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•SPAC had up to s480 times higher adsorption mass loading of PFAAs than GAC.•SPAC and GAC adsorption efficiency depends on PFAS chain length.•The ceramic MF membrane had minimal ...fouling during long-term filtration.•PFASs were effectively removed by the combined SPAC/MF system.
Contamination of drinking water sources with per- and polyfluoroalkyl substances (PFASs) is a major challenge for environmental engineers. While granular activated carbon (GAC) is an effective adsorbent-based treatment technology for long-chained PFASs, GAC is less effective for removal of short-chained compounds, necessitating a more complete treatment strategy. Super-fine powder activated carbon (SPAC; particle diameter <1 um) is potentially a superior adsorbent to GAC due to high specific surface area and faster adsorption kinetics. This study served to evaluate SPAC coupled with ceramic microfiltration (CMF) for PFAS removal in a continuous flow system. Comparison of PFAS mass loading rates onto SPAC and GAC to 10% breakthrough of PFASs using contaminated groundwater indicates that SPAC has nearly double the adsorption potential of GAC. Limitations reaching breakthrough for the SPAC system led to additional higher mass loading experiments where PFAS adsorption onto SPAC reached 2990 μg/g (for quantifiable PFASs), 480x greater than GAC and is thought to be a function of adsorbent size, pore content and PFAS chain length. Additional analysis of system performance through the application of liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QToF-MS) revealed the presence of additional PFASs in influent samples that were removed by the SPAC/CMF system.
Determining health risks associated with per-/polyfluoroalkyl substances (PFASs) is a highly complex problem requiring massive efforts for scientists, risk assessors, and regulators. Among the most ...poorly understood pressing questions is the relative importance of pre-PFAAs, which are PFASs that degrade to highly persistent perfluoroalkyl acids. How many of the vast number of existing pre-PFAAs are relevant for direct human exposure, and what are the predominant exposure pathways? What evidence of direct exposure to pre-PFAAs is provided by human biomonitoring studies? How important are pre-PFAAs and their biotransformation products for human health risk assessment? This article outlines recent progress and recommendations toward widening the lens on human PFAS exposure to include the pre-PFAA subclass.
Many environmentally relevant poly-/perfluoroalkyl substances (PFASs) including perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) exist in different isomeric (branched and ...linear) forms in the natural environment. The isomeric distribution of PFASs in the environment and source waters is largely controlled by the source of contamination and varying physicochemical properties imparted by their structural differences. For example, branched isomers of PFOS are relatively more reactive and less sorptive compared to the linear analogue. As a result, the removal of branched and linear PFASs during water treatment can vary, and thus the isomeric distribution in source waters can influence the overall efficiency of the treatment process. In this paper, we highlight the need to consider the isomeric distribution of PFASs in contaminated matrices while designing appropriate remediation strategies. We additionally summarize the known occurrence and variation in the physicochemical properties of PFAS isomers influencing their detection, fate, toxicokinetics, and treatment efficiency.
Understanding how exposure to aqueous film-forming foam (AFFF)-impacted drinking water translates to bioaccumulation of per- and polyfluoroalkyl substances (PFASs) is essential to assess health ...risks. To investigate spatial variability of PFAS exposure in communities near an AFFF source zone, blood serum was collected in 2018 from 220 adult residents of El Paso County (Colorado), as were raw water samples from several wells. C6 and C8 perfluoroalkyl sulfonates (PFSAs) were predominant in serum and water. PFASs were most elevated in the water district nearest the source zone (median ∑PFSA of 618 ng/L in water and 33 ng/mL in serum). A novel PFAS, unsaturated perfluorooctane sulfonate, was detected in >80% of water and serum samples at low concentrations (≤1.9 ng/mL in serum). Drinking water wells nearest the source zone displayed increased prevalence of perfluoroalkyl sulfonamide precursors not detected in serum. Serum-to-water ratios were the greatest for long-chain PFASs and were elevated in the least impacted water district. Additional serum samples collected from a subset of study participants in June 2019 showed that PFAS concentrations in serum declined after exposure ceased, although declines for perfluoropentane sulfonate were minimal. Our findings demonstrate that AFFF-impacted communities are exposed to complex, spatially variable mixtures of PFASs.
