFAS species by liquid chromatography coupled to electrospray ionization tandem mass spectrometry. Twelve emerging and ten legacy PFAS compounds were detected. Thirteen PFAS were found at higher concentrations in these nearfield samples than at regional background sites, suggesting a local source for these compounds. Five emerging and five legacy PFAS compounds had maximum concentrations exceeding 1 pg m -3 . PFBA, PFHxA, PFHxDA, PFOS, PMPA, NVHOS, PFO5DoA, and Nafion BP1 contributed the most to the total (legacy + emerging) PFAS concentration (86%). Six PFAS, specifically PFBA, PFOS, PFO5DoA, Nafion BP1, Nafion BP2, and Nafion BP4, provide a consistent representative profile of elevated species across the two sites (with detection frequency >50%). To our knowledge, this is the first study to report both legacy and emerging ionic PFAS in air in close proximity to a U.S. fluoropolymer manufacturing facility.

Over the past several years, the term PFAS (per- and polyfluoroalkyl substances) has grown to be emblematic of environmental contamination, garnering public, scientific, and regulatory concern. PFAS are synthesized by two processes, direct fluorination (e.g., electrochemical fluorination) and oligomerization (e.g., fluorotelomerization). More than a megatonne of PFAS is produced yearly, and thousands of PFAS wind up in end-use products. Atmospheric and aqueous fugitive releases during manufacturing, use, and disposal have resulted in the global distribution of these compounds. Volatile PFAS facilitate long-range transport, commonly followed by complex transformation schemes to recalcitrant terminal PFAS, which do not degrade under environmental conditions and thus migrate through the environment and accumulate in biota through multiple pathways. Efforts to remediate PFAS-contaminated matrices still are in their infancy, with much current research targeting drinking water.

To assess the effects of weathering on per- and polyfluoroalkyl substances (PFASs) from durable water repellent (DWR) clothing, thirteen commercial textile samples were exposed to elevated ultra violet (UV) radiation, humidity, and temperature in an aging device for 300 h, which mimics the lifespan of outdoor clothing. Before and after aging, the textile samples were extracted and analysed for the ionic PFASs (perfluoroalkyl acids (PFAAs), perfluorooctane sulfonamide (FOSA)) and volatile PFASs (fluorotelomer alcohols (FTOHs), acrylates (FTACs) and methacrylates (FTMACs)). Results showed that weathering can have an effect on PFASs used in DWR of outdoor clothing, both on the PFAS profile and on the measured concentrations. In most weathered samples the PFAA concentrations increased by 5- to more than 100-fold, while PFAAs not detected in the original textiles were detected in the weathered samples. DWR chemistries are based on side-chain fluorinated polymers. A possible explanation for the increase in concentration of the PFAAs is hydrolysis of the fluorotelomer based polymers (FTPs), or degradation of the FTOHs, which are used in the manufacturing of the FTPs. The concentrations of volatile PFASs also increased, by a factor up to 20. Suggested explanations are the degradation of the DWR polymers, making non-extractable fluorines extractable, or the transformation or degradation of unknown precursors. Further research is needed to unravel the details of these processes and to determine the transformation routes. This study shows that setting maximum tolerance limits only for a few individual PFASs is not sufficient to control these harmful substances in outdoor clothing., Competing Interests: Declaration of competing interest None., (Copyright © 2020 The Authors. Published by Elsevier Ltd.. All rights reserved.)

High concentrations of the main components in Scotchgard™ fabric protector products (pre-2002 and post-2002; side-chain fluorinated polymer surfactants, S1 and S2, respectively) were detected in biosolids samples from twenty pan-Canadian wastewater treatment plants (WWTPs). Based on mass spectrometric analysis, S1 and S2 can be named as side-chain perfluorooctane sulfonamide-urethane polymer and side-chain perfluorobutane sulfonamide-urethane polymer, respectively. S1 (with C 8 F 17 side-chain) concentrations ranged from 1.08-105 ng/g d.w. and S2 (with C 4 F 9 side-chain) concentrations ranged from 37.5-2051 ng/g d.w., which were much higher than that of other commonly monitored perfluoroalkyl substances (PFAS). S1 and S2 concentrations were significantly correlated (p < 0.001; r 2 = 0.6142) indicating similar source origins. A negative linear correlation was observed (p < 0.05) between concentrations of S1 (or S2) with the volume of WWTP treated wastewater per day per person (m 3 /person/day). The total concentration of 22 other PFAS ranged from 4.93 to 92.6 ng/g d.w., and approximately thirty times lower than S1 and S2 concentrations. The calculated elemental fluorine concentrations of ƩF S1&S2 were generally much higher than the sum of the other PFAS. PFAS concentrations in biosolids are likely underestimated without consideration of S1 and S2., (Crown Copyright © 2020. Published by Elsevier B.V. All rights reserved.)

