Fluorotelomer Acrylates Research Articles

Atmospheric concentrations of per- and polyfluoroalkyl substances and their emissions at a waste recycling facility producing refuse-derived paper and plastics densified fuel

To better understand the types and concentrations of per- and polyfluoroalkyl substances (PFAS) emitted into the air from waste recycling facilities that produce refuse-derived paper and plastics densified fuel (RPF) from industrial waste, we conducted an air sampling campaign at a waste recycling facility in Japan. Both passive and active air sampling were conducted, and the samples collected were used to quantify the PFAS emitted into the air during the production of RPF. Overall, few ionic PFAS were detected in the air at the facility; however, high levels of neutral PFAS (8.21–53.4 ng/m3; 20.7–130 pmol/m3) were measured in the air near the heat molding machines. The two neutral PFAS detected at the highest concentrations were 6:2 fluorotelomer alcohol and 6:2 fluorotelomer methacrylate, which are currently unregulated under the Stockholm Convention, suggesting that product manufacturers have shifted away from using regulated PFAS. Small amounts of regulated PFAS such as 8:2 fluorotelomer methacrylate and 8:2 fluorotelomer acrylate were measured in some parts of the facility. Analysis of the concentrations of PFAS in the exhaust gas from the heat molding machines revealed neutral PFAS concentrations (537–2160 ng/m3; 1350–5040 pmol/m3) that were 1–2 orders of magnitude higher than those in the surrounding indoor air. The total emission of neutral PFAS from the facility to the environment was estimated to be 0.066–0.260 g/day (0.168–0.607 mmol/day), depending on whether air volume discharged as exhaust gas or as indoor ventilation was considered. A contribution analysis of the emissions revealed that treating the exhaust gas from the heat molding machines, which constitutes over 94 % of the total emissions, is very effective at reducing PFAS emissions from the facility.

PFAS emissions from functional textiles using micro-chamber and thermal desorption coupled to two-dimensional gas chromatography-time of flight mass spectrometry (TD-GC×GC-TOF MS)

Per- and polyfluoroalkyl substances (PFAS), in the polymeric form, have been used extensively in functional textiles, including firefighter's turnout gear (e.g., jackets and pants), where PFAS are applied to confer oil and water resistance. However, growing concerns over the persistence, potential toxicity, and environmental impact of PFAS have prompted a thorough assessment of potential exposure pathways. Here, we report the emission of PFAS from three firefighter turnout gear jackets at 38 °C. Volatile emissions from the three layers (outer layer, moisture barrier, and thermal liner) were collected onto sorbent tubes via dynamic headspace sampling using a micro-scale chamber device kept at 38 °C for one hour. The emission was characterized using thermal desorption (TD) coupled to two-dimensional gas chromatography - time-of-flight mass spectrometry (GC×GC–TOF MS). The enhanced separation capacity of GC×GC was essential due to the high number of compounds present in each sample, especially for the fabrics from used turnout gear jackets. Based on the filtering expressions, including two-dimensional retention time (1tr and 2tr) and PFAS diagnostic fragment ions (m/z 69, 95, and 131), fluorotelomer alcohols (FTOHs) and fluorotelomer acrylates were identified using standards and spectral matching with the NIST database. After conducting a non-targeted tile-based workflow, jackets (both used and unused) and layers were compared, resulting in the identification of the top 15 discriminating features from over 400 chromatographic peaks. Finally, preliminary FTOH emission experiments showed some usage and layers trends that are aligned with those reported using solvent extraction. Highest levels of FTOHs were found in the moisture barrier, followed by the outer layer and the thermal liner. Older jackets emitted higher levels of 8:2 FTOH and 10:2 FTOH than a newer jacket. In contrast, a newer jacket used for one year had emissions containing higher levels of 6:2 FTOH. Investigating routes of exposure and identifying new PFAS targets are critical steps in evaluating the environmental and health impacts of these persistent chemicals.

