Chain Polyfluoroalkyl Substances Research Articles

Nanotubular clay minerals for simultaneous sorption of pesticides and PFCAs: a molecular simulation study.

Perfluoroalkyl and polyfluoroalkyl substances (PFAS) and herbicides are important persistent contaminants that require specific management. A variety of herbicides is stored in fluorinated containers in the form of aquatic solutions. In such environments, the simultaneous release of PFAS and herbicides takes place. Nature-based solutions, such as the use of clay materials as possible sorbents, are attractive for the immobilization of such contaminants and environmental protection. Nanotubular clay minerals, such as halloysite and imogolite, are sufficient sorbents for herbicides. Due to their structural morphology, such materials could be efficient sorbents for the simultaneous immobilization of PFAS and herbicides. In this study, the potential sorption of a short chain PFAS, perfluorobutanoic acid (PFBA), sorbent of PFBA, and herbicides (atrazine and diuron) were investigated. Forcefield calculations were used for the classical molecular simulation study. Different distributions, arrangements, and ratios of the investigated molecules were investigated for the complete structural and energy characterization of the systems. Both clay minerals created stable complexes with PFBA as well as with both PFBA and herbicide molecules. Halloysite mineral led to similar total energies of the system with sorbed PFBA molecules alone, herbicides alone, or both of the pollutants. In contrast, imogolite led to lower energies with sorbed herbicides and showed relatively higher energies when interacting with PFBA. The complexes with both of the pollutants presented moderate energies. Electrostatic interactions were dominant in all the investigated complexes.

µ-X-ray fluorescence (XRF) and fluorine K-edge µ-X-ray absorption near-edge structure (XANES) spectroscopy for detection of PFAS distribution in the impacted concrete

An improved understanding of the distribution of per- and polyfluoroalkyl substances (PFAS) in PFAS-impacted concrete is important for risk management and decontamination of PFAS. This study incorporates µ-X-ray fluorescence (µ-XRF) and fluorine K-edge µ-X-ray absorption near-edge structure (µ-XANES) spectroscopy to gain non-destructive insights into PFAS distribution in the impacted concrete. The μ-XRF and μ-XANES spectroscopy provided additional details on the detection of PFAS, which were not detected by the desorption electrospray ionization (DESI) imaging method conducted previously. The shorter chain PFAS were found on the top part of the concrete core (0.5 cm), and longer chain PFAS were mostly at the bottom part of the concrete core (5 cm). The inorganic fluorine fraction was also detected, and it likely hampered the detection of organic fluorine such as PFAS in the concrete. Thus, this non-destructive technique is an complementary approach to detect PFAS in contaminated concrete.

Determination of persistent and mobile organic compounds in the river–groundwater interface of the Besòs river delta, Spain, using a wide extraction approach

Climate change impacts the Mediterranean region, transforming it from region with a semi-arid climate to a region with an arid climate. Under this situation, while groundwater is an essential hydric resource, its existence is in danger due to anthropogenic pressures. Persistent mobile organic compounds (PMOCs) have recently been recognised as an emerging problem; however, PMOCs in groundwater need to be better characterised. Here, we present a new analytical method to characterise the profile of PMOCs in groundwater based on two parallel solid-phase extraction (SPE), using weak anion exchange and weak cation exchange. Extracts were analysed by ultraperformance liquid chromatography (UPLC) using mix-mode chromatography for those compounds analysed under negative ionisation conditions and hydrophilic interaction liquid chromatography (HILIC) under positive conditions coupled to high-resolution mass-spectrometry (HRMS) using a Q-Exactive Orbitrap™ analyser. For the suspect screening of PMOCs in groundwater, the acquisition mode was in full scan (FS) by “independent scan of all ion fragmentation”. For the tentative identification, different online databases such as Environmental and Food Safety (EFS) HRAM Compound database, PFAS NIST database, ChemSpider for chemical structural information, MzCloud as a mass spectral database, and an in-house list with 1280 PMOC structures have been used. The performance of the method was assessed with 29 representative PMOCs which were selected based on the previous literature. The recovery rates have been between 63 and 110 % for 90 % of the target compounds and method limits of quantification (MLQ) between 0.3 and 10.5 ng/L.The optimised approach was applied to assess PMOCs in the Besòs River aquifer, NE Spain, showing 148 tentatively identified structures at confidence levels 1–3. Among them, 66 suspects were tentatively identified at level 3, 54 at level 2, and 28 confirmed at level 1. Most of these compounds were polar and highly polar compounds which are difficult to retain with other extraction approaches. Major detected compounds were pharmaceuticals and personal care products (46), followed by perfluoroalkyl and polyfluoroalkyl substances (PFAS) (32), industrial additives (27), and pesticides (23), among other groups. Some compounds, such as ultrashort chain PFAS and fluorinated betaines, were detected for the first time in groundwaters in Spain.

