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Per- and Polyfluorinated Alkyl Substances (PFAS) Cycling within Michigan: Contaminated Sites, Landfills and Wastewater Treatment Plants
Abstract
Concentrations of Per- and Polyfluorinated Alkyl Substances (PFAS) from public and private sources in Michigan compiled for wastewater treatment plants (WWTPs) (influent, effluent, biosolids), contaminated sites, and landfill leachates reveal complex cycling within the natural and engineered environment. Analysis of 171 contaminated sites in Michigan by source release indicate four dominant PFAS sources – landfills, aqueous film-forming foams (AFFF), metal platers, and automotive/metal stamping – account for 75% of the contamination. Diverse chemical signatures were observed for leachates collected from 19 landfills (mostly type II municipal) with the dominant PFAS ranging from perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) to shorter-chained compounds, perfluorohexanoic acid (PFHxA), perfluorobutanoic acid (PFBA), and perfluorobutanesulfonic acid (PFBS). Analysis of PFAS carbon chain length as a function of landfill age shows the transition of C8s in leachate from older landfills to C4s and C6s in younger landfills, consistent with the phasing out and replacement of C8s. PFAS mass flux in leachate for landfills studied range between 5 – 2,000 g/yr and are highest for active landfills, which generate greater leachate volumes and contain fresh PFAS wastes. Detailed study of 10 WWTPs with industrial pretreatment programs indicate numerous chemical transformations across the plants that yield effluent PFAS concentrations as much as 19 times greater than influent, attributed to transformations of unmeasured precursors in the influent to measured, stable PFAS in the effluent. PFOA, PFHxA, perfluoropentanoic acid (PFPeA), PFBA, and PFBS show the greatest increases across the plant ranging from 20% to nearly 2,000%. PFOS concentrations decreased across 6 WWTPs, consistent with a strong tendency to adsorb onto biosolids. Estimated mass of discharge of (mostly unregulated) PFAS from WWTPs to receiving waters range from 40 g/yr to 128 kg/yr.
... Biosolids are typically disposed of through landfilling, incineration, or are used as a soil amendment (fertilizer) as they contain high concentrations of nitrogen, phosphorous, organic carbon, and other essential elements which are beneficial for soil quality and crop production [1][2][3]. Although the benefit of recycling nutrients necessary for crop production and avoiding the use of energy-intensive synthetic fertilizers is significant, biosolids also act as a sink for emerging pollutants [3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21]. Preventing harmful exposures to these emerging pollutants when land applied remains a challenge [10,20,22]. ...
... While the risk of direct human exposure to emerging pollutants in biosolids is low and realistically may involve only those who work with biosolids such as farmers and biosolids workers [32], the risk of indirect exposure is significantly higher. Not only can the land application of biosolids result in ingestion of contaminated food-crops, animal up-take in meat or milk, and drinking water contamination, but it can also lead to pollutant exposure via inhalation [14,19,[32][33][34][35][36]. Although exposure to individual synthetic organic pollutants in biosolids such as antimicrobials, pharmaceuticals, personal care products, surfactants and hormones would not accumulate in the food chain at concentrations that may pose a risk for human health, the sum of them could be of considerable concern [11,37]. ...
... Per-and Polyfluorinated Alkyl Substances (PFAS) is a broad term for manmade aliphatic compounds with at least one carbon-fluorine (C-F) bond [14,59]. PFAS have been mass produced since the 1940s [14,59]; however, due to environmental concerns, the production and use of long-chain (≥ 8 carbons) PFAS in North America, Europe, and Australia were voluntarily phased out in the early 2000s and replaced with shorter-chain PFAS [59,60]. ...
Background:
Over 40% of the six million dry metric tons of sewage sludge, often referred to as biosolids, produced annually in the United States is land applied. Biosolids serve as a sink for emerging pollutants which can be toxic and persist in the environment, yet their fate after land application and their impacts on human health have not been well studied. These gaps in our understanding are exacerbated by the absence of systematic monitoring programs and defined standards for human health protection.