Target and non-target analyses of neutral per- and polyfluoroalkyl substances from fluorochemical industries using GC-MS/MS and GC-TOF: Insights on their environmental fate

Novel and emerging per- and polyfluoroalkyl substances (PFAS) are a key issue of concern in global environmental studies. In this study, air, sediment, and wastewater samples were collected from areas in and/or surrounded by fluorochemical-related industrial facilities to characterize the contamination profiles of neutral and novel PFAS (n-PFAS) using a gas chromatograph-based target and non-target analyses. Fluorotelomer alcohols were predominant in the samples, accounting for 80 % of the n-PFAS, followed by fluorotelomer acrylates. Air samples collected proximate to the durable water repellent (DWR) facility had the highest concentration of n-PFAS, which was approximately two orders of magnitude higher than those found in others. Non-target analysis identified fluorotelomer iodides and fluorotelomer methacrylate in multiple matrices near DWR facilities, indicating significant contamination of n-PFAS. Levels of both C6- and C8-based PFAS reflected a shift in usage patterns from C8- to C6-based fluorochemicals. Matrix-dependent profiles of n-PFAS revealed that shorter-chain (e.g., C6) and longer-chain (>C8) PFAS were predominant in air and sediment, respectively, implying that air and sediment are mobile and secondary sources of PFAS. Untreated and treated industrial wastewater also contained n-PFAS and their transformation products. The findings shed light on our understanding of the multi-matrix distribution and transport of PFAS.

Querying the In Vitro Proteome Cysteine Reactivity of 8:2 Fluorotelomer Acrylate.

Despite the phase out of legacy per- and polyfluoroalkyl substances (PFAS), fluorotelomer-based polymers (FTP) have been used for many applications, notably textile surface coatings. FTPs are of a health concern due to their breakdown into legacy PFAS and the co-occurrence of fluorotelomer acrylate (FTAC) monomers, of which the latter may potentially react with cellular thiols. To evaluate this hypothesis, we employed fluorous-solid-phase extraction (FSPE), to enrich peptides covalently modified by 8:2 fluorotelomer acrylate (8:2 FTAC) and coupled it to a modified nano-liquid chromatography method for the identification of in vitro protein adducts using bottom-up data-dependent proteomics analysis. Using this method, over 100 unique peptides were detected with 8:2 FTAC modifications, although none of the modified cysteine residues were annotated active site nucleophiles. In parallel, a synthetic C6F13-iodoacetamide (F13-IAM) chemical probe was used to gauge the upper bound of PFAS-thiol reactivity. Over seven hundred peptides were detected with modifications but only 9 of 28 annotated active site cysteines in this dataset were modified by F13-IAM. Further exploration of the impacts of 8:2 FTAC adducts on protein function revealed that 8:2 FTAC modification promotes protein aggregation in vitro. These results suggest that 8:2 FTAC may exhibit significant proteome thiol reactivity and imply a more general mechanism of toxicity of PFAS-induced protein aggregation.

Henry’s Law constants of 15 per- and polyfluoroalkyl substances determined by static headspace analysis

While it is thought that some per- and polyfluoroalkyl substances (PFAS) may volatilize from aqueous solutions, experimentally measured Henry’s Law constants (kH, synonymous with air : water partition coefficient) are scarce. This leads to a lack of understanding of the partitioning of PFAS and an inability to predict concentrations above contaminated groundwater (e.g., vapor intrusion). We measured kH for 27 PFAS via headspace analysis and manipulations of the gas to liquid phase ratio. Fifteen PFAS produced mass spectrometry signals suitable for kH measurements. At 25 °C the experimentally measured dimensionless kH were: 0.31 – 2.82 for four fluorotelomer alcohols (FTOHs), 0.09 – 0.18 for three fluorotelomer sulfonates (FTSs), 0.30 – 1.01 for three iodinated PFAS, 0.43 – 0.92 for two sulfonamides, 3.86 for 6:2 fluorotelomer olefin, 0.69 for 8:2 fluorotelomer carboxylic acid, and 0.32 for 8:2 fluorotelomer acrylate. Longer fluoroalkyl chain length resulted in increased kH for FTOHs and FTSs, the only two groups in which chain length was studied. Perfluorinated sulfonates and carboxylates were generally not volatile enough to be measured, even at pH as low as 1, although fluorotelomers of both functional groups were measurably volatile. Temperature effects were well described by the van’t Hoff equation. kH was not significantly different in various environmentally relevant matrices demonstrating the broad applicability of the produced constants.