Permeation of per- and polyfluoroalkyl substances (PFAS)-laden leachate in landfills as an outcome of puncture failures of high-density polyethylene geomembranes

In response to growing environmental concerns regarding the presence of per- and polyfluoroalkyl substances (PFAS) in landfills, this study explores PFAS permeation through pinhole defects of high-density polyethylene (HDPE) geomembranes (GMs) experimentally. Specifically, this study aims to: (i) investigate the adsorption of PFAS onto HDPE GMs, (ii) evaluate the effectiveness of GMs experimentally in retaining PFAS-laden leachate in the event of a puncture failure, (iii) assess the critical conditions leading to puncture failure of GM using mechanical characterization testing with complementary finite element method (FEM) analyses with the input data from mechanical characterization. Our findings show limited intermolecular attractive interactions between PFAS and GMs, and surfactant properties of PFAS contribute to higher leachate permeation through pinholes. In general, highly fluorinated, short chain PFAS exhibit increased permeation rates, which was attributed to their size and greater propensity to align at the water-air interface. This study underlines the environmental implications of PFAS-laden leachates especially when there are no proper liner systems or leachate collection systems in place underscoring the necessity for modern landfill design and management practices to mitigate environmental risks associated with PFAS.

Analysis of wastewater treatment plant data identifies the drivers of PFAS enrichment in foams

The concept of incorporating foam fractionation in aerated bioreactors at wastewater treatment plants (WWTPs) for the removal of per- and polyfluoroalkyl substances (PFAS) has recently been proposed. The extent of PFAS enrichment in aerated bioreactors’ foams, as indicated by enrichment factors (EFs), has been observed to vary widely. Laboratory evidence has shown that factors affecting PFAS enrichment in foams include conductivity, surfactant concentrations and initial PFAS concentrations. However, real wastewaters are complex heterogenous matrices with physical, chemical and biological characteristics potentially contributing to the phenomenon of PFAS partitioning into foams. In this study, we characterised mixed liquor suspensions, including conductivity, filament content, aqueous PFAS concentrations, surface tension and total suspended solids concentrations (TSS) as well as foams, including bubble size and half-life. We used statistical tools – linear mixed-effects model – to establish relationships between PFAS enrichment in aerated bioreactor foams and the examined characteristics. We found that some of the examined characteristics, specifically filament content, surface tension and TSS concentrations measured in mixed liquor suspension and foam half-life, are negatively and significantly associated with the enrichment of longer chain PFAS (with perfluorinated carbon number ≥ 6). Of these, filament content is the important determinant of PFAS enrichment, potentially leading to an increase in, for example, perfluorooctanoic acid (PFOA) EF from 3 to 100 between typical filamentous and non-filamentous suspended biomass. However, enrichment of shorter chain PFAS (with perfluorinated carbon number ≤ 5) is negligible and is not affected by the characteristics that were measured. The findings of our study may serve as valuable information for the implementation of foam fractionation at WWTPs by elucidating the drivers that contribute to the enrichment of longer chain PFAS, under conditions typically found at WWTPs.