Our previous report on pharmacokinetic (PK) evaluation of 6:2 fluorotelomer alcohol (6:2 FTOH) examined the biopersistence potential of its metabolites based on data published from single inhalation and occupational 6:2 FTOH exposure studies. We calculated internal exposure estimates of three key metabolites of 6:2 FTOH, of which 5:3 fluorotelomer carboxylic acid (5:3 acid) had the highest internal exposure and the slowest clearance. No oral repeated 6:2 FTOH exposure data were available at the time to fully characterize the biopersistence potential of the metabolite 5:3 acid. We recently received additional data on 6:2 FTOH and 5:3 acid, which included a 90-day toxicokinetic study report on repeated oral 6:2 FTOH exposure to rats. We reviewed the study and analyzed the reported 5:3 acid concentrations in plasma, liver, and fat using one-compartment PK modeling and calculated elimination rate constants (k el ), elimination half-lives (t 1/2 ) and times to steady state (t ss ) of 5:3 acid at three 6:2 FTOH doses. Our results showed that t ss of 5:3 acid in plasma and evaluated tissues were approximately close to 1 year, such that the majority of highest values were observed at the lowest 6:2 FTOH dose, indicating its association with the biopersistence of 6:2 FTOH. The results of our PK analysis are the first to characterize biopersistence potential of the 5:3 acid after repeated oral exposure to the parent compound 6:2 FTOH based on steady state PK parameters, and therefore, may have an impact on future study designs when conducting toxicity assays for such compounds., Competing Interests: Declaration of competing interest The authors disclose that they have no competing financial and other interests., (Published by Elsevier Inc.)

Poly- and per-fluoroalkyl substances (PFAS) and volatile methyl siloxanes (VMS) were monitored at 21 sites in the Global Atmospheric Passive Sampling (GAPS) Network. Atmospheric concentrations previously reported from 2009 were compared to concentrations measured at these sites in 2013 and 2015, to assess trends over 7 years of monitoring. Concentrations of the fluorotelomer alcohols (FTOHs) and fluorinated sulfonamides and sulfonamidoethanols (FOSAs and FOSEs) were stable at these sites from 2009 to 2015 with no significant difference (p > 0.05) in concentrations. Elevated concentrations of all the neutral PFAS were detected at the urban sites as compared to the polar/background sites. The perfluorosulfonic acids (PFSAs), meanwhile, saw a significant increase (p < 0.001) in concentrations from 2009 to 2015. The perfluorocarboxylic acids (PFCAs) had elevated concentrations in 2015, however, the difference was not statistically significant (p > 0.05). Concentrations of the PFSAs and the PFCAs were similar at all location types, showing the global reach of these persistent compounds. Concentrations of the cyclic VMS (cVMS) were at least an order of magnitude higher than the linear VMS (lVMS) and the PFAS. Octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) saw a weak significant increase in concentrations from 2009 to 2013 (p < 0.05), however, hexamethylcyclotrisiloxane (D3) had a strong significant decrease in concentrations from 2009 to 2015 (p < 0.01)., (Copyright © 2018 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Fluorinated durable water repellent (DWR) agents are used to obtain water and stain repellent textiles. Due to the on-going phase-out of DWRs based on side-chain fluorinated polymers (SFP) with "long" perfluoroalkyl chains, the textile industry lacks suitable alternatives with comparable material characteristics. The constant development and optimization of SFPs for textile applications initiated more than half a century ago has resulted in a robust and very efficient DWR-technology and textiles with exceptional hydro- and oleo-phobic properties. The industry is now in the predicament that the long-chain SFPs with the best technical performance have undesirable toxicological and environmental behaviour. This study provides a comprehensive overview of the technical performance of presently available fluorinated and non-fluorinated DWRs as part of a chemical alternatives assessment (CAA). The results are based on a study with synthetic outdoor fabrics treated with alternative DWRs and tested for repellency using industrial standard and complementary methods. Using this approach, the complex structure-property relationships of DWR-polymers could be explained on a molecular level. Both short-chain SFPs and non-fluorinated DWRs showed excellent water repellency and durability in some cases while short-chain SFPs were the more robust of the alternatives to long-chain SFPs. A strong decline in oil repellency and durability with perfluoroalkyl chain length was shown for SFP DWRs. Non-fluorinated alternatives were unable to repel oil, which might limit their potential for substitution in textile application that require repellency towards non-polar liquids., (Copyright © 2017. Published by Elsevier Ltd.)

