Unknown Polyfluoroalkyl Substances Research Articles

Machine learning-enhanced molecular network reveals global exposure to hundreds of unknown PFAS.

Unknown forever chemicals like per- and polyfluoroalkyl substances (PFASs) are difficult to identify. Current platforms designed for metabolites and natural products cannot capture the diverse structural characteristics of PFAS. Here, we report an automatic PFAS identification platform (APP-ID) that screens for PFAS in environmental samples using an enhanced molecular network and identifies unknown PFAS structures using machine learning. Our networking algorithm, which enhances characteristic fragment matches, has lower false-positive rate (0.7%) than current algorithms (2.4 to 46%). Our support vector machine model identified unknown PFAS in test set with 58.3% accuracy, surpassing current software. Further, APP-ID detected 733 PFASs in real fluorochemical wastewater, 39 of which are previously unreported in environmental media. Retrospective screening of 126 PFASs against public data repository from 20 countries show PFAS substitutes are prevalent worldwide.

Suspect, Nontarget Screening, and Toxicity Prediction of Per- and Polyfluoroalkyl Substances in the Landfill Leachate.

Landfills are the final stage of urban wastes containing perfluoroalkyl and polyfluoroalkyl substances (PFASs). PFASs in the landfill leachate may contaminate the surrounding groundwater. As major environmental pollutants, emerging PFASs have raised global concern. Besides the widely reported legacy PFASs, the distribution and potential toxic effects of numerous emerging PFASs remain unclear, and unknown PFASs still need discovery and characterization. This study proposed a comprehensive method for PFAS screening in leachate samples using suspect and nontarget analysis. A total of 48 PFASs from 10 classes were identified; nine novel PFASs including eight chloroperfluoropolyether carboxylates (Cl-PFPECAs) and bistriflimide (HNTf2) were reported for the first time in the leachate, where Cl-PFPECA-3,1 and Cl-PFPECA-2,2 were first reported in environmental media. Optimized molecular docking models were established for prioritizing the PFASs with potential activity against peroxisome proliferator-activated receptor α and estrogen receptor α. Our results indicated that several emerging PFASs of N-methyl perfluoroalkyl sulfonamido acetic acids (N-MeFASAAs), n:3 fluorotelomer carboxylic acid (n:3 FTCA), and n:2 fluorotelomer sulfonate (n:2 FTSA) have potential health risks that cannot be ignored.

A targeted and non-targeted discovery screening approach for poly-and per-fluoroalkyl substances in model environmental biota samples

A comprehensive analytical approach for targeted and non-targeted discovery screening of per- and polyfluoroalkyl substances (PFAS) was developed and applied to model complex environmental biotic samples. Samples were extracted by formic acid-acetonitrile solution and cleaned up and fractionated by SPE (WAX). Target PFAS quantification was performed by ultra-high performance liquid chromatography interfaced with a triple quadrupole mass spectrometer (UPLC-QqQ-MS/MS). Non-targeted analysis (NTA) PFAS screening was performed with UPLC coupled with a quadrupole-Exactive orbitrap high resolution mass spectrometer (UPLC-Q-Exactive-HRMS). An iterative exclusion (IE) approach was applied to data acquisition for NTA suspect screening to increase the potential for unknown PFAS discovery with MS/MS. A complex workflow in Compound Discoverer was set up to automate data processing of the PFAS suspects search. New mass lists and MS/MS databases, which included a large number of PFAS, were set up and introduced into the search for high-throughput structure identification using HRMS techniques. The integrated targeted-NTA method successfully analyzed for legacy and alternative PFAS in model environmental biota samples, namely polar bear liver and bird egg samples. Targeted analysis provided unequivocal identification of well known/established PFAS (mainly perfluoroalkyl acids) with quantification at very low levels. The NTA suspect screening was able to determine a broader range of PFAS. The data analysis method offered high-confidence annotations for PFAS despite lacking available authentic standards. Overall, the analytical coverage of PFAS was greater and elucidated other PFAS present in these model apex predators.