Theoretical evidence for the formation of perfluorocarboxylic acids form atmospheric oxidation degradation of fluorotelomer acrylates.

The atmospheric oxidation degradation of fluorotelomer acrylates (FTAcs) has been proposed as a potential source of perfluorocarboxylic acids (PFCAs) in remote locations. In this paper, detailed reactions of the main oxidant OH radicals with 4:2 FTAc in the atmosphere have been investigated by using density functional theory (DFT) calculation. All possible pathways involved in the oxidation process were presented and discussed. Based on the mechanism, transition state theory (TST) was used to predict the rate constants of the key elementary steps including the initial reactions of OH radical with n:2 FTAcs and the subsequent reactions of the main intermediates. Studies show that the reaction processes of OH radical addition to C = C bond are dominant and the fluorotelomer glyoxylate and formaldehyde are the major products. At 296K, the calculated overall rate constant of 4:2 FTAc with OH radical is 1.19 × 10-11 cm3 molecule-1s-1 with an atmospheric lifetime of 23.3h. In the atmosphere, fluorotelomer glyoxylate will continue to be oxidized, which will lead to the formation of PFCAs ultimately. In addition, atmospheric reactions of more carbons FTAc (CnF2n+1CH2CH2OC(O)CH = CH2, n = 6, 8, 10) are also discussed in the presence of O2/NOx.

Simultaneous determination of 11 volatile perfluorinated compound precursors in textiles using gas chromatography-triple quadrupole mass spectrometry

以甲醇为提取溶剂,超声辅助提取纺织品中的全氟化合物前体物,建立了一种气相色谱-三重四极杆质谱(GC-MS/MS)法同时测定纺织品中11种挥发性全氟化合物前体物:4种氟调聚物醇(FTOHs)、3种氟调聚丙烯酸酯(FTAs)、2种全氟辛基磺酰胺(FOSAs)和2种全氟辛基磺酰胺乙醇(FOSEs)。考察了超声提取溶剂、提取温度和提取时间对提取效率的影响,最终确定用甲醇为提取溶剂,70 ℃下超声提取60 min,目标物经VF-WAXms毛细管柱(30 m×0.25 mm×0.25 μm)程序升温分离,GC-MS/MS多反应监测(MRM)模式检测,外标法定量。实验结果表明:11种挥发性全氟化合物前体物在10~500 μg/L范围内线性关系良好,相关系数(r)均不低于0.9984;以信噪比为3计算,检出限(LOD)为0.002~0.04 mg/kg;以信噪比为10计算,定量限(LOQ)为0.006~0.1 mg/kg;不同材质纺织品中,11种挥发性全氟化合物前体物在高、中、低3个添加水平下的回收率为73.2%~117.2%,相对标准偏差(RSD)为0.1%~9.4%(n=6)。该方法前处理简单,定性、定量准确,灵敏度高,重现性好,可有效用于纺织品中11种挥发性全氟化合物前体物的同时检测。实际样品分析发现,当前全氟化合物前体物已被应用于纺织品整理当中。该方法的建立对我国纺织品中全氟化合物前体物风险物质的管控和检测标准的制定具有一定的理论和现实意义。

Side-chain fluorotelomer-based polymers in children car seats.

Fabric and foam samples from popular children car seats marketed in the United States during 2018 were tested for fluorine content by particle-included gamma ray emission spectroscopy (PIGE, n=93) and X-ray photoelectron spectroscopy (XPS, n=36), as well as for per- and polyfluoroalkyl substances (PFAS) by liquid and gas chromatography mass spectrometry (LC/MS and GC/MS, n=36). PFAS were detected in 97% of the car seat samples analyzed with MS, with total concentrations of 43 PFAS (∑PFAS) up to 268ng/g. Fabric samples generally had greater ∑PFAS levels than foam and laminated composites of foam and fabric. The three fabric samples with the highest total fluorine content as represented by the highest PIGE signal were also subjected to ultraviolet (UV) irradiation and the total oxidizable precursor (TOP) assay. Results from these treatments, as well as the much higher organofluorine levels measured by PIGE compared to LC/MS and GC/MS, suggested the presence of side-chain fluorotelomer-based polymers (FTPs), which have the potential to readily degrade into perfluoroalkyl acids (PFAAs) under UV light. Furthermore, fluorotelomer (meth)acrylates were found to be indicators for the presence of (meth)acrylate-linked FTPs in consumer products, and thus confirmed that at least half of the tested car seats had FTP-treated fabrics. Finally, extraction of selected samples with synthetic sweat showed that ionic PFAS, particularly those with fluorinated carbons ≤8, can migrate from fabric to sweat, suggesting a potential dermal route of exposure.