Following the phase-out of long-chain per- and polyfluoroalkyl substances (PFASs), the textile industry had to find alternatives for side-chain fluorinated polymer based durable water repellent (DWR) chemistries that incorporated long perfluoroalkyl side chains. This phase-out and subsequent substitution with alternatives has resulted in a market where both fluorinated and non-fluorinated DWRs are available. These DWR alternatives can be divided into four broad groups that reflect their basic chemistry: side-chain fluorinated polymers, silicones, hydrocarbons and other chemistries (includes dendrimer and inorganic nanoparticle chemistries). In this critical review, the alternative DWRs are assessed with regards to their structural properties and connected performance, loss and degradation processes resulting in diffuse environmental emissions, and hazard profiles for selected emitted substances. Our review shows that there are large differences in performance between the alternative DWRs, most importantly the lack of oil repellence of non-fluorinated alternatives. It also shows that for all alternatives, impurities and/or degradation products of the DWR chemistries are diffusively emitted to the environment. Our hazard ranking suggests that hydrocarbon based DWR is the most environmentally benign, followed by silicone and side-chain fluorinated polymer-based DWR chemistries. Industrial commitments to reduce the levels of impurities in silicone based and side-chain fluorinated polymer based DWR formulations will lower the actual risks. There is a lack of information on the hazards associated with DWRs, in particular for the dendrimer and inorganic nanoparticle chemistries, and these data gaps must be filled. Until environmentally safe alternatives, which provide the required performance, are available our recommendation is to choose DWR chemistry on a case-by-case basis, always weighing the benefits connected to increased performance against the risks to the environment and human health., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

High resolution mass spectrometry (HRMS) was successfully applied to elucidate the structure of a polyfluorinated polyether (PFPE)-based formulation. The mass spectrum generated from direct injection into the MS was examined by identifying the different repeating units manually and with the aid of an instrument data processor. Highly accurate mass spectral data enabled the calculation of higher-order mass defects. The different plots of MW and the nth-order mass defects (up to n = 3) could aid in assessing the structure of the different repeating units and estimating their absolute and relative number per molecule. The three major repeating units were -C2H4O-, -C2F4O-, and -CF2O-. Tandem MS was used to identify the end groups that appeared to be phosphates, as well as the possible distribution of the repeating units. Reversed-phase HPLC separated of the polymer molecules on the basis of number of nonpolar repeating units. The elucidated structure resembles the structure in the published manufacturer technical data. This analytical approach to the characterization of a PFPE-based formulation can serve as a guide in analyzing not just other PFPE-based formulations but also other fluorinated and non-fluorinated polymers. The information from MS is essential in studying the physico-chemical properties of PFPEs and can help in assessing the risks they pose to the environment and to human health. Graphical Abstract ᅟ.