Advanced oxidation processes may transform unknown PFAS in groundwater into known products

Per- and polyfluoroalkyl substances (PFAS) are a group of fluorinated organic contaminants classified as persistent in the aquatic environment. Early studies using targeted analysis approaches to evaluate the degradation of PFAS by advanced oxidation processes (AOP) in real water matrices may have been misinterpreted due to the presence of undetected or unknown PFAS in these matrices. The aims of the present study were to (1) screen selected commercially available AOPs (UV, UV + H2O2, O3/H2O2) and UV photocatalysis in a pilot system using commercially used and novel photocatalysts (TiO2, boron nitride [BN]) for removing PFAS contaminants and (2) evaluate their role on the conversion of non-detected/unknown to known PFAS compounds in real groundwater used as drinking water supplies. Results indicated that, while AOPs have the potential to achieve removal of the EPA method 533 target PFAS compounds (PFDA [100%], PFNA [100%], PFOA [85–94%], PFOS [25–100%], PFHxS [3–100%], PFPeS [100%], PFBS [100%]), AOPs transformed non-detected/unknown longer-chain PFAS compounds to detectable shorter-chain ones under very high-dose AOP operating conditions, leading to an increase in ∑PFAS concentration ranging from 95% to 340%. As emerging PFAS treatment processes transition from lab-scale investigations of target PFAS to pilot testing of real water matrices, studies will need to consider impact of the presence of non-target long-chain PFAS to transform into targeted PFAS compounds. A promising approach to address the potential risks and unforeseen consequences could involve an increased reliance on adsorbable organic fluorine (AOF) analysis before and after advanced oxidation process (AOP) treatment.

Uncovering per- and polyfluoroalkyl substances (PFAS) with nontargeted ion mobility spectrometry-mass spectrometry analyses.

Because of environmental and health concerns, legacy per- and polyfluoroalkyl substances (PFAS) have been voluntarily phased out, and thousands of emerging PFAS introduced as replacements. Traditional analytical methods target a limited number of mainly legacy PFAS; therefore, many species are not routinely assessed in the environment. Nontargeted approaches using high-resolution mass spectrometry methods have therefore been used to detect and characterize unknown PFAS. However, their ability to elucidate chemical structures relies on generation of informative fragments, and many low concentration species are not fragmented in typical data-dependent acquisition approaches. Here, a data-independent method leveraging ion mobility spectrometry (IMS) and size-dependent fragmentation was developed and applied to characterize aquatic passive samplers deployed near a North Carolina fluorochemical manufacturer. From the study, 11 PFAS structures for various per- and polyfluorinated ether sulfonic acids and multiheaded perfluorinated ether acids were elucidated in addition to 36 known PFAS. Eight of these species were previously unreported in environmental media, and three suspected species were validated.

Untargeted Screening of Per- and Polyfluoroalkyl Substances (PFASs) in Airborne Particulate of Three Italian E-Waste Recycling Facilities

Poly- and perfluorinated alkyl substances (PFASs) are widely used in the electrical and electronic appliance industry to the point that waste of electrical and electronic equipment (WEEE), also known as e-waste, creates significant potential for PFAS exposure (by inhalation, ingestion, or dermal exposure) for people handling and recycling e-waste. The aim of this work was the development of an untargeted analytical approach in order to detect the presence of possible unknown PFASs in particulate matter collected in three Italian e-waste facilities through liquid chromatography coupled to high-resolution tandem mass spectrometry (LC-HR-MS/MS) in negative ionization mode. By means of three acquisition experiments, nine compounds were detected as candidate PFASs, and three were definitively confirmed by comparison with their authentic standards. Among these, bistriflimide (bis (trifluoromethylsulfonyl) imide), an ionic liquid with several promising technological applications, was the most abundant compound detected in all three recycling plants. This is the first study associating the presence of fluorinated ionic liquids with e-waste, and as these chemicals are not only toxic and persistent but also highly mobile, our results indicate the need to include them in future PFAS research. Only further data on their actual environmental diffusion will determine whether they are emerging pollutants or not.