Comparing occurrence of per- and polyfluoroalkyl substances (PFAS) in municipal biosolids and industrial wastewater sludge: A City of Los Angeles study

Biosolids and sludge are what remain after the liquid fraction of wastewater is separated during wastewater treatment. These high organic content matrices are known to contain organic contaminants, a few of which are the hazardous and environmentally persistent per- and polyfluoroalkyl substances (PFAS). The current study investigates whether sludge from a treatment facility serving mostly industrial establishments and biosolids from a facility serving mostly domestic dwellings retain these ‘forever chemicals’ similarly. Using 31 markers covering different classes of PFAS, the sludge was found to contain higher levels of PFAS (869 ± 791 ng/g; 21 of 31) than biosolids (31 ± 7 ng/g, 11 of 31). The most abundant overall was perfluorooctane sulfonic acid (PFOS), mostly in sludge (range: 71–1300 ng/g versus 0–18 ng/g in biosolids). The large PFAS concentration variability in sludge was seasonal and sinusoidal. Sludge, additionally, contained all long chain PFAS, precursors (mostly surfactant ingredients and their transformation byproducts) and short chain PFAS (perhaps because of higher moisture content). By regression, the sludge is shown to consistently contain twice as much PFAS as biosolids when the same amounts are exposed to increasing levels of PFAS. Factors observed to cause differential PFAS retention between sludge and biosolids were moisture (98.6 % and 72.1 %, respectively), chain length, input quality (industrial versus residential) and functional group. Sulfonic acids for instance are one C atom shorter than carboxylates with similar occurrence in sludge and biosolids. More studies are needed to define the roles that organic carbon of sludge/biosolids, water chemistry, temperature and factors not considered here play in partitioning PFAS between the two matrices with respect to inputs. Existing Koc values could not help in explaining observed trends, but the ratio of biosolids-to-influent concentrations was found to correlate positively with PFAS size. Using influent in the ratio, and not effluent, is novel. SynopsisSludge and biosolids are soil amendments; they contain hazardous and persistent PFAS. Methods of decoupling PFAS from these matrices start with understanding matrix-driven PFAS partitioning as shown here.

Rapid and simultaneous determination of ultrashort-, short- and long- chain perfluoroalkyl substances by a novel liquid chromatography mass spectrometry method

Per- and Polyfluoroalkyl Substances (PFAS) are a group of persistent organic pollutants that have received considerable attention from public and regulatory groups. Due to regulations of long-chain PFAS, the use of short-chain and ultrashort-chain PFAS is rapidly growing. Thus, there is an urgent need to develop quantitative methods for determining PFAS with different chain lengths in various environmental matrices. This study introduces an innovative liquid chromatography-mass spectrometry (LC-MS) system combining large volume injection (LVI) and online solid phase extraction (SPE). This system incorporates three columns: a reverse-phase (RP) column, a weak anion exchange (WAX) trap column, and a hybrid HILIC/ion-exchange (HILIC/IE) column, controlled by two valves. With valve switching, ultrashort-chain PFAS that are not retained by the RP column are enriched by the trap column, while other PFAS are separated by the RP column. The trapped ultrashort PFAS are then transferred to the HILIC/IE column for further separation. The LVI significantly enhances the method's sensitivity, allowing for rapid and simultaneous determination of ultrashort-, short- and long- chain PFAS in aqueous samples. The matrix effects from various environmental samples were evaluated, and the results indicate that this unique LC-MS method is suitable for analyzing all chain-length PFAS in various matrices, including surface water, sewage effluent, and seawater. Finally, this novel LC-MS method was applied to quantify PFAS in various water samples.