Methods:
The purpose of this paper is to call critical attention to the knowledge gaps that currently exist regarding emerging pollutants in biosolids and to underscore the need for evidence-based testing standards and regulatory frameworks for human health protection when biosolids are land applied. A scoping review methodology was used to identify research conducted within the last decade, current regulatory standards, and government publications regarding emerging pollutants in land applied biosolids.
Results:
Current research indicates that persistent organic compounds, or emerging pollutants, found in pharmaceuticals and personal care products, microplastics, and per- and polyfluoroalkyl substances (PFAS) have the potential to contaminate ground and surface water, and the uptake of these substances from soil amended by the land application of biosolids can result in contamination of food sources. Advanced technologies to remove these contaminants from wastewater treatment plant influent, effluent, and biosolids destined for land application along with tools to detect and quantify emerging pollutants are critical for human health protection.
Conclusions:
To address these current risks, there needs to be a significant investment in ongoing research and infrastructure support for advancements in wastewater treatment; expanded manufacture and use of sustainable products; increased public communication of the risks associated with overuse of pharmaceuticals and plastics; and development and implementation of regulations that are protective of health and the environment.
... Following the Unregulated Contaminant Monitoring Rules (UCMR), this monitoring has taken place every five years since 2013 (USEPA, 2021). However, several states, such as California, New Hampshire, and Michigan, have implemented more comprehensive measurements (George and Dixit, 2021;Helmer et al., 2022;Hu et al., 2021). ...
... Most of the sites are landfills and industrial sites (>130), while the remaining include WWTP, airports, AFFF discharge sites, military, and air force bases, and places where the exact PFAS source is still uncertain (EGLE, 2023a). Among these confirmed sources, AFFF discharge sites, landfills, and the metal plating and automotive stamping industries were found to account for the largest portion of contamination (Helmer et al., 2022). However, EGLE did not identify automotive stamping plants as a major contamination source in Michigan (EGLE 2023a). ...
The monitoring of Per and Polyfluoroalkyl substances (PFAS) in drinking water sources has significantly increased due to their recognition as a major public health concern. This information has been utilized to assess the importance of potential explanatory variables in determining the presence and concentration of PFAS in different regions. Nevertheless, the significance of these variables and the reliability of the methods in regions beyond where they were initially tested is still uncertain. Hence, our research pursues two main objectives: 1) to evaluate the validity of the aforementioned variables and methods for several PFAS species in a different area and 2) to build on existing modeling work; a new PFAS predictive model is introduced which is more reliable in determining the presence and concentration of PFAS at a regional level. To achieve these goals, we reconstructed four state-of-the-art models using a statewide dataset available for Michigan. These models involve spatial regression techniques, classification and regression random forest algorithms, and boosted regression trees. They also include numerous explanatory variables, such as features of local soil and hydrology and the number of nearby contamination sources. Then, we use a Bayesian selection approach to find the most relevant among these variables. Finally, we employ the most relevant covariates to assess PFAS occurrence and estimate their concentration using a novel combination of machine learning algorithms and conditional autoregressive (CAR) modeling. In the first case, PFAS occurrence was assessed with an accuracy comparable to the reconstructed models (>90%) while using significantly fewer variables. In the second case, by maintaining low data requirements, the estimated concentrations of most PFAS compounds were more closely aligned with available observations compared to previous methods, with correlation coefficients ρ > 0.90 and R2 > 0.77.
... Wastewater Treatment Plants (WWTPs) passively receive Per-and Polyfluorinated Alkyl Substances (PFAS) from consumer products, landfills, local industries, and remediation sites. Perfluoroalkyl acids (e. g., PFOS and PFOA) do not breakdown in WWTPs treating municipal wastewater (Bennett, 2003;Ateia et al., 2019;Zhou et al., 2019;Letcher et al., 2020), and effluent from individual WWTPs may contribute kilograms per year of PFAS to the environment (Gallen et al., 2018;Helmer et al., 2022). Biosolids generated at WWTPs may also be enriched with PFAS and either landfilled, where PFAS-laden leachate often cycles back to WWTPs, or land applied with the potential to contaminate agricultural crops, livestock, dairy products, and surface water and groundwater resources (Brusseau et al., 2020;Death et al., 2021;Jha et al., 2021;Podder et al., 2021;Xu et al., 2021). ...