The elemental characteristics of the fluorine atom tell us that replacing an alkyl chain by a perfluoroalkyl or polyfluorinated chain in a molecule or polymer is consequential. A brief reminder about perfluoroalkyl chains, fluorocarbons and fluorosurfactants is provided. The outstanding, otherwise unattainable physicochemical properties and combinations thereof of poly and perfluoroalkyl substances (PFASs) are outlined, including extreme hydrophobic and lipophobic character; thermal and chemical stability in extreme conditions; remarkable aptitude to self-assemble into sturdy thin repellent protecting films; unique spreading, dispersing, emulsifying, anti-adhesive and levelling, dielectric, piezoelectric and optical properties, leading to numerous industrial and technical uses and consumer products. It was eventually discovered, however, that PFASs with seven or more carbon-long perfluoroalkyl chains had disseminated in air, water, soil and biota worldwide, are persistent in the environment and bioaccumulative in animals and humans, raising serious health and environmental concerns. Further use of long-chain PFASs is environmentally not sustainable. Most leading manufacturers have turned to shorter four to six carbon perfluoroalkyl chain products that are not considered bioaccumulative. However, many of the key performances of PFASs decrease sharply when fluorinated chains become shorter. Fluorosurfactants become less effective and less efficient, provide lesser barrier film stability, etc. On the other hand, they remain as persistent in the environment as their longer chain homologues. Surprisingly little data (with considerable discrepancies) is accessible on the physicochemical properties of the PFASs under examination, a situation that requires consideration and rectification. Such data are needed for understanding the environmental and in vivo behaviour of PFASs. They should help determine which, for which uses, and to what extent, PFASs are environmentally sustainable., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Fire training facilities are potential sources of per- and polyfluoroalkyl substances (PFASs) to the nearby environment due to the usage of PFAS-containing aqueous fire-fighting foams (AFFFs). The multimedia distribution of perfluoroalkyl carboxylates (PFCAs), perfluoroalkyl sulfonates (PFSAs), perfluorooctanesulfonamide (PFOSA) and 6:2 fluorotelomer sulfonate (FTSA) was investigated near a fire training facility at Stockholm Arlanda Airport in Sweden. The whole body burden of PFASs in European perch (Perca fluviatilis) was 334±80μg absolute and was distributed as follows: Gonad>liver≈muscle>blood>gill. The bioconcentration factor (BCF) and sediment/water partition coefficient (Kd) increased by 0.6-1.7 and 0.2-0.5 log units, respectively, for each additional CF2 moiety for PFCAs and PFSAs. PFAS concentrations in water showed no significant decreasing trend between 2009 and 2013 (p>0.05), which indicates that Stockholm Arlanda Airport may be an important source for long-term contamination of the nearby environment with PFASs., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Concentrations and spatial distribution of PFOS and PFOA in surface water from East Lake in Wuhan, Hubei, China were studied. The total concentration of PFCs ranged from 31.1 to 237 ng x L(-1), and the mean value was 115 ng x L(-1), revealing lake-wide contamination in East Lake. PFOS and PFOA were detected in all samples with maximum values of 132 ng x L(-1) and 158 ng x L(-1), respectively, whereas the mean values of PFOS and PFOA were 60.4 and 55.0 ng x L(-1), respectively. The highest concentrations of PFOS and PFOA were found in the eastern area of lake, followed by the southern area of lake, and the western and northern areas of East Lake were the least contaminated regions. The specific distribution and composition profile of PFOS and PFOA, and the lack of significant correlation between PFOS and PFOA, suggested that there were various sources of PFCs. The PFOS concentrations at 30 sample sites (63%) were greater than 43 ng x L(-1), which was used to estimate an avian wildlife value for PFOS. The PFOA concentrations at 20 sample sites (42%) were greater than 40 ng x L(-1), which was a health-based guidance level recommended by the State of New Jersey for PFOA.

Fluoropolymer based tile and fabric spray sealants were evaluated for the release of airborne fluoropolymer constituents and volatile organic compounds (VOCs) during typical product use scenarios in a simulated bathroom and a simulated recreational vehicle. Fluoride was quantified after oxygen bomb digestion of airborne spray collected from personal, area, and surface samples. VOCs were quantified by gas chromatography/mass spectrometry (GC/MS) and gas chromatography/flame ionization spectrometry (GC/FID). Tile grout sealant contained approximately 1% acrylic fluoropolymer resin and 90% VOCs not including propellants. VOCs were short- and medium- chain methylated isoparaffinic hydrocarbons. When horizontally spraying a bathroom shower floor, grout spray sealant released a non-detectable amount of fluoride (<0.8 µg/m3) and 400-1400 mg/m3 total VOCs. When vertically spraying a shower wall, up to 2.0 µg/m3 of fluoride and from 1000 to 2300 mg/m3 total VOCs were detected. Fabric spray sealant contained 1% acrylic fluoropolymer resin and approximately 90% VOCs including perchloroethylene (PERC). Fabric spray released from 0.5 to 2.3 µg/m3 fluoride inside a recreational vehicle in the absence of crosswinds and less than 0.5 µg/m3 fluoride in the presence of a 10 mph crosswind. VOC release measured 240-938 mg/m3 without crosswinds and 161-522 mg/m3 with crosswinds. These studies show that fluoropolymer constituents from fluorinated spray sealants were near non-detectable levels in the breathing zone in nearly all samples while VOCs were measured at elevated levels (>400 mg/m3). The toxicological consequences of elevated VOCs during sealant spraying and the effects of certain fluoropolymer constituents are discussed.