Structural investigation of the complexation between vitamin B12 and per- and polyfluoroalkyl substances: Insights into degradation using density functional theory

Environmental remediation of per- and polyfluoroalkyl substances (PFAS) has become a significant research topic in recent years due to the fact that these materials are omnipresent, resistant to degradation and thus environmentally persistent. Unfortunately, they have also been shown to cause health concerns. PFAS are widely used in industrial applications and consumer products. Vitamin B12 (B12) has been identified as being catalytically active towards a variety of halogenated compounds such as PFAS. It has also been shown to be effective when using sulfide as a reducing agent for B12. This is promising as sulfide is readily available in the environment. However, there are many unknowns with respect to PFAS interactions with B12. These include the reaction mechanism and B12's specificity for PFAS with certain functionalization(s). In order to understand the specificity of B12 towards branched PFAS, we examined the atomistic interactions between B12 and eight different PFAS molecules using Density Functional Theory (B3LYP/cc-pVDZ). The PFAS test set included linear PFAS and their branched analogs, carboxylic acid and sulfonic acid headgroups, and aromatic and non-aromatic cyclic structures. Conformational analyses were carried out to determine the lowest energy configurations. This analysis showed that small chain PFAS such as perfluorobutanoic acid interact with the cobalt center of B12. Bulkier PFAS prefer to interact with the amine and carbonyl groups on the sidechains of the B12 ring system. Furthermore, computed complexation energies determined that, in general, branched PFAS (e.g. perfluoro-5-methylheptane sulfonic acid) interact more strongly than linear molecules (e.g. perfluorooctanesulfonic acid). Our results indicate that it may be possible to alter the interactions between B12 and PFAS by synthetically modifying the sidechains of the ring structure.

Impact of four surfactants on the uptake of per- and polyfluoroalkyl substances (PFAS) by red fescue grass

Per- and polyfluoroalkyl substances (PFAS) pose great risks to human health and the ecosystem, necessitating effective remediation strategies such as phytoremediation. Surfactants, due to their ability to increase the bioavailability of hydrophobic contaminants, are considered as potential agents to improve phytoremediation for PFAS. In this research, we explored the impact of four surfactants (sodium dodecyl sulfate (SDS), rhamnolipid, Triton X-100, and Glucopone 600 CS UP) on plant growth and the uptake of PFAS by red fescue over 110 days. The results showed that while surfactants at lower concentrations did not negatively affect plant growth, the highest dose (2,500 mg/kg) significantly reduced the dry weight of plant shoots. Although none of the four surfactants led to an increased overall removal efficiency of ∑PFAS by red fescue over 110 days, SDS did enhance the uptake of PFAS compounds with long carbon chain lengths. With SDS addition at 2,500 mg/kg, the average fold increases of long chain PFAS removal were 1.99 for perfluorooctanoic acid (PFOA), 2.44 for perfluorononanoic acid (PFNA), 2.11 for perfluorodecanoic acid (PFDA), 1.52 for perfluoroundecanoic acid (PFUnA), 1.88 for perfluorohexanesulphonic acid (PFHxS), and 2.97 for perfluorooctanesulfonic acid (PFOS). The research indicated that using surfactants, such as SDS at appropriate doses could improve phytoremediation effectiveness in mitigating long-chain PFAS, which is a known challenge in soil remediation.

Occurrence and fate of perfluoroalkyl and polyfluoroalkyl substances (PFAS) in an urban aquifer located at the Besòs River Delta (Spain)

Urban aquifers are at risk of contamination from persistent and mobile organic compounds (PMOCs), especially per- and polyfluoroalkyl substances (PFAS), which are artificial organic substances widely used across various industrial sectors. PFAS are considered toxic, mobile and persistent, and have therefore gained significant attention in environmental chemistry. Moreover, precursors could transform into more recalcitrant products under natural conditions. However, there is limited information about the processes which affect their behaviour in groundwater at the field-scale. In this context, the aim of this study is to assess the presence of PFAS in an urban aquifer in Barcelona, and identify processes that control their evolution along the groundwater flow. 21 groundwater and 6 river samples were collected revealing the presence of 16 PFAS products and 3 novel PFAS. Short and ultra-short chain PFAS were found to be ubiquitous, with the highest concentrations detected for perfluorobutanesulfonic acid (PFBS), trifluoroacetic acid (TFA) and trifluoromethanesulfonic acid (TFSA). Long chain PFAS and novel PFAS were found to be present in very low concentrations (<50 ng/L). It was observed that redox conditions influence the behaviour of a number of PFAS controlling their attenuation or recalcitrant behaviour. Most substances showed accumulation, possibly explained by sorption/desorption processes or transformation processes, highlighting the challenges associated with PFAS remediation. In addition, the removal processes of different intensities for three PFAS were revealed. Our results help to establish the principles of the evolution of PFAS along the groundwater flow, which are important for the development of conceptual models used to plan and adopt site specific groundwater management activities (e.g., Managed Aquifer Recharge).