A modified TOP assay to detect per- and polyfluoroalkyl substances in aqueous film-forming foams (AFFF) and soil.

Total oxidisable precursor (TOP) assay can oxidise some per- and polyfluoroalkyl substances (PFASs) and their precursors, most of which cannot be quantitatively detected so far, and convert them to detectable PFASs, such as perfluoroalkyl acids (PFAAs). However, the conversion is constrained by the complexity of the target samples, including co-existent organics, unknown PFAS precursors, and background. In this study, the TOP assay is modified to increase the oxidation and conversion efficiency by changing the initial concentration of target sample, increasing oxidising doses, time, temperature, etc. The modified TOP assay is applied to test several aqueous film-forming foams (AFFF) and a PFAS-contaminated soil extract. The sum concentrations of the detectable PFASs are increased by up to ∼534× in the AFFF samples and ∼7× in the PFAS-contaminated soil extract. The detectable fluorotelomer sulfonate (FTS, such as 6:2/8:2 FTS) is accounted as an oxidation indicator to monitor the oxidation and conversion progress of the oxidisable PFASs precursors to the detectable PFASs. Overall, the modified TOP assay could be an appropriate method for identifying missing PFASs mass in complex matrices by detecting the PFASs precursors effectively.

Comprehensive characterization of per- and polyfluoroalkyl substances in wastewater by liquid chromatography-mass spectrometry and screening algorithms

Per- and polyfluoroalkyl substances (PFASs) constitute a large category of synthetic environmental pollutants, many of which remain unknown and warrant comprehensive investigation. This study comprehensively characterized PFASs in fluorinated-industrial wastewater by nontarget, quasi-target and target analyses using liquid chromatography-high-resolution mass spectrometry and data-processing algorithms. The algorithms based on characteristic in-source neutral losses and isotopologue distributions were applied to screening and identifying PFASs, while semiquantitative and quantitative analyses were utilized to determine their concentrations and distributions in the wastewater. In total, 175 formulae of PFASs, including traditional, little-known and unknown species were identified and further ascertained in terms of concentrations and distributions. The total concentrations of PFASs in the wastewater were 5.3–33.4 μg mL−1, indicating serious pollution of PFASs. This study not only provides an efficient approach for screening and identification of unknown PFASs, but also presents a practicable and simple way to comprehensively depict environmental pollution signatures of PFASs.

Suspect Screening and Nontargeted Analysis of Per- and Polyfluoroalkyl Substances in a Lake Ontario Food Web.

Per- and polyfluoroalkyl substances (PFAS) are globally distributed in the natural environment, and their persistent and bioaccumulative potential illicit public concern. The production of certain PFAS has been halted or controlled by regulation due to their adverse effect on the health of humans and wildlife. However, new PFAS are continuously developed as alternatives to legacy PFAS. Additionally, many precursors are unknown, and their metabolites have not been assessed. To better understand the PFAS profiles in the Lake Ontario (LO) aquatic food web, a quadrupole time-of-flight mass spectrometer (QToF) coupled to ultrahigh-performance liquid chromatography (UPLC) was used to generate high-resolution mass spectra (HRMS) from sample extracts. The HRMS data files were analyzed using an isotopic profile deconvoluted chromatogram (IPDC) algorithm to isolate PFAS profiles in aquatic organisms. Fourteen legacy PFAAs (C5-C14) and 15 known precursors were detected in the LO food web. In addition, over 400 unknown PFAS features that appear to biomagnify in the LO food web were found. Profundal benthic organisms, deepwater sculpin(Myoxocephalus thompsonii), and Mysis were found to have more known precursors than other species in the food web, suggesting that there is a large reservoir of fluorinated substances in the benthic zone.