Indoor exposure to per- and polyfluoroalkyl substances (PFAS) in the childcare environment

Per- and polyfluoroalkyl substances (PFAS) are widely used in stain-resistant carpets, rugs, and upholstery, as well as in waxes and cleaners, and are potential contaminants in the childcare environment. However, limited knowledge exists on the occurrence of PFAS in indoor environments, apart from residential homes. Here, we determined the occurrence and distribution of 37 neutral and ionic PFAS, including perfluoroalkyl carboxylates (PFCAs) perfluoroalkyl sulfonates (PFSAs), fluorotelomer alcohols (FTOHs), fluorotelomer sulfonates (FTSs), perfluorooctane sulfonamides and perfluorooctane sulfonamidoethanols (FOSAs/FOSEs), and fluorotelomer acrylates and fluorotelomer methacrylates (FTACs/FTMACs) in the childcare environment and estimated children’s exposure through dust ingestion and dermal absorption. We analyzed dust and nap mats, a commonly used item in many childcares, from eight facilities located in the United States. Twenty-eight PFAS were detected in dust with total PFAS concentrations (ΣPFAS) ranging from 8.1 to 3,700 ng/g and were dominated by the two neutral PFAS groups: ΣFTOH (n.d. – 3,100 ng/g) and ΣFOSA/FOSE (n.d. – 380 ng/g). The ionic PFAS were detected at lower concentrations and were dominated by 6:2 FTS and 8:2 FTS (median 12 and 5.8 ng/g, respectively). ΣPFAS concentrations in mats (1.6–600 ng/g) were generally an order of magnitude lower than in dust and were dominated by ΣFOSA/FOSE concentrations (n.d. – 220 ng/g). Daily intake of neutral PFAS in the childcare environment via dust ingestion was estimated at 0.20 ng/kg bw/day and accounted for 75% of the ΣPFAS intake. This higher exposure to neutral PFAS is concerning considering that many neutral PFAS are the precursors of toxic ionic PFAS, such as PFOA.

Sampling and simultaneous determination of volatile per- and polyfluoroalkyl substances in wastewater treatment plant air and water

Volatile per- and polyfluoroalkyl substances (PFASs) are often used as precursors in the synthesis of nonvolatile PFASs. The volatile PFASs, which include the perfluoroalkyl iodides (PFAIs), fluorotelomer iodides (FTIs), fluorotelomer alcohols (FTOHs), fluorotelomer olefins (FTOs), fluorotelomer acrylates (FTACs), and fluorotelomer methacrylates (FTMACs), are often produced starting from the telomerization process. These volatile compounds can be present in the air and water environment and can be transformed into highly persistent perfluoroalkyl carboxylic acids. With the exception of FTOHs, which are well studied, the determination of other volatile PFASs is also of prime importance in studying the sources and fate of PFASs. In this study, a method was developed to determine representative precursor compounds that included PFAIs, FTIs, FTOs, FTACs, and FTMACs in wastewater treatment plant (WWTP) air and water samples. The sampling and sample preparation step involved the use of solid-phase extraction (SPE) cartridges with HLB™ material to enrich the analyte. Gas chromatography with mass spectrometry was employed for the detection and quantification of the analytes. Method validation results showed high linearity and sensitivity in the positive electron ionization-selected ion monitoring mode (+EI-SIM). The absolute instrumental limits of detection were in the range of 0.5 to 2 pg. The method detection limit (MDL) in air was 1 ng/m3 with the exception of the FTACs which could be only be detected at concentrations higher than 40 ng/m3. The MDL in water was 10 ng/L. Direct spiking of the cartridges and analyte introduction by volatilization from the glass surface onto the SPE material had recoveries between 86 and 100%. The volatile PFASs were shown to readily partition into the air rather than into water. Consequently, large losses in the amount of PFASs were observed when these were spiked into the water.Graphical abstractWastewater treatment plant air and water samples were passed through HLB™ solid-phase materials. The eluates were injected onto a GC-MS system to simultaneously determine the volatile PFASs.