Per- and polyfluoroalkyl substances (PFASs) are widespread in the blood of the general human population, and their bioaccumulation is of considerable scientific and regulatory interest. PFAS exposure ...resulting from aqueous film-forming foam (AFFF) ingestion is poorly understood due to the complexity of AFFF mixtures and the presence of polyfluorinated substances that may undergo metabolic transformation. C57BL/6 mice were dosed with an AFFF primarily containing electrochemically fluorinated PFASs for 10 days, followed by a 6 day depuration. Urine was collected throughout the study and serum was collected post-depuration. Samples were analyzed via high-resolution mass spectrometry. Relative to the dosing solution, C6 and C7 perfluoroalkyl sulfonates (PFSAs) were enriched in dosed mouse serum, suggesting in vivo transformation of sulfonamide precursors. Some substituted C8 PFSAs keto-perfluorooctane sulfonate (PFOS), hydrogen-PFOS, and unsaturated PFOS appeared to be more bioaccumulative than linear PFOS, or were formed in vivo from unidentified precursors. A series of seven peaks in dosed mouse serum was tentatively identified as sulfonimide dimers that were either a minor component of the AFFF or were formed via metabolism of other AFFF components. This work highlights the importance of sulfonamide precursors in contributing to bioaccumulation of AFFF-associated PFSAs and identifies several classes of potentially bioaccumulative novel PFASs that warrant further investigation.
Per- and polyfluoroalkyl substances (PFAS) are a chemical class widely used in industrial and commercial applications because of their unique physical and chemical properties. Between 2013 and 2016 ...PFAS were detected in public water systems and private wells in El Paso County, Colorado. The contamination was likely due to aqueous film forming foams used at a nearby Air Force base.
To cross-sectionally describe the serum concentrations of PFAS in a highly exposed community, estimate associations with drinking water source, and explore potential demographic and behavioral predictors.
In June 2018, serum PFAS concentrations were quantified and questionnaires administered in 213 non-smoking adult (ages 19–93) participants residing in three affected water districts. Twenty PFAS were quantified and those detected in >50% of participants were analyzed: perfluorohexane sulfonate (PFHxS), perfluorooctane sulfonate (PFOS), perfluorooctanoate (PFOA), perfluorononanoate (PFNA) and perfluoroheptane sulfonate (PFHpS). Unadjusted associations were estimated between serum PFAS concentrations and several predictors, including water consumption, demographics, personal behaviors and employment. A multiple linear regression model estimated adjusted associations with smoking history.
Study participants’ median PFHxS serum concentration (14.8 ng/mL) was approximately 12 times as high as the U.S. national average. Median serum concentrations for PFOS, PFOA, PFNA and PFHpS were 9.7 ng/mL, 3.0 ng/mL, 0.4 ng/mL and 0.2 ng/mL, respectively. Determinants of PFHxS serum concentrations were water district of residence, frequency of bottled water consumption, age, race/ethnicity, and smoking history. Determinants of serum concentrations for the other four PFAS evaluated included: water district of residence, bottled water consumption, age, sex, race/ethnicity, smoking history, and firefighter or military employment.
Determinants of serum concentrations for multiple PFAS, including PFHxS, included water district of residence and frequency of bottled water consumption. Participants’ dominant PFAS exposure route was likely consumption of PFAS-contaminated water, but certain demographic and behavioral characteristics also predicted serum concentrations.