Targeted analysis and Total Oxidizable Precursor assay of several insecticides for PFAS

Targeted analysis for 24 Per- and Polyfluoroalkyl Substances (PFAS) was conducted on 10 insecticide formulations used on a United States Department of Agriculture crop research field. Perfluorooctane sulfonic acid (PFOS) was found in 6 of the 10 formulations with concentrations ranging from 3.92 to 19.2 mg/kg. Further analysis of soil and plant samples collected at the site found several additional PFAS, with PFOS being the most prominent. Suspect screening was then conducted on the formulations and provided several suspected PFAS in addition to the 24 targeted analyzed PFAS in 7 of the 10 samples, one of which showed no PFAS during targeted analysis. PFAS-precursor oxidation was then conducted on the two insecticide formulations with the greatest lists of suspected PFAS as validation of potential unknown PFAS in the formulations. This study revealed a previously unknown potential PFAS contamination source for rural and agricultural environments.

Gas Chromatography-(Cyclic) Ion Mobility Mass Spectrometry: A Novel Platform for the Discovery of Unknown Per-/Polyfluoroalkyl Substances.

Per- and polyfluoroalkyl substances (PFASs) have been widely used since the 1940s in industry and everyday household products. They also persist in the environment and bioaccumulate in humans and wildlife. Despite these concerns, the identities of most PFASs in environmental and biological samples are unknown. Herein, we describe a novel cyclic ion mobility mass spectrometer (cIMS), hyphenated with gas chromatography (GC) atmospheric pressure chemical ionization, that can reveal the presence of unknown PFASs on the basis of the ratio of their mass and collision cross section (CCS). Prediction of the CCS of ca. 20,000 chemicals used in industry and commerce indicates that most compounds characterized by CCS values that are less than the sum of 100 Å2 and one-fifth of their mass are either PFASs or polybrominated flame retardants. When this filter is applied to GC-cIMS data collected from a set of 20 indoor dust samples, PFAS compounds are revealed without prior knowledge of their occurrence. Validation of this approach was performed using SRM 2585, a standard reference material of household dust, by comparing the PFASs detected with those (tentatively) identified in previous studies. Chlorofluoro phthalimides tentatively identified previously were confirmed with a synthesized standard. The method also reveals the presence of chlorofluoro n-alkanes as an emerging class of "forever chemicals" that contaminate the indoor environment.

FindPFΔS: Non-Target Screening for PFAS─Comprehensive Data Mining for MS2 Fragment Mass Differences.

The limited availability of analytical reference standards makes non-target screening approaches based on high-resolution mass spectrometry increasingly important for the efficient identification of unknown PFAS (per- and polyfluoroalkyl substances) and their TPs. We developed and optimized a vendor-independent open-source Python-based algorithm (FindPFΔS = FindPolyFluoroDeltas) to search for distinct fragment mass differences in MS/MS raw data (.ms2-files). Optimization with PFAS standards, two pre-characterized paper and soil samples (iterative data-dependent acquisition), revealed Δ(CF2)n, ΔHF, ΔCnH3F2n-3, ΔCnH2F2n-4, ΔCnHF2n-5, ΔCnF2nSO3, ΔCF3, and ΔCF2O as relevant and selective fragment differences depending on applied collision energies. In a PFAS standard mix, 94% (36 of 38 compounds from 10 compound classes) could be found by FindPFΔS. The use of fragment differences was applicable to a wide range of PFAS classes and appears as a promising new approach for PFAS identification. The influence of mass tolerance and intensity threshold on the identification efficiency and on the detection of false positives was systematically evaluated with the use of selected HR-MS2-spectra (20,998) from MassBank. To this end, with the use of FindPFΔS, we could identify different unknown PFAS homologues in the paper extracts. FindPFΔS is freely available as both Python source code on GitHub (https://github.com/JonZwe/FindPFAS) and as an executable windows application (https://doi.org/10.5281/zenodo.6797353) with a graphical user interface on Zenodo.

Extractable organofluorine analysis: A way to screen for elevated per- and polyfluoroalkyl substance contamination in humans?