Introduction: In this study, we explore the identity of a range of polyfluorinated surfactants (PFS) used for food contact materials, primarily to impart oil and water repellency on paper and board. PFS are of interest, as they can be precursors of poly- and perfluorinated alkyl substances (PFAS), of which several are persistent and are found worldwide in human blood and in the environment., Materials and Methods: To determine the elemental composition of PFS, we combined information from patents, chemical suppliers and analyses of industrial blends using ultra performance liquid chromatography-negative electrospray ionisation quadrupole time-of-flight mass spectrometry., Results: At a high pH of 9.7, both non-ionic and anionic PFS were ionised and were recognised by negative mass defects of exact masses, and neutral fragment losses of n × 20 or n × 100 Da. More than 115 molecular structures were found in industrial blends from the EU, US and China, belonging to the groups of polyfluoroalkyl-mono- and di-ester phosphates (monoPAPS, diPAPS and S-diPAPS), -ethoxylates, -acrylates, -amino acids, -sulfonamide phosphates and -thio acids, together with residuals and synthesis byproducts. In addition, a number of starting materials such as perfluorooctane sulfonamide N-alkyl esters were analysed. Di- and trialkylated PAPS and S-diPAPS were found in migrates from European food contact materials., Conclusion: This study highlights the need to monitor for more types of PFS in order to map the sources of PFAS in humans and the environment.

The evolution of hydrogen from many hydrated cryo-preserved soft materials under electron irradiation in the transmission electron microscope can be observed at doses of the order of 1000 e nm(-2) and above. Such hydrogen causes artefacts in conventional transmission electron microscope or scanning transmission electron microscopy (STEM) imaging as well as in analyses by electron energy-loss spectroscopy. Here we show that the evolution of hydrogen depends on specimen thickness. Using wedge-shaped specimens of frozen-hydrated Nafion, a perfluorinated ionomer, saturated with the organic solvent DMMP together with both thin and thick sections of frozen-hydrated porcine skin, we show that there is a thickness below which hydrogen evolution is not detected either by bubble observation in transmission electron microscope image mode or by spectroscopic analysis in STEM electron energy-loss spectroscopy mode. We suggest that this effect is due to the diffusion of hydrogen, whose diffusivity remains significant even at liquid nitrogen temperature over the length scales and time scales relevant to transmission electron microscopy analysis of thin specimens. In short, we speculate that sufficient hydrogen can diffuse to the specimen surface in thin sections so that concentrations are too low for bubbling or for spectroscopic detection. Significantly, this finding indicates that higher electron doses can be used during the imaging of radiation-sensitive hydrated soft materials and, consequently, higher spatial resolution can be achieved, if sufficiently thin specimens are used in order to avoid the evolution of hydrogen-based artefacts.

Fluorotelomer polymers are used in a broad array of products in modern societies worldwide and, if they degrade at significant rates, potentially are a significant source of perfluorooctanoic acid (PFOA) and related compounds to the environment To evaluate this possibility, we incubated an acrylate-linked fluorotelomer polymer in soil microcosms and monitored the microcosms for possible fluorotelomer (FT) and perfluorinated-compound (PFC) degradation products using GC/MS and LC/MS/MS. This polymer scavenged FTs and PFCs aggressively necessitating development of a multistep extraction using two solvents. Aged microcosms accumulated more FTs and PFCs than were present in the fresh polymer indicating polymer degradation with a half-life of about 870-1400 years for our coarse-grained test polymer. Modeling indicates that more-finely grained polymers in soils might have half-lives of about 10-17 years assuming degradation is surface-mediated. In our polymer-soil microcosms, PFOA evidently was lost with a half-life as short as 130 days, possibly by polymer-catalyzed degradation. These results suggest that fluoratelomer-polymer degradation is a significant source of PFOA and other fluorinated compounds to the environment.

