Inputs, amplification and sinks of perfluoroalkyl substances at coastal Antarctica.

The sources, biogeochemical controls and sinks of perfluoroalkyl substances, such as perfluoroalkyl acids (PFAAs), in polar coastal regions are largely unknown. These were evaluated by measuring a large multi-compartment dataset of PFAAs concentrations at coastal Livingston and Deception Islands (maritime Antarctica) during three austral summers. PFAAs were abundant in atmospheric-derived samples (aerosols, rain, snow), consistent with the importance of atmospheric deposition as an input of PFAAs to Antarctica. Such PFAAs deposition was unequivocally demonstrated by the occurrence of PFAAs in small Antarctic lakes. Several lines of evidence supported the relevant amplification of PFAAs concentrations in surface waters driven by snow scavenging of sea-spray aerosol-bound PFAAs followed by snow-melting. For example, vertical profiles showed higher PFAAs concentrations at lower-salinity surface seawaters, and PFAAs concentrations in snow were significantly higher than in seawater. The higher levels of PFAAs at Deception Island than at Livingston Island are consistent with the semi-enclosed nature of the bay. Concentrations of PFOS decreased from 2014 to 2018, consistent with observations in other oceans. The sink of PFAAs due to the biological pump, transfer to the food web, and losses due to sea-spray aerosols alone are unlikely to have driven the decrease in PFOS concentrations. An exploratory assessment of the potential sinks of PFAAs suggests that microbial degradation of perfluoroalkyl sulfonates should be a research priority for the evaluation of PFAAs persistence in the coming decade.

A field-validated equilibrium passive sampler for the monitoring of per- and polyfluoroalkyl substances (PFAS) in sediment pore water and surface water.

A simple equilibrium passive sampler, consisting of water in an inert container capped with a rate-limiting barrier, for the monitoring of per- and polyfluoroalkyl substances (PFAS) in sediment pore water and surface water was developed and tested through a series of laboratory and field experiments. The objectives of the laboratory experiments were to determine (1) the membrane type that could serve as the sampler's rate-limiting barrier, (2) the mass transfer coefficient of environmentally relevant PFAS through the selected membrane, and (3) the performance reference compounds (PRCs) that could be used to infer the kinetics of PFAS diffusing into the sampler. Of the membranes tested, the polycarbonate (PC) membrane was deemed the most suitable rate-limiting barrier, given that it did not appreciably adsorb the studied PFAS (which have ≤8 carbons), and that the migration of these compounds through this membrane could be described by Fick's law of diffusion. When employed as the PRC, the isotopically labelled PFAS M2PFOA and M4PFOS were able to predict the mass transfer coefficients of the studied PFAS analytes. In contrast, the mass transfer coefficients were underpredicted by Br- and M3PFPeA. For validation, the PC-based passive samplers consisting of these four PRCs, as well as two other PRCs (i.e., M8PFOA and C8H17SO3-), were deployed in the sediment and water at a PFAS-impacted field site. The concentration-time profiles of the PRCs indicated that the samplers deployed in the sediment required at least 6 to 7 weeks to reach 90% equilibrium. If the deployment times are shorter (e.g., 2 to 4 weeks), PFAS concentrations at equilibrium could be estimated based on the concentrations of the PRCs remaining in the sampler at retrieval. All PFAS concentrations determined via this approach were within a factor of two compared to those measured in the mechanically extracted sediment pore water and surface water samples obtained adjacent to the sampler deployment locations. Neither biofouling of the rate-limiting barrier nor any physical change to it was observed on the sampler after retrieval. The passive sampler developed in this study could be a promising tool for the monitoring of PFAS in pore water and surface water.

The NORMAN Suspect List Exchange (NORMAN-SLE): facilitating European and worldwide collaboration on suspect screening in high resolution mass spectrometry.