The ubiquitous occurrence of a few per- and polyfluoroalkyl substances (PFAS) in humans and the environment has been previously reported. However, the number of PFAS humans and the environment are potentially exposed to is much higher, making it difficult to investigate every sample in detail. More importantly, recent studies have shown an increasing fraction of potentially unknown PFAS in human samples. A screening tool for identifying samples of concern that may contain high PFAS levels, to be studied more thoroughly, is needed. This study presents a simplified workflow to detect elevated PFAS levels using extractable organofluorine (EOF) analysis. A fluorine mass balance analysis on samples with high EOF, targeting 63 PFAS, can then confirm the PFAS contamination. Whole blood samples from a cohort of individuals with historical drinking water contamination from firefighting foams (n=20) in Ronneby (Sweden) and a control group (n=9) with background exposure were used as a case study. The average EOF concentration in the Ronneby group was 234ng/mLF (<107-592ng/mLF) vs 24.8ng/mLF (17.6-37.8ng/mL F) in the control group. The large difference (statistically significant, p<0.05) in the EOF levels between the exposed and control groups would have made it possible to identify samples with high PFAS exposure only using EOF data. This was confirmed by target analysis, which found an average ∑PFAS concentration of 346ng/mL in the exposed group and 7.9ng/mL in the control group. The limit of quantification for EOF analysis (up to 107ng/mLF using 0.5mL whole blood) did not allow for the detection of PFAS levels in low or sub parts per billion (ng/mL) concentrations, but the results indicate that EOF analysis is a suitable screening method sensitive enough to detect elevated/significant/exposure above background levels by known or unknown PFAS.

Addressing Urgent Questions for PFAS in the 21st Century.

Despite decades of research on per- and polyfluoroalkyl substances (PFAS), fundamental obstacles remain to addressing worldwide contamination by these chemicals and their associated impacts on environmental quality and health. Here, we propose six urgent questions relevant to science, technology, and policy that must be tackled to address the "PFAS problem": (1) What are the global production volumes of PFAS, and where are PFAS used? (2) Where are the unknown PFAS hotspots in the environment? (3) How can we make measuring PFAS globally accessible? (4) How can we safely manage PFAS-containing waste? (5) How do we understand and describe the health effects of PFAS exposure? (6) Who pays the costs of PFAS contamination? The importance of each question and barriers to progress are briefly described, and several potential paths forward are proposed. Given the diversity of PFAS and their uses, the extreme persistence of most PFAS, the striking ongoing lack of fundamental information, and the inequity of the health and environmental impacts from PFAS contamination, there is a need for scientific and regulatory communities to work together, with cooperation from PFAS-related industries, to fill in critical data gaps and protect human health and the environment.

“Simultaneous targeted and non-targeted analysis of per- and polyfluoroalkyl substances in environmental samples by liquid chromatography-ion mobility-quadrupole time of flight-mass spectrometry and mass defect analysis”

Per- and polyfluoroalkyl substances (PFAS) represent a large group of synthetic organic compounds which exhibit unique properties and have been extensively used for consumer and industrial products, resulting in a widespread presence in the environment. Regulation requiring PFAS monitoring has been implemented worldwide due to their potential health and eco-toxicological effects. Targeted methods are commonly used to monitor between twenty to forty PFAS compounds, representing only a small fraction of the number of compounds that may be present. Consequently, there is an increasing interest in complementary non-targeted methods to screen and identify unknown PFAS compounds with the aim to improve knowledge and to generate more accurate models regarding their environmental mobility and persistence. This work details the development of a method that simultaneously provided targeted and non-targeted PFAS analysis. Ultra-high performance liquid chromatography (UHPLC) was coupled to ion mobility-quadrupole time of flight-mass spectrometry (IMS-QTOF-MS) and used to quantify known and screen unknown PFAS in environmental samples collected within the greater Sydney basin (Australia). The method was validated for the quantification of 14 sulfonate-based PFAS, and a non-targeted data analysis workflow was developed using a combination of mass defect analysis with common fragment and neutral loss filtering to identify fluorine-containing species. The optimised method was applied to the environmental samples and enabled the determination of 3–7 compounds from the targeted list and the detection of a further 56–107 untargeted PFAS. This simultaneous analysis reduces the complexity of multiple analyses, and allows for greater interrogation of the full PFAS load in environmental samples.