... Known statewide as '537 Modified', this method, similar to USEPA 537 but not approved for drinking water analysis by the USEPA, utilizes high-performance liquid chromatography tandem mass spectrometry (HPLC/MS-MS), isotope dilution, and additional standards to expand the analyte suite. 537 Modified has been used statewide to analyze PFAS in various nondrinking water and solid matrices, including biota, landfill leachate, WWTP influent, effluent and biosolids (Bogdan et al., 2021;Treat, 2021;Helmer et al., 2022). Similar to ASTM D7968 (ASTM, 2017), all biosolid samples were subjected to a methanol solvent extraction followed by filtration and HPLC/MS-MS analysis for 537 Modified analytes. ...
Approximately 760 liters (200 gallons) of first-generation, PFOS-dominant, Aqueous Film-Forming Foam (AFFF) concentrate entered the sanitary sewer after an accidental release at the Kalamazoo/Battle Creek International Airport and migrated 11.4 km to the Kalamazoo Water Reclamation Plant. Near-daily sampling of influent, effluent, and biosolids generated a high-frequency, long-duration dataset used to understand the transport and fate of accidental PFAS releases to wastewater treatment plants, identify AFFF concentrate composition, and perform a plant-wide PFOS mass balance. Monitored influent concentrations exhibited sharp PFOS declines after 7 days post-spill, yet effluent discharges remained elevated due to return activated sludge (RAS) recirculation, resulting in the exceedance of Michigan's Surface Water Quality Value for 46 days. Mass balance estimates indicate 1.292 kg PFOS entering the plant and 1.368 kg leaving. Effluent discharge and sorption to biosolids account for 55% and 45% of estimated PFOS outputs, respectively. Identification of AFFF formulation and reasonable agreement between computed influent mass and reported spill volume demonstrates effective isolation of the AFFF spill signal and increases confidence in the mass balance estimates. These findings and related considerations provide critical insight for performing PFAS mass balances and developing operational procedures for accidental spills that minimize PFAS releases to the environment.
... In Australian wastewater, PFAS levels were lower with PFPeA, PFHxA, PFHpA, PFOA, PFNA, and PFDA increasing significantly between influent and final effluent (Coggan et al., 2022). PFAS contamination was lower than those found in WWTPs in Michigan (Helmer et al., 2022) and in Southeast United States (Kim et al., 2022), showing in both cases an increase of concentration across WWTPs after biological treatments (Helmer et al., 2022;Kim et al., 2022). For sludge, the concentration of PFOA found in our study was much lower than those reported in previous studies (see Fig. S2) carried out in Spain through 2010 (Campo et al., 2014), in Australia throughout 2017 (Coggan et al., 2022) in Sweden through 2004(Fredriksson et al., 2022, in Southeast United State during 2020-2021 (Kim et al., 2022), and in China during 2015-2016 (Jiang et al., 2023). ...
... In Australian wastewater, PFAS levels were lower with PFPeA, PFHxA, PFHpA, PFOA, PFNA, and PFDA increasing significantly between influent and final effluent (Coggan et al., 2022). PFAS contamination was lower than those found in WWTPs in Michigan (Helmer et al., 2022) and in Southeast United States (Kim et al., 2022), showing in both cases an increase of concentration across WWTPs after biological treatments (Helmer et al., 2022;Kim et al., 2022). For sludge, the concentration of PFOA found in our study was much lower than those reported in previous studies (see Fig. S2) carried out in Spain through 2010 (Campo et al., 2014), in Australia throughout 2017 (Coggan et al., 2022) in Sweden through 2004(Fredriksson et al., 2022, in Southeast United State during 2020-2021 (Kim et al., 2022), and in China during 2015-2016 (Jiang et al., 2023). ...