Aqueous film-forming foams (AFFFs) are complex per- and polyfluoroalkyl substance (PFAS)-containing mixtures used extensively as fire suppressants. AFFF-impacted groundwater and surface water have ...contaminated drinking water with PFASs in many communities, raising concerns about health effects from drinking water exposures. As individual PFASs have been identified as immune hazards, the immunotoxicity of complex PFAS mixtures is also a concern. Adult female and male C57BL/6 mice were given a commercial AFFF formulation for 10 days via gavage; administered dose was based on combined content of perfluorooctanoate (PFOA) and perfluorooctane sulfonate (PFOS) measured in the formulation (0, 1.88, 3.75, 7.5, or 10 mg PFOS+PFOA/kg body weight). A PFOA positive control of 7.5 mg/kg body weight was also given. Compared with the 0 mg/kg group, the following changes were noted: Body weights of males exposed to 7.5 and 10 mg PFOS+PFOA/kg were reduced by 15%, on average; female body weights did not differ. Average relative liver weights were increased 50%-200% in males and 37.5%-193% in females and liver peroxisome proliferation was increased 2- to 12-fold in all doses of both sexes. Antigen-specific antibody production was suppressed, on average, by 13% in males and by 12.4% in females across all doses. Spleen cellularity and lymphocyte subpopulations did not differ by dose for either sex. Our data indicate that though this complex PFAS mixture contained fairly low PFOA content, it induced changes in C57BL/6 mice similar to changes induced by PFOA alone, likely due to the presence of PFOS and many other PFASs.
Organophosphate esters (OPEs) have been found in remote environments at unexpectedly high concentrations, but very few measurements of OPE concentrations in seawater are available, and none are ...available in subsurface seawater. In this study, passive polyethylene samplers (PEs) deployed on deep-water moorings in the Fram Strait and in surface waters of Canadian Arctic lakes and coastal sites were analyzed for a suite of common OPEs. Total OPEs ( ∑11OPE) at deep-water sites were dominated by chlorinated OPEs, and ranged from 6.3 to 440 pg/L. Concentrations were similar in eastern and western Fram Strait. Chlorinated OPEs were also dominant in Canadian Arctic surface waters (mean concentration ranged from < DL to 4400 pg/L), while nonhalogenated alkyl/aryl-substituted OPEs remained low (1.3–55 pg/L), possibly due to the greater long-range transport potential of chlorinated OPEs. Polybrominated diphenyl ethers (PBDEs) were found at much lower concentrations than OPEs (<DL-14 pg/L). Surface-water concentrations of tris(2-chloroethyl) phosphate (TCEP) and tris(1,3-dichloroisopropyl) phosphate (TDCIPP) were similar for both active and passive sampling approaches. Several OPEs were estimated to be undergoing net transport out of the Arctic, ranging from 17 kg/yr for ethylhexyldiphenylphosphate (EHDPP) to 3400 kg/yr for tris (2-chloroisopropyl) phosphate (TCIPP). This study highlights the importance of OPEs as poorly understood contaminants present at unexpectedly high concentrations in remote marine environments.
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•Fish consumption is a major source of human PFAS exposure.•Lack of harmonization within legislations for PFAS.•Consuming small amounts of fish can lead to exceedance of PFAS safety ...thresholds.•PFAS exposure via fish consumption pose a challenge for risk communication.
Per- and polyfluoroalkyl substances (PFAS) receive global attention due to their adverse effects on human health and the environment. Fish consumption is a major source of human PFAS exposure. The aim of this work was to address the lack of harmonization within legislations (in the EU and the USA) and highlight the level of PFAS in fish exposed to pollution from diffuse sources in the context of current safety thresholds. A non-exhaustive literature review was carried out to obtain PFAS concentrations in wild fish from the Norwegian mainland, Svalbard, the Netherlands, the USA, as well as sea regions (North Sea, English Channel, Atlantic Ocean), and farmed fish on the Dutch market. Median sum wet weight concentrations of PFOA, PFNA, PFHxS, and PFOS ranged between 0.1 µg kg−1 (farmed fish) and 22 µg kg−1 (Netherlands eel). Most concentrations fell below the EU environmental quality standard (EQSbiota) for PFOS (9.1 µg kg−1) and would not be defined as polluted in the EU. However, using recent tolerable intake or reference dose values in the EU and the USA revealed that even limited fish consumption would lead to exceedance of these thresholds – possibly posing a challenge for risk communication.