Background: The NORMAN Association (https://www.norman-network.com/) initiated the NORMAN Suspect List Exchange (NORMAN-SLE; https://www.norman-network.com/nds/SLE/) in 2015, following the NORMAN collaborative trial on non-target screening of environmental water samples by mass spectrometry. Since then, this exchange of information on chemicals that are expected to occur in the environment, along with the accompanying expert knowledge and references, has become a valuable knowledge base for "suspect screening" lists. The NORMAN-SLE now serves as a FAIR (Findable, Accessible, Interoperable, Reusable) chemical information resource worldwide. Results: The NORMAN-SLE contains 99 separate suspect list collections (as of May 2022) from over 70 contributors around the world, totalling over 100,000 unique substances. The substance classes include per- and polyfluoroalkyl substances (PFAS), pharmaceuticals, pesticides, natural toxins, high production volume substances covered under the European REACH regulation (EC: 1272/2008), priority contaminants of emerging concern (CECs) and regulatory lists from NORMAN partners. Several lists focus on transformation products (TPs) and complex features detected in the environment with various levels of provenance and structural information. Each list is available for separate download. The merged, curated collection is also available as the NORMAN Substance Database (NORMAN SusDat). Both the NORMAN-SLE and NORMAN SusDat are integrated within the NORMAN Database System (NDS). The individual NORMAN-SLE lists receive digital object identifiers (DOIs) and traceable versioning via a Zenodo community (https://zenodo.org/communities/norman-sle), with a total of > 40,000 unique views, > 50,000 unique downloads and 40 citations (May 2022). NORMAN-SLE content is progressively integrated into large open chemical databases such as PubChem (https://pubchem.ncbi.nlm.nih.gov/) and the US EPA's CompTox Chemicals Dashboard (https://comptox.epa.gov/dashboard/), enabling further access to these lists, along with the additional functionality and calculated properties these resources offer. PubChem has also integrated significant annotation content from the NORMAN-SLE, including a classification browser (https://pubchem.ncbi.nlm.nih.gov/classification/#hid=101). Conclusions: The NORMAN-SLE offers a specialized service for hosting suspect screening lists of relevance for the environmental community in an open, FAIR manner that allows integration with other major chemical resources. These efforts foster the exchange of information between scientists and regulators, supporting the paradigm shift to the "one substance, one assessment" approach. New submissions are welcome via the contacts provided on the NORMAN-SLE website (https://www.norman-network.com/nds/SLE/). Supplementary Information: The online version contains supplementary material available at 10.1186/s12302-022-00680-6.

Certain Perfluoroalkyl and Polyfluoroalkyl Substances Associated with Aqueous Film Forming Foam Are Widespread in Canadian Surface Waters.

The presence of perfluoroalkyl and polyfluoroalkyl substances (PFASs) commonly associated with aqueous film forming foams (AFFFs) at sites without known AFFF contamination is a largely unexplored area, which may reveal widespread environmental contaminants requiring further investigation. Sensitive liquid chromatography-tandem mass spectrometry (LC-MS/MS) screening for 23 classes of PFASs, followed by quantitative analysis was used to investigate surface waters from rural, urban, and AFFF-impacted sites in Canada. The PFASs detected included perfluorohexane sulfonamide (FHxSA), 6:2 fluorotelomer sulfonamide (FTSAm), fluorotelomer sulfonamide alkylbetaines (FTABs), fluorotelomer betaines (FTBs), 6:2 fluorotelomer mercaptoalkylamido sulfonate sulfone (FTSAS-SO2), 6:2 fluorotelomerthiohydroxyl ammonium sulfoxide (FTSHA-SO), 6:2 fluorotelomer sulfonamide alkylamine (FTAA) and C3 to C6 perfluoroalkane sulfonamido amphoterics. Detection of FHxSA in all urban and AFFF-impacted sites (0.04-19 ng/L) indicates the widespread presence of rarely considered perfluorohexanesulfonate (PFHxS) precursors in Canadian waters. FTABs and FTBs were especially abundant with up to 16-33 ng/L of 6:2 FTAB in urban and AFFF-impacted water suggesting it may have additional applications, while FTBs were only in AFFF-impacted sites (qualitative; ∑FTBs 80 ng/L). The distributions of PFASs moving downstream along the AFFF-impacted Welland River and between water and sediment suggested differences in the persistence of various AFFF components and enhanced sorption of long-chain fluorotelomer betaines. Total organofluorine combustion-ion chromatography (TOF-CIC) revealed that fluorotelomer betaines were a substantial portion of the organofluorine in some waters and 36-99.7% of the total organofluorine was not measured in the targeted analysis.

Aerobic biodegradation of 2 fluorotelomer sulfonamide-based aqueous film-forming foam components produces perfluoroalkyl carboxylates.

The biodegradation of 2 common fluorotelomer surfactants used in aqueous film forming foams (AFFFs), 6:2 fluorotelomer sulfonamide alkylamine (FTAA) and 6:2 fluorotelomer sulfonamide alkylbetaine (FTAB), was investigated over 109 d with aerobic wastewater-treatment plant (WWTP) sludge. Results show that biodegradation of 6:2 FTAA and 6:2 FTAB produces 6:2 fluorotelomer alcohol (FTOH), 6:2 fluorotelomer carboxylic acid (FTCA), 6:2 fluorotelomer unsaturated carboxylic acid (FTUCA), 5:3 FTCA, and short-chain perfluoroalkyl carboxylates (PFCAs). Additional degradation products included 6:2 fluorotelomer sulfonamide (FTSAm), which was a major degradation product in the presence of either active or sterilized sludge, whereas 6:2 fluorotelomer sulfonate (FTSA) production was measured with sterilized sludge only. Six additional degradation products were tentatively identified by quadrupole time-of-flight mass spectrometry (qTOF-MS) and attributed to N-dealkylation and oxidation of 6:2 FTAA. Environ Toxicol Chem 2017;36:2012-2021. © 2017 SETAC.