Wastewater treatment plants are known to be relevant input sources of per- and polyfluoroalkyl substances (PFAS) in the aquatic environment. This study aimed to investigate the occurrence, fate, and seasonal variability of twenty-five PFAS in four municipal wastewater treatment plants (WWTP A, B, C, and D) surrounding the city of Milan (Northern, Italy). Composite 24-h wastewater samples were collected in July and October 2021 and May and February 2022 from influents and effluents of the four WWTPs. PFAS were detected at concentrations ranging between 24.1 and 66.9 μg L-1 for influent and 13.4 and 107 μg L-1 for effluent wastewater samples. Perfluoropentanoic acid was the most abundant (1.91-30.0 μg L-1) in influent samples, whereas perfluorobutane sulfonic acid predominated (0.80-66.1 μg L-1) in effluent samples. In sludge, PFOA was detected in plant A at concentrations in the range of 96.6-165 ng kg-1 dw in primary sludge samples and 98.6-440 ng kg-1 dw in secondary treatment sludge samples. The removal efficiency of total PFAS varied between 6 % and 96 %. However, an increase of PFAS concentrations was observed from influents to effluents for plant D (during July and October), plant A (during October and May), and plant C (during May) indicating that biotransformation of PFAS precursors can occur during biological treatments. This was supported by the observed increase in concentrations of PFOA from primary to secondary treatment sludge samples in plant A. Moreover, the plant operating at shorter hydraulic retention times (plant D) showed lower removal efficiency (<45 %). Seasonal variation of PFAS in influent and effluent appears rather low and more likely due to pulse release instead of seasonal factors.
... The term per-and polyfluoroalkyl substances (PFAS) refers to a wide range of manmade aliphatic compounds with at least one carbon-fluorine (C-F) bond which are highly resistant to other degradation processes [80]. A number of PFAS are harmful to human health as they bioaccumulate in humans and animals, primarily through ingestion. ...
... Samples from these two landfills fell outside the 95% confidence ellipse, indicating that closed landfills may release a different mixture of PFASs than those that are still in operation, a trend that was recently observed elsewhere. 66 Following the long-chain PFAS phase-out, production of short-chain precursors with C 4 and C 6 perfluorinated chains increased. 67 It is possible that this manufacturing trend was responsible for the influence of fourcarbon compounds on the signature of active landfill samples. ...
... Landfills and WWTP are well-known sources of PFAS in watersheds. 60,61 Results from this study highlight the smaller but significant contributions of waste sector sources to PFAS contamination in drinking water systems across the 18 states. ...
Drinking water contaminated by per- and polyfluoroalkyl substances (PFAS) is a widespread public health concern, and exposure-response relationships are known to vary across sociodemographic groups. However, research on disparities in drinking water PFAS exposures and the siting of PFAS sources in marginalized communities is limited. Here, we use monitoring data from 7873 U.S. community water systems (CWS) in 18 states to show that PFAS detection is positively associated with the number of PFAS sources and proportions of people of color who are served by these water systems. Each additional industrial facility, military fire training area, and airport in a CWS watershed was associated with a 10-108% increase in perfluorooctanoic acid and a 20-34% increase in perfluorooctane sulfonic acid in drinking water. Waste sector sources were also significantly associated with drinking water PFAS concentrations. CWS watersheds with PFAS sources served higher proportions of Hispanic/Latino and non-Hispanic Black residents compared to those without PFAS sources. CWS serving higher proportions of Hispanic/Latino and non-Hispanic Black residents had significantly increased odds of detecting several PFAS. This likely reflects disparities in the siting of PFAS contamination sources. Results of this work suggest that addressing environmental justice concerns should be a component of risk mitigation planning for areas affected by drinking water PFAS contamination.