Samples of precipitation events (snow and rain) in Dalian, a typical coastal town in China, were analyzed for perfluorosulfonates (PFSAs) and perfluorocarboxylates (PFCAs) to investigate atmospheric contamination by these compounds. In the snow event on December 16, 2006, samples were collected from 21 different sites and in another 6 precipitation events, samples were collected from a single location. Four PFSAs (C4, C6, C8, C10) and seven PFCAs (C6-12) were analyzed. Among the homologues, perfluorooctane sulfonate (PFOS) concentrations were the highest with a geometric mean (GM) of 145 ng/L (n=21) during the snow event on December 16, 2006, followed by perfluorooctanoate (PFOA) with a GM of 24.7 ng/L (n=21). Concentrations of perfluorobutane sulfonate (PFBS), perfluorohexane sulfonate (PFHxS) and perfluoroheptanoate (PFHpA) were more than two orders of magnitude lower than that of PFOS. Other PFSAs and PFCAs were found to be below the limit of detection in all the samples. In other 6 precipitation events, PFSAs and PFCAs were detected approximately in the same order of magnitude in both snow and rain. The results indicate that wet deposition may be a potential transport mechanism of perfluorinated chemicals in the environment.

The temporal trends of perfluoroalkyl compounds (PFCs), including C7-C15 perfluorocarboxylates (PFCAs), perfluorosulfonates (PFSAs) and heptadecafluorooctane sulfonamide (PFOSA), were determined in lake trout collected between 1979 and 2004 from Lake Ontario. The average concentrations of total PFSAs (+/- standard error of the mean; range) increased from 20 ng g(-1) wet weight (+/- 4; 8-26) in 1979, peaked at 70 ng g(-1) (+/- 7; 58-91) in 1993, and were 46 ng g(-1) (+/- 10; 30-83) in 2004, with perfluorooctane sulfonate (PFOS) asthe most abundant PFC. The PFCAs exhibited similar temporal variation, with concentrations increasing from 1.4 ng g(-1) (+/- 0.1; 0.9-1.9) in 1979 to 9.4 ng g(1) (+/- 3.1; 3-17) in 1988, and were 6.8 ng g(-1) (+/- 1.0; 4.5-9.8) in 2004. Individual mean PFCA concentrations varied between 0.2 and 2 ng g(-1) (wet weight). Perfluorodecane sulfonate (PFDS) and PFOSA were the only compounds showing a declining trend in the past decade, after reaching a peak value in 1993. Branched C11 and C13 PFCA isomers were detected in the lake trout and confirmed in Niagara River suspended sediments, with trends in both matrices suggesting that declining emissions or use of products containing these isomers in part account for the observed PFCA trends in the mid-1990s. However, the most recent samples, comprised almost exclusively of linear isomers, indicate that current PFCA sources to Lake Ontario result from the telomerization process of linear telogens.

Flow cytometric measurements were used to investigate the toxic effect of perfluorobutanoic sulfonate (PFBS), perfluorooctane sulfonate (PFOS), perfluorohexanoic acid (PFHxA), perfluorooctanoic acid (PFOA), perfluorododecanoic acid (PFDoA), and perfluorotetradecanoic acid (PFTeA) on some membrane systems of the freshwater alga species Scenedesmus obliquus. Among the test compounds, PFOS, PFDoA, and PFTeA inhibited algal growth rate in a concentration-dependent manner while PFBS, PFHxA, and PFOA did not inhibit algal growth within the test concentration ranges. An enhancement of the mitochondrial membrane potential (MMP) and cell membrane permeability in S. obliquus was observed caused by exposure to PFOS, PFOA, PFDoA, and PFTeA. Both carbon chain length and acid group influenced the toxicity of PFAAs, where the toxicity increased with increasing carbon chain length for the compounds belonging to the same class. The observed effective concentrations lie in the micromole range and the test compounds disrupted membrane properties at concentrations below those associated with algal growth inhibition. Flow cytometry is proved to be a useful technique for toxicity testing with microalgae and provide additional information regarding the mode of action of PFAAs to algal species.