Is there a human health risk associated with indirect exposure to perfluoroalkyl carboxylates (PFCAs)?

The production and widespread use of poly- and perfluoroalkyl substances (PFAS) has led to their presence in the environment, wildlife, and humans. Particularly, the perfluoroalkyl carboxylates (PFCAs) are pervasive throughout the world and have been found at ng/mL concentrations in human blood. PFCAs, especially those having longer carbon chain lengths (≥C6), are associated with developmental and hormonal effects, immunotoxicity, and promote tumor growth in rodents through their role as PPARα agonists. Humans are directly exposed to PFCAs primarily through contaminated food, drinking water, and house dust. However, indirect exposure to PFCAs through the biotransformation of fluorotelomer-based substances may also be a significant, yet relatively underappreciated pathway. We are exposed to fluorotelomer-based substances through use of consumer products, ingestion of food, or from inhalation of dust particles, but the risk of this exposure has been largely uncharacterized. Here, we summarize the work that has been done to characterize toxicity of the classes of fluorotelomer-based substances shown to biotransform to PFCAs: the polyfluoroalkyl phosphate esters (PAPs), fluorotelomer alcohols (FTOHs), fluorotelomer iodides (FTIs), and fluorotelomer acrylate monomers (FTAcs). These fluorotelomer-based substances biotranform to yield PFCAs, yet also form bioactive intermediate metabolites, which have been observed to be more toxic than their corresponding PFCAs. We address what is known regarding the toxicity of the fluorotelomer-based substances and their metabolites, with focus on covalent binding to biological nucleophiles, such as glutathione, proteins, and DNA, as a possible mechanism of toxicity that may influence the risk of indirect exposure to PFCAs.

Neutral polyfluoroalkyl substances in the atmosphere over the northern South China Sea

Neutral Polyfluoroalkyl substances (PFASs) in the atmosphere were measured during a cruise campaign over the northern South China Sea (SCS) from September to October 2013. Four groups of PFASs, i.e., fluorotelomer alcohols (FTOHs), fluorotelomer acrylates (FTAs), fluorooctane sulfonamides (FOSAs) and fluorooctane sulfonamidoethanols (FASEs), were detected in gas samples. FTOHs was the predominant PFAS group, accounting for 95.2–99.3% of total PFASs (ΣPFASs), while the other PFASs accounted for a small fraction of ΣPFASs. The concentrations of ΣPFASs ranged from 18.0 to 109.9 pg m−3 with an average of 54.5 pg m−3. The concentrations are comparable to those reported in other marine atmosphere. Higher concentrations of ΣPFASs were observed in the continental-influenced samples than those in other samples, pointing to the substantial contribution of anthropogenic sources. Long-range transport is suggested to be a major pathway for introducing gaseous PFASs into the atmosphere over the northern SCS. In order to further understand the fate of gaseous PFASs during transport, the atmospheric decay of neutral PFASs under the influence of reaction with OH radicals and atmospheric physical processes were estimated. Concentrations of 8:2 FTOH, 6:2 FTOH and MeFBSE from selected source region to the atmosphere over the SCS after long-range transport were predicted and compared with the observed concentrations. It suggests that the reaction with OH radicals may play an important role in the atmospheric decay of PFAS during long-range transport, especially for shorted-lived species. Moreover, the influence of atmospheric physical processes on the decay of PFAS should be further considered.