... Due to the high stability of the C-F bond, PFAS are extremely resistant to oxidation and are recognized as persistent pollutants. Besides, PFAS have been proven to have significant bioaccumulation effects and toxicity to the environment (Ghisi et al., 2019;Helmer et al., 2022). It has been reported that the serum perfluorooctanesulfonate (PFOS) concentration (889 ± 56 ng/mL) of turtles exposed to PFAS-contaminated water was 235 times higher than that in the contaminated site (ΣPFAS 32.0 μg/L) (Beale et al., 2022). ...
Per- and polyfluoroalkyl substances (PFAS) are stable organic chemicals, which have been used globally since the 1940s and have caused PFAS contamination around the world. This study explores perfluorooctanoic acid (PFOA) enrichment and destruction by a combined method of sorption/desorption and photocatalytic reduction. A novel biosorbent (PG-PB) was developed from raw pine bark by grafting amine groups and quaternary ammonium groups onto the surface of bark particles. The results of PFOA adsorption at low concentration suggest that PG-PB has excellent removal efficiency (94.8%-99.1%, PG-PB dosage: 0.4 g/L) to PFOA in the concentration range of 10 μg/L to 2 mg/L. The PG-PB exhibited high adsorption efficiency regarding PFOA, being 456.0 mg/g at pH 3.3 and 258.0 mg/g at pH 7 with an initial concentration of 200 mg/L. The groundwater treatment reduced the total concentration of 28 PFAS from 18 000 ng/L to 9900 ng/L with 0.8 g/L of PG-PB. Desorption experiments examined 18 types of desorption solutions, and the results showed that 0.05% NaOH and a mixture of 0.05% NaOH +20% methanol were efficient for PFOA desorption from the spent PG-PB. More than 70% (>70 mg/L in 50 mL) and 85% (>85 mg/L in 50 mL) of PFOA were recovered from the first and second desorption processes, respectively. Since high pH promotes PFOA degradation, the desorption eluents with NaOH were directly treated with a UV/sulfite system without further adjustment. The final PFOA degradation and defluorination efficiency in the desorption eluents with 0.05% NaOH +20% methanol reached 100% and 83.1% after 24 h reaction. This study proved that the combination of adsorption/desorption and a UV/sulfite system for PFAS removal is a feasible solution for environmental remediation.
... There was no significant difference between influent and effluent total quantifiable PFAS-associated fluorine concentrations (t = 0.79, p = 0.43), when all facilities are considered (Fig. 2). These results differ from that observed by Xiao et al., (2012) and Helmer et al., (2022), for which the latter observed that PFAS levels in the effluent were several-times greater than in the influent. However, results presented herein are consistent with several other studies documenting that the total PFAS concentration in the effluent was similar to that of the influent ( PFOS and PFOA, which are the focus of most regulatory attention in the United States, were detected in the influent, effluent or biosolids of 84% and 100% of the facilities, respectively. ...
Both quantifiable and semi-quantifiable poly- and perfluoroalkyl substances (PFAS) were evaluated in the influent, effluent, and biosolids of 38 wastewater treatment plants. PFAS were detected in all streams at all facilities. For the means of the sums of detected, quantifiable PFAS concentrations were 98 ± 28 ng/L, 80 ± 24 ng/L, and 160,000 ± 46,000 ng/kg (dry weight basis) in the influent, effluent, and biosolids (respectively). In the aqueous influent and effluent streams this quantifiable PFAS mass was typically associated with perfluoroalkyl acids (PFAAs). In contrast, quantifiable PFAS in the biosolids were primarily polyfluoroalkyl substances that potentially serve as precursors to the more recalcitrant PFAAs. Results of the total oxidizable precursor (TOP) assay on select influent and effluent samples showed that semi-quantified (or, unidentified) precursors accounted for a substantial portion (21 to 88%) of the fluorine mass compared to that associated with quantified PFAS, and that this fluorine precursor mass was not appreciably transformed to perfluoroalkyl acids within the WWTPs, as influent and effluent precursor concentrations via the TOP assay were statistically identical. Evaluation of semi-quantified PFAS, consistent with results of the TOP assay, showed the presence of several classes of precursors in the influent, effluent, and biosolids; perfluorophosphonic acids (PFPAs) and fluorotelomer phosphate diesters (di-PAPs) occurred in 100 and 92% of biosolid samples, respectively. Analysis of mass flows showed that, for both quantified (on a fluorine mass basis) and semi-quantified PFAS, the majority of PFAS exited WWTPs through the aqueous effluent compared to the biosolids stream. Overall, these results highlight the importance of semi-quantified PFAS precursors in WWTPs, and the need to further understand the impacts of their ultimate fate in the environment.