Identification of novel fluorinated surfactants in aqueous film forming foams and commercial surfactant concentrates.

Recent studies comparing the results of total organofluorine-combustion ion chromatography (TOF-CIC) to targeted analysis of perfluoroalkyl and polyfluoroalkyl substances (PFASs) by liquid chromatography tandem mass spectrometry (LC-MS/MS) have shown that a significant yet variable portion of the total organofluorine in environmental and biological samples is in the form of unknown PFASs. A portion of this unknown organofluorine likely originates in proprietary fluorinated surfactants not included in LC-MS/MS analyses and not fully characterized by the environmental science community, which may enter the environment through use in aqueous film forming foams (AFFFs) for firefighting. Contamination of water, biota, and soils with various PFASs due to AFFF deployment has been documented. Ten fluorinated AFFF concentrates, 9 of which were obtained from fire sites in Ontario, Canada, and two commercial fluorinated surfactant concentrates were characterized in order to identify novel fluorinated surfactants. Mixed-mode ion exchange solid phase extraction (SPE) fractionated fluorinated surfactants based on ionic character. High resolution mass spectrometry assigned molecular formulas to fluorinated surfactant ions, while collision induced dissociation (CID) spectra assisted structural elucidation. LC-MS/MS detected isomers and low abundance fluorinated chain lengths. In total, 12 novel and 10 infrequently reported PFAS classes were identified in fluorinated chain lengths from C3 to C15 for a total of 103 compounds. Further research should examine the environmental fate and toxicology of these PFASs, especially their potential as perfluoroalkyl acid (PFAA) precursors.

Comprehensive plasma thiol redox status determination for metabolomics.

Thiol homeostasis plays an important role in human health and aging by regulation of cellular responses to oxidative stress. Due to major constraints that hamper reliable plasma thiol/disulfide redox status assessment in clinical research, we introduce an improved strategy for comprehensive thiol speciation using capillary electrophoresis-electrospray ionization-mass spectrometry (CE-ESI-MS) that overcomes sensitivity, selectivity and dynamic range constraints of conventional techniques. This method integrates both specific and nonspecific approaches toward sensitivity enhancement for artifact-free quantification of labile plasma thiols without complicated sample handling. A multivariate model was developed to predict increases in ionization efficiency for reduced thiols when conjugated to various maleimide analogs based on their intrinsic physicochemical properties. Optimization of maleimide labeling in conjunction with online sample preconcentration allowed for simultaneous analysis of nanomolar levels of reduced thiols and free oxidized thiols as their intact symmetric or mixed disulfides. Identification of low-abundance thiols and various other polar metabolites detected in plasma was supported by prediction of their relative migration times using CE as a qualitative tool complementary to ESI-MS. Plasma thiol redox status determination together with untargeted metabolite profiling offers a systemic approach for elucidation of the causal role of dysregulated thiol metabolism in the etiology of human diseases.

Comparison of peak integration methods for the determination of enantiomeric fraction in environmental samples.

Enantiomeric fractions (EFs) are used extensively in environmental pollutant research because of the insights on biochemical weathering available from quantifying enantiomeric composition. While this analysis is powerful, it can also be subject to significant error, depending on how chromatographic peaks are integrated. Two methods of integration, the common valley drop method (VDM) and the deconvolution method (DM) were compared using both instrumental and simulated chromatograms to assess their performance when integrating pairs of enantiomers. The effect of peak parameters such as true EF, peak resolution, signal-to-noise ratio, and asymmetry were also investigated. The VDM biased EFs by up to +6% to -4% (relative to the 0-1 EF scale) for symmetric peaks, and as low as -20% for asymmetric peaks. For both instrumental and simulated data, biases tended to increase with decreasing resolution and more extreme (nonracemic) EFs. In contrast, the DM produced biases that were less than 1% in most cases, including at very low resolutions. Estimates from previously published studies based on EF, such as biotransformation rate and source apportionment, could be dramatically affected by small errors in EF. Our results suggest that a deconvolution-based integration method is preferable for the handling of enantiomer compositions. Caution is also advised when comparing published studies on chiral environmental pollutants as most do not specify how chromatographic data is processed.