An in silico insight on inhibitory potential of short-chain PFHxA and PFHxS against endogenous antioxidant enzymes

Per- and polyfluoroalkyl substances (PFAS) are a large group of synthetic chemicals that are globally used in various commercial products like cloths, carpets, cookware, firefighting foams, cosmetics, electronic products, etc. Inappropriate disposal of these consumer products could lead to environmental contamination with PFAS. Nowadays short-chain PFAS are substituting the long chain PFAS due to their short half-life. However, multiple studies have suggested that short-chain PFAS such as Perfluorohexanoic acid (PFHxA) and Perfluorohexanesulfonic acid (PFHxS) modulate antioxidant enzyme activities, induce Reactive Oxygen Species production, and contribute to oxidative stress in organisms. Notably, experimental set-ups aiming to investigate the mode of action of these compounds on antioxidants are entirely lacking. Hence in the present study, a ligand-docking approach was adopted to investigate the potential intermolecular interactions between short-chain PFAS and major antioxidants such as Glutathione peroxidase-4, Glutathione reductase, Glutathione S-Transferase, Catalase, and Superoxide dismutase-1. Three-dimensional structures of proteins were processed and docked individually with PFHxA and PFHxS using the AutoDock vina.. Results indicated significant binding affinities between various antioxidant proteins and PFAS. Interestingly, non-covalent interactions such as H-bonds, van der Waals, CH bonds, halogen bonds, and alkyl/pi-alkyl were apparent at protein-ligand interface. Hence, these results suggest that both PFHxA and PFHxS may potentially interact with the endogenous antioxidants and this outcome can be detrimental to the redox homeostasis of living organisms.

Advancing the Use of Suction Lysimeters to Inform Soil Leaching and Remediation of PFAS Source Zones

AbstractPorewater in soil vadose zones is an integrator of the fundamental processes governing the transport and partitioning of per and poly‐fluoroalkyl substances (PFAS) as they move from source zones to groundwater. Suction lysimeters are being advanced as a method to provide reliable and representative PFAS porewater samples, to inform PFAS leaching and for monitoring remedial approaches. We report outcomes of lysimeter investigations across 3 sites and 18 lysimeters within fine‐textured soil profiles. Soil cores were recovered from the same locations, and PFAS concentrations in soils and lysimeter porewater were compared and compared with prior laboratory investigations. Variable concentration distributions with depth of PFAS in soils were found with a maximum sum of PFAS of ~56 mg/kg dominated by perfluorooctane sulfonic acid (PFOS). The maximum sum of PFAS in porewater was 13.5 mg/L. Comparison across all collocated soil and porewater concentrations did not provide consistent trends. PFAS mass fractions within lysimeter porewater samples were much higher for most PFAS than mass fractions determined from laboratory investigations, but the fraction was lower for PFOS. The results indicate preferential recovery of individual shorter chain PFAS via leaching at lower liquid: soil ratios such as those experienced under suction during recovery of porewater by lysimeters. Suggestions are offered to advance the use of suction lysimeters in promoting porewater PFAS concentrations as an alternative for regulatory compliance, and in closing the gap between field and laboratory approaches. There is merit in using lysimeters at PFAS field sites with improvements and considerations embraced.

Investigation of the Link between Per- and Polyfluoroalkyl Substances and Stress Biomarkers in Bottlenose Dolphins (Tursiops truncatus).