Simultaneous determination of perfluoroalkyl iodides, perfluoroalkane sulfonamides, fluorotelomer alcohols, fluorotelomer iodides and fluorotelomer acrylates and methacrylates in water and sediments using solid-phase microextraction-gas chromatography/mass spectrometry

Here, we developed and validated a headspace-solid-phase microextraction-gas chromatography/mass spectrometry (HS-SPME-GC/MS) method for the determination of 14 volatile perfluorinated alkylated substances (PFASs) in water and sediment samples according to SANTE 11945/2015 guidelines. Three fluorotelomer alcohols (FTOHs), two perfluoroalkyl iodides (PFIs), three fluorotelomer iodides (FTIs), four fluorotelomer acrylates and methacrylates (FTACs and FTMACs) and two perfluoroalkyl sulfonamides (FASAs) were analysed simultaneously to assess the occurrence of these compounds from their emission sources to the outlets in water treatment plants. Several SPME parameters were optimised for both water and sediment to maximise responses and keep analysis time to a minimum. In tap water, the limits of quantification (LOQs) were found to be between 20ng/L and 100ng/L depending on the analyte, with mean recoveries ranging from 76 to 126%. For sediments, LOQs ranged from 1 to 3ng/g dry weight depending on the target compound, with mean recoveries ranging from 74 to 125%. SPME considerably reduced sample preparation time and its use provided a sensitive, fast and simple technique. We then used this HS-SPME-GC/MS method to investigate the presence of volatile PFASs in the vicinity of an industrial facility. Only 8:2 FTOH and 10:2 FTOH were detected in a few water and sediment samples at sub-ppb concentration levels. Moreover, several non-target fluorotelomers (12:2 FTOH, 14:2 FTOH and 10:2 FTI) were identified in raw effluent samples. These long-chain fluorotelomers have high bioaccumulative potential in the aquatic environment compared with short-chain fluorotelomers such as 6:2 FTOH and 6:2 FTI.

Aqueous phase hydration and hydrate acidity of perfluoroalkyl and n:2 fluorotelomer aldehydes

ABSTRACTThe SPARC software program and comparative density functional theory (DFT) calculations were used to investigate the aqueous phase hydration equilibrium constants (Khyd) of perfluoroalkyl aldehydes (PFAlds) and n:2 fluorotelomer aldehydes (FTAlds). Both classes are degradation products of known industrial compounds and environmental contaminants such as fluorotelomer alcohols, iodides, acrylates, phosphate esters, and other derivatives, as well as hydrofluorocarbons and hydrochlorofluorocarbons. Prior studies have generally failed to consider the hydration, and subsequent potential hydrate acidity, of these compounds, resulting in incomplete and erroneous predictions as to their environmental behavior. In the current work, DFT calculations suggest that all PFAlds will be dominantly present as the hydrated form in aqueous solution. Both SPARC and DFT calculations suggest that FTAlds will not likely be substantially hydrated in aquatic systems or in vivo. PFAld hydrates are expected to have pKa values in the range of phenols (ca. 9 to 10), whereas n:2 FTAld hydrates are expected to have pKa values ca. 2 to 3 units higher (ca. 12 to 13). In order to avoid spurious modeling predictions and a fundamental misunderstanding of their fate, the molecular and/or dissociated hydrate forms of PFAlds and FTAlds need to be explicitly considered in environmental, toxicological, and waste treatment investigations. The results of the current study will facilitate a more complete examination of the environmental fate of PFAlds and FTAlds.

Neutral polyfluorinated compounds in indoor air in Germany – The LUPE 4 study

Perfluoroalkyl- and polyfluoroalkyl-substances (PFAS) have been detected in many types of environmental media and biota including humans. We determined volatile PFAS, including fluorotelomer alcohols (FTOHs), fluorotelomer acrylates (FTACs), perfluorooctane sulfonamides (FOSAs), and perfluorooctane sulfonamidoethanols (FOSEs), in indoor air of residences and schools in Germany.FTOHs, FTACs, FOSEs, and FOSAs were quantified with median levels in schools (in residences) of 11,783pg/m3 (13,198pg/m3), 737pg/m3 (450pg/m3), 130pg/m3 (278pg/m3), and 243pg/m3 (110pg/m3), respectively.Using our data and previously published results in a simplified model based on the medians and 95th percentiles, the “typical” and “high” daily non-dietary exposures were calculated to be 4.2ng/kg body weight (9.9ng/kgb.w.) for Σ-FTOHs and 0.1ng/kgb.w. (0.8ng/kgb.w.) for Σ-FOSEs/FOSAs in children. Inhalation was the dominant intake pathway for FTOHs; however, dust ingestion contributed significantly to the total intake of FOSEs/FOSAs.In organisms, 8:2 FTOH is degraded to perfluorooctanoate (PFOA). Assuming that 1% of 8:2 FTOH is converted to PFOA, 8:2 FTOH exposure in Germany has a negligible contribution to the total daily PFOA exposure, which is mainly driven by dietary intake.