Extractable Organofluorine Analysis in Pooled Human Serum and Placental Tissue Samples from an Austrian Subpopulation-A Mass Balance Analysis Approach.

Embryos and fetuses are of major concern due to their high vulnerability. Previous studies demonstrated that human exposure to per- and polyfluoroalkyl substances (PFAS) may be underestimated because only a limited number of known PFAS can be measured. This investigation studied the total PFAS exposure by measuring the extractable organofluorine (EOF) in pooled maternal serum, placental tissue, and cord serum samples (total number of pooled samples: n = 45). The EOF was analyzed using combustion ion chromatography, and the concentrations of known PFAS were determined using ultraperformance liquid chromatography coupled with a tandem mass spectrometer. Using a mass balance analysis approach, the amount of unknown PFAS was estimated between the levels of known PFAS and EOF. The EOF levels ranged from 2.85 to 7.17 ng F/mL (21 PFAS were quantified) in the maternal serum, from 1.02 to 1.85 ng F/g (23 PFAS were quantified) in the placental tissue, and from 1.2 to 2.10 ng F/mL (18 PFAS were quantified) in the cord serum. An average of 24, 51, and 9% of EOF is unidentified in the maternal serum, placental tissue, and cord serum, respectively. The results show that the levels of unidentified EOF are higher in the placental tissue, suggesting accumulation or potential transformation of precursors in the placenta.

Per- and polyfluoroalkyl substances (PFAS) and total fluorine in fire station dust.

Per- and polyfluoroalkyl substances (PFAS) are a class of over 4,700 fluorinated compounds used in industry and consumer products. Studies have highlighted use of aqueous film-forming foams (AFFFs) as an exposure source for firefighters, but little is known about PFAS occurrence inside fire stations, where firefighters spend most of their shifts. In this study, we aimed to characterize PFAS concentrations and sources inside fire stations. We measured 24 PFAS (using LC-MS/MS) and total fluorine (using particle-induced gamma ray emission) in dust from multiple rooms of 15 Massachusetts stations, many of which (60%) no longer use PFAS-containing AFFF at all and the rest of which only use it very rarely. Compared to station living rooms, turnout gear locker rooms had higher dust levels of total fluorine (p<0.0001) and three PFAS: perfluorohexanoate (PFHxA), perfluoroheptanoate (PFHpA), and perfluorodecanoate (PFDoDA) (p<0.05). These PFAS were also found on six wipes of station turnout gear. By contrast, the dominant PFAS in living rooms was N-ethyl perfluorooctane sulfonamidoacetic acid (N-MeFOSAA), a precursor to perfluorooctane sulfonate (PFOS) that still persists despite phase-outs almost two decades ago. The Σ24PFAS accounted for less than 2% of fluorine in dust (n=39), suggesting the potential presence of unknown PFAS. Turnout gear may be an important PFAS source in stations due to intentional additives and/or contamination from firefighting activities.

Legacy and emerging per- and polyfluoroalkyl substances (PFASs) in Dagang Oilfield: Multimedia distribution and contributions of unknown precursors

A systematic survey was conducted on twenty-six per- and polyfluoroalkyl substances (PFASs) in fifty-one paired samples of surface water, sediment, and soil from Dagang Oilfield, Tianjin, China. Perfluorooctanoic acid, perfluorooctane sulfonic acid, p-perfluorous nonenoxybenzenesulfonate (OBS), and 6:2 fluorotelomer sulfonamidoalkyl betaine (6:2 FTAB) were ubiquitous in the oilfield with field log Kd of 1.3–2.2, indicating a high partition potential from surface water to sediment. Total petroleum hydrocarbons (TPH) are a predictor for PFAS contamination at oilfield. The concentrations of OBS and 6:2 FTAB were higher in surface water and sediment with elevated TPH level. With total oxidizable precursor assay, unknown precursors for C2–C3 perfluoroalkyl carboxylic acids (PFCAs) (57–99 mol%) contributed more than those for C4–C12 PFCAs in the three mediums. The unknown C4-, C6-, and C8-based precursors tended to be precursors for perfluoroalkyl sulfonates at the oilfield, and C8 fluorotelomer-based precursors particularly occurred in the surface water. The concentrations of C4- and C8-based precursors were found positively correlated with TPH levels (r = 0.67–0.72, p < 0.05), while C6 precursors may also come from other sources. Further studies are necessary to clarify the mass balance and risk assessment for unknown PFASs.