Bottlenose dolphins (Tursiops truncatus) are keystone and sentinel species in the world's oceans. We studied correlations between per- and polyfluoroalkyl substances (PFAS) and their stress axis. We investigated associations between plasma biomarkers of 12 different PFAS variants and three cortisol pools (total, bound, and free) in wild T. truncatus from estuarine waters of Charleston, South Carolina (n = 115) and Indian River Lagoon, Florida (n = 178) from 2003 to 2006, 2010-2013, and 2015. All PFAS and total cortisol levels for these dolphins were previously reported; bound cortisol levels and free cortisol calculations have not been previously reported. We tested null hypotheses that levels of each PFAS were not correlated with those of each cortisol pool. Free cortisol levels were lower when PFOS, PFOA, and PFHxS biomarker levels were higher, but free cortisol levels were higher when PFTriA was higher. Bound cortisol levels were higher when there were higher PFDA, PFDoDA, PFDS, PFTeA, and PFUnDA biomarkers. Total cortisol was higher when PFOA was lower, but total cortisol was higher when PFDA, PFDoDA, PFTeA, and PFTriA were higher. Additional analyses indicated sex and age trends, as well as heterogeneity of effects from the covariates carbon chain length and PFAS class. Although this is a cross-sectional observational study and, therefore, could reflect cortisol impacts on PFAS toxicokinetics, these correlations are suggestive that PFAS impacts the stress axis in T. truncatus. However, if PFAS do impact the stress axis of dolphins, it is specific to the chemical structure, and could affect the individual pools of cortisol differently. It is critical to conduct long-term studies on these dolphins and to compare them to populations that have no or little expose to PFAS.

Are Geotextiles Silent Contributors of Ultrashort Chain PFASs to the Environment?

We investigated the presence of per- and poly fluoroalkyl substances (PFASs) in woven and nonwoven polypropylene geotextiles and four nonwoven polyester geotextiles commonly used in modern geosynthetic composite lining systems for waste containment facilities such as landfills. Targeted analysis for 23 environmentally significant PFAS molecules and methods for examining "PFAS total" concentrations were utilized to assess their occurrence in geotextiles. This analysis showed that most geotextile specimens evaluated in the current investigation contained the ultrashort chain PFAS compound pentafluoropropionic acid (PFPrA). While the concentrations ranged from nondetectable to 10.84 μg/g, the average measured concentrations of PFPrA were higher in polypropylene than in polyester geotextiles. "PFAS total" parameters comprising total fluorine (TF) and total oxidizable precursors (TOPs) indicate that no significant precursor mass nor untargeted intermediates were present in geotextiles. Therefore, this study identified geotextiles as a possible source of ultrashort PFASs in engineered lined waste containment facilities, which may contribute to the overall PFAS total concentrations in leachates or liquors they are in contact with. The findings reported for the first time herein may lead to further implications on the fate and migration of PFASs in geosynthetic composite liners, as previously unidentified concentrations, particularly of ultrashort-chain PFASs, may impact the extent of PFAS migration through and attenuation by constituents of geosynthetic composite liner systems. Given the widespread use of geotextiles in various engineering activities, these findings may have other unknown impacts. The significance of these findings needs to be further elucidated by more extensive studies with larger geotextile sample sizes to allow broader, generalized conclusions to be drawn.

Fate of perfluoroalkyl and polyfluoroalkyl substances (PFAS) through two full-scale wastewater sludge incinerators.