Matrix normalized MALDI-TOF quantification of a fluorotelomer-based acrylate polymer.

The degradation of fluorotelomer-based acrylate polymers (FTACPs) has been hypothesized to serve as a source of the environmental contaminants, perfluoroalkyl carboxylates (PFCAs). Studies have relied on indirect measurement of presumed degradation products to evaluate the environmental fate of FTACPs; however, this approach leaves a degree of uncertainty. The present study describes the development of a quantitative matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry method as the first direct analysis method for FTACPs. The model FTACP used in this study was poly(8:2 FTAC-co-HDA), a copolymer of 8:2 fluorotelomer acrylate (8:2 FTAC) and hexadecyl acrylate (HDA). Instead of relying on an internal standard polymer, the intensities of 40 poly(8:2 FTAC-co-HDA) signals (911-4612 Da) were normalized to the signal intensity of a matrix-sodium cluster (659 Da). We termed this value the normalized polymer response (P(N)). By using the same dithranol solution for the sample preparation of poly(8:2 FTAC-co-HDA) standards, calibration curves with coefficient of determinations (R(2)) typically >0.98 were produced. When poly(8:2 FTAC-co-HDA) samples were prepared with the same dithranol solution as the poly(8:2 FTAC-co-HDA) standards, quantification to within 25% of the theoretical concentration was achieved. This approach minimized the sample-to-sample variability that typically plagues MALDI-TOF, and is the first method developed to directly quantify FTACPs.

Neutral poly-/perfluoroalkyl substances in air and snow from the Arctic.

Levels of neutral poly-/perfluoroalkyl substances (nPFASs) in air and snow collected from Ny-Ålesund were measured and their air-snow exchange was determined to investigate whether they could re-volatilize into the atmosphere driven by means of air-snow exchange. The total concentration of 12 neutral PFASs ranged from 6.7 to 39 pg m−3 in air and from 330 to 690 pg L−1 in snow. A significant log-linear relationship was observed between the gas/particle partition coefficient and vapor pressure of the neutral PFASs. For fluorotelomer alcohol (FTOHs) and fluorotelomer acrylates (FTAs), the air-snow exchange fluxes were positive, indicating net evaporative from snow into air, while net deposition into snow was observed for perfluorooctane sulfonamidoethanols (Me/EtFOSEs) in winter and spring of 2012. The air-snow exchange was snow-phase controlled for FTOHs and FTAs, and controlled by the air-phase for FOSEs. Air-snow exchange may significantly interfere with atmospheric concentrations of neutral PFASs in the Arctic.

Microbial transformation of 8:2 fluorotelomer acrylate and methacrylate in aerobic soils

Biotransformation of fluorotelomer (FT) compounds, such as 8:2 FT alcohol (FTOH) is now recognized to be a source of perfluorooctanoic acid (PFOA) as well as other perfluoroalkyl acids. In this study, microbially mediated hydrolysis of FT industrial intermediates 8:2 FT acrylate (8:2 FTAC) and 8:2 FT methacrylate (8:2 FTMAC) was evaluated in aerobic soils for up to 105d. At designated times, triplicate microcosms were sacrificed by sampling the headspace for volatile FTOHs followed by sequential extraction of soil for the parent monomers as well as transient and terminal degradation products. Both FTAC and FTMAC were hydrolyzed at the ester linkage as evidenced by 8:2 FTOH production. 8:2 FTAC and FTMAC degraded rapidly with half-lives ⩽5d and 15d, respectively. Maximum 8:2 FTOH levels were 6–13mol% within 3–6d. Consistent with the known biotransformation pathway of 8:2 FTOH, FT carboxylic acids and perfluoroalkyl carboxylic acids were subsequently generated including up to 10.3mol% of PFOA (105d). A total mass balance (parent plus metabolites) of 50–75mol% was observed on the last sampling day. 7:2 sFTOH, a direct precursor to PFOA, unexpectedly increased throughout the incubation period. The likely, but unconfirmed, concomitant production of acrylic acids was proposed as altering expected degradation patterns. Biotransformation of 8:2 FTAC, 8:2 FTMAC, and previously reported 8:2 FT-stearate for the same soils revealed the effect of the non-fluorinated terminus group linked to the FT chain on the electronic differences that affect microbially-mediated ester cleavage rates.