Neutral, volatile polyfluorinated alkyl substances (PFAS) were measured in environmental air samples at two different sites in Northern Germany in spring 2005. The sampling locations were chosen to cover a metropolitan and a rural site, the Hamburg city center, and Waldhof, a background monitoring site. An optimized and validated analytical protocol was used to analyze two sets of parallel high-volume air samples. For both sampling locations as well as for individual samples, field blanks were taken to monitor possible background contamination. Gas chromatography coupled to mass spectrometry using positive chemical ionization (GC/ PCI-MS) was used for quantitative analyses. This article describes the first air concentration data of volatile PFAS outside North America reported in the peer-reviewed literature. The wide distribution of fluorotelomer alcohols (FTOHs), fluorinated sulfonamides, and sulfonamidoethanols (FOSAs/FOSEs) in German environmental air is presented. Furthermore, two volatile PFAS, i.e., N-methyl fluorooctane sulfonamide (NMeFOSA) and 4:2 FTOH, were determined for the first time in environmental air. Minimum-maximum sigmaFTOH concentrations of 64-311 pg/m3 (remote) up to 150-546 pg/m3 (urban) and minimum-maximum sigmaFOSA + FOSE concentrations between 12 and 54 pg/m3 (remote) and 29 and 151 pg/m3 (urban) were determined. 8:2 FTOH and 6:2 FTOH were found to be the predominant POPs determined in Waldhof so far. Blank contamination was found to be negligible. A significant correlation was found with the ambient temperature for the partitioning of airborne FOSEs between the gaseous and particulate phase (R = 0.853), whereas FTOHs and FOSAs were almost exclusively found in the gaseous phase. Furthermore, highest airborne PFAS concentrations were determined at relatively high ambient temperatures. Correlation coefficients (R) for sigmaFTOH and sigmaFOSA + FOSE concentrations with temperature were 0.954 and 0.968, respectively. Finally, the PFAS concentrations determined in this study are set into context with levels of "classical" persistent organic pollutants (POPs) in the same region and PFAS data available for North America.

This article describes the optimisation and validation of an analytical method for the determination of volatile polyfluorinated alkyl substances (PFAS) in environmental air samples. Airborne fluorinated telomer alcohols (FTOHs) as well as fluorinated sulfonamides and sulfonamidoethanols (FOSAs/FOSEs) were enriched on glass-fibre filters (GFFs), polyurethane foams (PUFs) and XAD-2 resin by means of high-volume air samplers. Sensitive and selective determination was performed using gas chromatography/chemical ionisation-mass spectrometry (GC/CI-MS). Five mass-labelled internal standard (IS) compounds were applied to ensure the accuracy of the analytical results. No major blank problems were encountered. Recovery experiments were performed, showing losses of the most volatile compounds during extraction and extract concentration as well as strong signal enhancement for FOSEs due to matrix effects. Breakthrough experiments revealed losses of the most volatile FTOHs during sampling, while FOSAs/FOSEs were quantitatively retained. Both analyte losses and matrix effects could be remediated by application of adequate mass-labelled IS. Method quantification limits (MQLs) of the optimised method ranged from 0.2 to 2.5 pg/m(3) for individual target compounds. As part of the method validation, an interlaboratory comparison of instrumental quantification methods was conducted. The applicability of the method was demonstrated by means of environmental air samples from an urban and a rural location in Northern Germany.

In the presence of Nafion, single-walled carbon nanotubes (SWNTs) were easily dispersed into ethanol, resulting in a homogeneous SWNTs/Nafion suspension. After evaporating ethanol, a SWNTs/Nafion film with bifunctionality was constructed onto glassy carbon electrode (GCE) surface. Attributing to the strong cation-exchange ability of Nafion and excellent properties of SWNTs, the SWNTs/Nafion film-coated GCE remarkably enhances the sensitivity of determination of Cd(2+). Based on this, an electrochemical method was developed for the determination of trace levels of Cd(2+) by anodic stripping voltammetry (ASV). In pH 5.0 NaAc-HAc buffer, Cd(2+) was firstly exchanged and adsorbed onto SWNTs/Nafion film surface, and then reduce at -1.10 V. During the positive potential sweep, reduced cadmium was oxidized, and a well-defined stripping peak appeared at -0.84 V, which can be used as analytical signal for Cd(2+). The linear range is found to be from 4.0 x 10(-8) to 4.0 x 10(-6) mol L(-1), and the lowest detectable concentration is estimated to be 4.0 x 10(-9) mol L(-1). Finally, this method was successfully employed to detect Cd(2+) in water samples.