Rapid Characterization of Emerging Per- and Polyfluoroalkyl Substances in Aqueous Film-Forming Foams Using Ion Mobility Spectrometry-Mass Spectrometry.

Aqueous film-forming foams (AFFF) are mixtures formulated with numerous hydrocarbon- and fluoro-containing surfactants. AFFF use leads to environmental releases of unknown per- and polyfluoroalkyl substances (PFAS). AFFF composition is seldom disclosed, and their use elicits concerns from both regulatory agencies and the public because PFAS are persistent in the environment and potentially associated with adverse health effects. In this study, we demonstrate the use of coupled liquid chromatography, ion mobility spectrometry, and mass spectrometry (LC-IMS-MS) to rapidly characterize both known and unknown PFAS in AFFF. Ten AFFF formulations from seven brands were analyzed using LC-IMS-MS in both negative and positive ion modes. Untargeted analysis of the formulations was followed by feature identification of PFAS-like features utilizing database matching, mass defect and homologous series evaluation, and MS/MS fragmentation experiments. Across the tested AFFF formulations, we identified 33 homologous series; only ten of these homologous series have been previously reported. Among tested AFFF, the FireStopper (n = 85) contained the greatest number of PFAS-like features and Phos-Check contained zero. This work demonstrates that LC-IMS-MS-enabled untargeted analysis of complex formulations, followed by feature identification using data-processing algorithms, can be used for rapid exposure characterization of known and putative PFAS during fire suppression-related contamination events.

Per- and polyfluoroalkyl substances in Chinese and German river water – Point source- and country-specific fingerprints including unknown precursors

This study aimed at comparing source-specific fingerprints of per- and polyfluoroalkyl substances (PFASs) in river water from China and Germany, selected as countries with different histories of PFAS production. Samples were collected from up- and downstream of seven suspected point sources in autumn 2018. Amongst the 29 analyzed legacy and emerging PFASs, 24 were detected, with a sum ranging from 2.7 ng/L (Alz River) to 420,000 ng/L (Xiaoqing River). While mass flow estimates for the Xiaoqing River and Yangtze River (mean: 20 and 43 t/y, respectively) indicated ongoing high emissions of the legacy compound PFOA in China, its ether-based replacements HFPO-DA and DONA showed the highest contribution downstream of a German fluoropolymer manufacturing site (50% and 40% of ΣPFASs measured, respectively). In river water impacted by manufacturing sites for pharmaceutical and pesticide intermediates, the short-chain compound PFBS was the most prevalent substance in both countries. The German Ruhr River, receiving discharges from the electroplating industry, was characterized by the PFOS replacement 6:2 FTSA. Isomer profiling revealed a higher proportion of branched isomers in the Chinese Xi River and Xiaoqing River than in other rivers. This points to different synthesis routes and underlines the importance of differentiating between linear and branched isomers in risks assessments. Upon oxidative conversion in the total oxidizable precursor (TOP) assay, the increase of the short-chain compound PFBA was higher in German samples than in Chinese samples (88 ± 30% versus 12 ± 14%), suggesting the presence of a higher proportion of unknown precursors to PFBA in the German environment. Amongst the ether-based replacements, DONA and 6:2 Cl-PFESA were fully or partially degraded to non-targeted oxidation products, whereas HFPO-DA showed no degradation. This indicates that the inclusion of ether-based PFASs and their oxidation products in the TOP assay can help in capturing a larger amount of the unknown PFAS fraction.