Perfluoroalkyl and polyfluoroalkyl substances (PFAS) are an emerging issue in wastewater treatment. High-temperature thermal processes, incineration being time-tested, offer the opportunity to destroy and change the composition of PFAS. The fate of PFAS has been documented through wastewater sludge incinerators, including a multiple hearth furnace (MHF) and a fluidized bed furnace (FBF). The dewatered wastewater sludge feedstock averaged 247- and 1280-μmol targeted PFAS per sample run in MHF and FBF feed, respectively. Stack emissions (reportable for all targeted PFAS from MHF only) averaged 5% of that value with shorter alkyl chain compounds comprising the majority of the targeted PFAS. Wet scrubber water streams accumulated nonpolar fluorinated organics from the furnace exhaust with an average of 0.740- and 0.114-mol F- per sample run, for the MHF and FBF, respectively. Simple alkane PFAS measured at the stack represented 0.5%-4.5% of the total estimated facility greenhouse gas emissions. PRACTITIONER POINTS: The MHF emitted six short chain PFAS from the stack, which were shorter alkyl chain compounds compared with sludge PFAS. The FBF did not consistently emit reportable PFAS from the stack, but contamination complicated the assessment. Five percent of the MHF sludge molar PFAS load was reported in the stack. MHF and FBF wet scrubber water streams accumulated nonpolar fluorinated organics from the furnace exhaust. Ultra-short volatile alkane PFAS measured at the stack represented 0.5%-4.5% of the estimated facility greenhouse gas emissions.

Differential Developmental Neurotoxicity and Tissue Uptake of the Per- and Polyfluoroalkyl Substance Alternatives, GenX and PFBS.

Per- and polyfluoroalkyl substances (PFAS) are a class of synthetic chemicals with several applications. Multiple adverse health effects are reported for longer carbon chain (≤C8) PFAS. Shorter carbon chain PFAS, [e.g., hexafluoropropylene oxide dimer acid (HFPO-DA; GenX) and perfluorobutanesulfonic acid (PFBS)] were introduced as alternatives. Past studies indicate that longer-chain PFAS are neurotoxic targeting the dopamine pathway, but it is not known if shorter-chain PFAS act similarly. This study aimed to evaluate developmental neurotoxicity and tissue uptake of GenX and PFBS using the zebrafish (Danio rerio). First, acute toxicity was assessed by measuring LC50 at 120 h postfertilization (hpf). Body burden was determined after embryonic exposure (1-72 hpf) to sublethal concentrations of GenX or PFBS by LC-ESI-MS/MS. Locomotor activity using a visual motor response assay at 120 hpf and dopamine levels at 72 hpf was assessed after embryonic exposure. PFBS was more acutely toxic and bioaccumulative than GenX. GenX and PFBS caused hyperactivity at 120 hpf, but stronger behavioral alterations were observed for PFBS. An increase in whole organism dopamine occurred at 40 ppb of GenX, while a decrease was observed at 400 ppb of PFBS. Differences detected in dopamine for these two PFAS indicate differential mechanisms of developmental neurotoxicity.

Exploration of functionalizing graphene and the subsequent impact on PFAS adsorption capabilities via molecular dynamics

Per- and polyfluoroalkyl substances (PFAS) are extremely stable compounds due to their strong C–F bonds. They are used in water and stain proof coatings, aqueous film forming foams for fire suppression, cosmetics, paints, adhesives, etc. PFAS have been found in soils and waterways around the world due to their widespread usage and recalcitrance to degradation. Development of selective adsorbent materials is necessary to effectively capture a vast family of PFAS structures in order to remediate PFAS contamination in the environment. The work herein is focused on extracting design principles from molecular dynamics simulations of PFAS with functionalized graphene materials. Simulations examined how PFBA, PFOA, and PFOS interact with graphene, graphene oxide, nitrogen group-functionalized graphene oxide, partially fluorinated graphene flakes, and fully fluorinated flakes. Five flakes were used in each simulation to examine how interactions between flakes may lead to competitive interactions with respect to PFAS or formation of pores. Our study revealed that both the clustering mechanisms of the flakes and functional groups on the flake play a role in PFAS adsorption. The most effective functionalizations for PFAS adsorption are as follows: pristine graphene ≈ fully fluorinated > graphene oxide ≈ partially fluorinated > amine and amide functionalized graphene oxide flake. Long chain PFAS and sulfonate PFAS had higher propensity to adsorb to the materials compared to short chain PFAS and carboxylic head groups.