To understand the role of surface wettability in adhesion of cells, the attachment of two different marine algae was studied on hydrophobic and hydrophilic polymer surfaces. Adhesion of cells of the diatom Navicula and sporelings (young plants) of the green macroalga Ulva to an underwater surface is mainly by interactions between the surface and the adhesive exopolymers, which the cells secrete upon settlement and during subsequent colonization and growth. Two types of block copolymers, one with poly(ethylene glycol) side-chains and the other with liquid crystalline, fluorinated side-chains, were used to prepare the hydrophilic and hydrophobic surfaces, respectively. The formation of a liquid crystalline smectic phase in the latter inhibited molecular reorganization at the surface, which is generally an issue when a highly hydrophobic surface is in contact with water. The adhesion strength was assessed by the fraction of settled cells (Navicula) or biomass (Ulva) that detached from the surface in a water flow channel with a wall shear stress of 53 Pa. The two species exhibited opposite adhesion behavior on the same sets of surfaces. While Navicula cells released more easily from hydrophilic surfaces, Ulva sporelings showed higher removal from hydrophobic surfaces. This highlights the importance of differences in cell-surface interactions in determining the strength of adhesion of cells to substrates.

A rapid and simple method for separating and determining various environmentally harmful perfluorocarboxylic acids and perfluorosulfonates was successfully developed using high- performance liquid chromatography with conductimetric detection, for product and waste management of these compounds at manufacturing and processing sites. Compounds having C(3)-C(8) perfluoroalkyl groups were separated using a Tosoh TSKgel Super-ODS column and a mobile phase consisting of a mixture of methanol and aqueous NaH(2)PO(4) at several mixing ratios. The best detection limits for the compounds ranged from 0.12 to 0.66 mg l(-1) (ppm), and linear calibration graphs were obtained up to 87-109 mg l(-1). The combination of this method with concentration of the sample by solid-phase extraction with cartridges based on styrene-divinylbenzene-copolymer enabled the determination of approximately 50 microg l(-1) (ppb) for compounds with C(4)-C(8) perfluoroalkyl groups. This method was successfully used to monitor the artificial decomposition of the perfluorocarboxylic acid n-C(4)F(9)COOH induced by a photocatalyst.

Recent research in our group has shown that mixture-casting Nafion with quaternary ammonium bromides can increase the electrochemical flux of redox couples through the membrane and allow for larger redox species to diffuse to the electrode surface. The research has also suggested that when these salts are cast with Nafion micellar pore size is changing. Therefore, it was proposed that the quaternary ammonium salts could be employed to tailor the structure of the Nafion membrane for immobilizing enzymes in the polymer. For cations with a high affinity for the sulfonic acid groups of Nafion, the modified structure of Nafion can also help to stabilize the enzyme and increase activity by providing a protective outer shell and an ideal chemical environment that resists a decrease in pH within the pore structure. This research examines the ability to immobilize dehydrogenase enzymes in Nafion that has been modified with quaternary ammonium bromides. Fluorescence assays, fluorescence microscopy, and cyclic voltammetric studies were employed to analyze the ability to immobilize an enzyme within the membrane, to determine the activity of the immobilized enzyme and to examine the transport of coenzyme within the membrane. Dehydrogenase enzymes immobilized in tetrabutylammonium bromide/Nafion membranes have shown high catalytic activity and enzyme active lifetimes of greater than 45 days. A variety of dehydrogenase enzymes have been successfully immobilized in the membrane, including: alcohol dehydrogenase, aldehyde dehydrogenase, glucose dehydrogenase, and lactic dehydrogenase.

The quantities of chlorofluorocarbons (FCC's) used commercially in the United States and globally are reviewed, and estimates of environmental release from the applications are made. The results indicate that sizable quantities of the FCC's that have been produced have not yet reached the environment and that regulation of U.S. applications would partly reduce, but not end, the possible destruction of stratospheric ozone.

This report describes the death of a teenager due to inhalation of fluorocarbon aerosol propellants and presents a method for the determination of trichlorofluoromethane (fluorocarbon 11) and dichlorodifluoromethane (fluorocarbon 12) in post-mortem samples. The post-mortem blood and tissue levels of these fluorocarbons are also presented. The distribution of fluorocarbon 11 and fluorocarbon 12 is similar to that observed in chloroform deaths.

Because fluorocarbons can dissolve relatively large quantities of oxygen and carbon dioxide, there is considerable interest in utilizing them to develop new methods of extracorporael circulation, artificial red blood cells, and liquid breathing techniques. A method for the assay of fluorocarbon in blood is presented. The fluorocarbon is extracted from the blood with toluene, and fluoride is released from the fluorocarbon in the toluene extract by reaction with sodium biphenyl. The inorganic fluoride is then extracted with aqueous sodium acetate, the pH of the extract is adjusted, and the activity of the fluoride ion is read with a fluoride-specific ion electrode. The assay was effective for fluorocarbon concentrations in the range of 1 to 30 ppm.