Investigating the biodegradability of a fluorotelomer-based acrylate polymer in a soil-plant microcosm by indirect and direct analysis.

Fluorotelomer-based acrylate polymers (FTACPs) are a class of side-chain fluorinated polymers used for a variety of commercial applications. The degradation of FTACPs through ester hydrolysis, cleavage of the polymer backbone, or both could serve as a significant source of perfluoroalkyl carboxylates (PFCAs). The biodegradation of FTACPs was evaluated in a soil-plant microcosm over 5.5 months in the absence/presence of wastewater treatment plant (WWTP) biosolids using a unique FTACP determined to be a homopolymer of 8:2 fluorotelomer acrylate (8:2 FTAC). Although structurally different from commercial FTACPs, the unique FTACP possesses 8:2 fluorotelomer side chain appendages bound to the polymer backbone via ester moieties. Liberation and subsequent biodegradation of the 8:2 fluorotelomer appendages was indirectly determined by monitoring for PFCAs of varying chain lengths (C6-C9) and known fluorotelomer intermediates by liquid chromatography tandem mass spectrometry (LC-MS/MS). A FTACP biodegradation half-life range of 8-111 years was inferred from the 8:2 fluorotelomer alcohol (8:2 FTOH) equivalent of the unique FTACP and the increase of degradation products. The progress of FTACP biodegradation was also directly monitored qualitatively using matrix-assisted laser desorption/ionization (MALDI-TOF) time-of-flight mass spectrometry. The combination of indirect and direct analysis indicated that the model FTACP biodegraded predominantly to perfluorooctanoate (PFOA) in soils and at a significantly higher rate in the presence of a plant and WWTP biosolids.

Atmospheric concentrations and gas/particle partitioning of neutral poly- and perfluoroalkyl substances in northern German coast

Total 58 high volume air samples were collected in Büsum, Germany, from August 2011 to October 2012 to investigate air concentrations of 12 per- and polyfluoroalkyl substances (PFASs) and their gas/particle partitioning. The total concentration (vapor plus particle phases) of the 12 PFASs (ΣPFASs) ranged from 8.6 to 155 pg/m3 (mean: 41 pg/m3) while fluorotelomer alcohols 8:2 (8:2 FTOH) dominated all samples accounting for 61.9% of ΣPFASs and the next most species were 10:2 FTOH (12.7%). Air mass back trajectory analysis showed that atmospheric PFASs in most samples were from long range atmospheric transport processes and had higher ratios of 8:2 to 6:2 FTOH compared to the data obtained from urban/industrial sources. Small portion of particle PFASs in the atmosphere was observed and the average percent to ΣPFASs was 2.0%. The particle-associated fractions of different PFASs decreased from perfluorooctane sulfonamidoethanols (FOSEs) (15.5%) to fluorotelomer acrylates (FTAs) (7.6%) to perfluorooctane sulfonamides (FOSAs) (3.1%) and FTOHs (1.8%), indicating the functional group obviously influenced their gas/particle partitioning. For neutral compounds with acid dissociation constant (pKa) > 7.0 (i.e., FTOHs, FOSEs and FOSAs), a significant log-linear relationship was observed between their gas/particle partition coefficients (KSP) and vapor pressures (pºL), suggesting the gas/particle partitioning of neutral PFASs agreed with the classical logKSP–logpºL relation. Due to the pKa values of 6:2 and 8:2 FTA below the typical environmental pH conditions, they mainly exist as ionic form in aerosols, and the corrected logKSP (neutral form) were considerably lower than those of FTOHs, FOSEs and FOSAs with similar vapor pressures. Considering the strong partitioning potential to aqueous phases for ionic PFASs at higher pH values, a need exists to develop a model taking account of the ad/absorption mechanism to the condensed phase of aerosols for ionizable PFASs (e.g., FTAs).