Emerging and legacy perfluoroalkyl and polyfluoroalkyl substances (PFAS) in surface water around three international airports in China

Perfluoroalkyl and polyfluoroalkyl substances (PFAS) are a large category of crucial environmental contaminants of global concerns. There are limited data on PFAS in surface water around international airports in China. The present study investigated the concentrations, distributions, and sources of emerging and legacy PFAS in surface waters around Beijing Capital International Airport (BC), Shanghai Pudong International Airport (SP), and Guangzhou Baiyun International Airport (GB) in China. Twenty-seven target compounds were quantified. The Σ27PFAS concentrations ranged from 19.0 to 62.8 ng/L (mean 36.1 ng/L) in BC, 25.6–342 ng/L (mean 76.0 ng/L) in SP, 7.35–72.7 ng/L (mean 21.6 ng/L) in GB. The dominant compound was perfluorooctanoic acid (PFOA), which accounted for an average of 27% (5%–65%) of the Σ27PFAS concentrations. The alternatives with –C6F12- group had detection frequencies ranging from 72% to 100%. The partition coefficient results indicate that the longer chain PFAS (C > 8) tend to be more distributed in the particle phase. Fifty suspect and nontarget PFAS were identified. In GB, 44 PFAS were identified, more than SP of 39 and BC of 38. An ultra short-chain (C = 2) precursor, N-methylperfluoroethanesulfonamido acetic acid (MeFEtSAA), was identified and semi-quantified. Domestic wastewater discharges might be the main sources around BC, while industrial and aviation activities might be the main sources around SP and GB.

Flushing Home Plumbing Pipes Contaminated with Aqueous Film-Forming Foam Containing Per- and Polyfluoroalkyl Substances.

Per- and polyfluoroalkyl substances (PFAS) from aqueous film forming foam (AFFF) can be accidentally backflushed into drinking water systems during firefighting operations or at industrial facilities. If this contaminated water enters household plumbing systems, homeowners may need to decontaminate their plumbing. This study examines the persistence of PFAS from AFFF on home plumbing, along with the effects of flushing and stagnation. Two sources of AFFF were investigated, representing older formulations (that contain longer chain PFAS) and newer formulations (that contain shorter chain PFAS). Experiments were conducted in copper, polyvinyl chloride (PVC), and cross-linked polyethylene (PEX) pipes with flushing after contamination followed by intermittent flow and periods of stagnation meant to mimic typical household use. Flushing immediately reduced the PFAS concentration in water leaving the pipe by 99.95% to 99.99%. However, PFAS concentration increased after periods of stagnation, corresponding to slow release of adhered PFAS. Flushing may be a valuable part of the decontamination process, but flushing parameters and duration need to be optimized for local conditions.

Fluorine mass balance analysis of PFAS in communal waters at a wastewater plant from Austria

Wastewater treatment plants are a major source of per and polyfluoroalkyl substances (PFAS) in the environment; moreover, long chain PFAS are known to accumulate in sewage sludge. Although publications on PFAS in wastewater are available from around the globe, little information is available from Central Europe. In this study influent, effluent, and sludge from two wastewater treatment plants from Austria were analysed for target PFAS compounds with HPLC MS/MS and extractable organic fluorine (EOF) content with combustion ion chromatography (CIC). The sum of 31 target PFAS increased from 22 to 47 ng L–1 in influent to 140 – 213 ng L–1 in effluent and around 10 ng g–1 in sludge, while EOF were found to be consistent (2.3 – 3.5 µg F L–1) in influent/effluent and 280 ng F g–1 in sludge. Mass balance analysis showed an increase in the identified PFAS compounds in the effluent compared to the influent (from 0.9% - 1.3% to 3.6% - 6.1%), suggesting biotransformation of non-targeted PFAS precursor compounds. In conclusion, wastewater treatment plants transform some PFAS, and wastewater effluent is a source of PFAS contamination in surface water.