... We caution that air mass back trajectories are not direct indications of PFAS origins; rather, the frequency plots in Appendix B are intended to simply illustrate patterns in meteorological conditions. Although it is reasonable to detect high PFAS levels in precipitation from air masses that have crossed Michigan, where PFAS contamination from industrial activities is well-established,118 such evidence is circumstantial for rainwater from the Ohio sites.Insufficient samples were collected to identify trends in air mass trajectories at Jackson Hole, WY or Whitestown, IN. ...
High-resolution mass spectrometry was used to screen for emerging per- and polyfluorinated alkyl substances (PFAS) in precipitation samples collected in summer 2019 at seven sites in the United States. We previously quantified the concentration of ten PFAS in the rainwater samples using the method of isotopic dilution (Pike et al., 2021). Nine of these targeted analytes belonged to the U.S. Environmental Protection Agency Regional Screening Level list, herein referred to as EPA-monitored analytes. In this new work, we identify emerging PFAS compounds by liquid chromatography quadrupole time-of-flight mass spectrometry. Several emerging PFAS were detected across all samples, with the most prevalent compounds being C3-C8 hydrogen-substituted perfluorocarboxylic acids (H-PFCAs) and fluorotelomer carboxylic acids (FTCAs). Concentrations of emerging PFAS were in the 10-1000 ng L-1 range (approximately 1-2 orders of magnitude greater than EPA-monitored PFAS) at all sites except Wooster, OH, where concentrations were even higher, with a maximum estimated ΣPFAS of 16 400 ng L-1. The elevated levels of emerging PFAS in the Wooster samples were predominantly even and odd chain-length H-PFCAs and FTCAs comprised of complex mixtures of branched isomers. This unique composition did not match any known manufactured PFAS formulation reported to date, but it could represent thermally transformed by-products emitted by a local point source. Overall, the results indicate that PFAS outside of the standard analyte lists make up a significant and previously unappreciated fraction of contaminants in rainwater collected within the central U.S.-and potentially world-wide-especially in proximity to localized point sources.
... Post-TOP assay Δ ∑ PFCA increased by 244%-878% although changes could not be accounted for by the decrease in PFCA precursors suggesting the contribution of non-measurable precursor compounds. Similarly, Helmer et al. (2022) determined significantly higher PFCA concentrations (PFOA, PFHxA, PFPeA, PFBA) in wastewater treatment plant effluents compared to influents (up to 19-fold) which was attributed to the transformation of unknown precursors. ...
In this study, changes in PFAS leachability and bioavailability were determined following the application of RemBind®100 (R100) and RemBind®300 (R300; 1–10% w/w) to PFAS-contaminated soil (Ʃ28 PFAS 3.093–32.78 mg kg⁻¹). Small differences were observed in PFAS immobilization efficacy when soil was amended with RemBind® products although adding 5% w/w of either product resulted in a >98% reduction in ASLP PFAS leachability. Variability in immobilization efficacy was attributed to differences in activated carbon composition which influenced physicochemical properties of RemBind® formulations and PFAS sorption. PFOS, PFHxS and PFOA relative bioavailability was also assessed in unamended and amended soil (5% w/w) using an in vivo mouse model. In unamended soil, PFAS relative bioavailability was >60% with differences attributed to physicochemical properties of soil which influenced electrostatic and hydrophobic interactions. However, when PFAS relative bioavailability was assessed in soil amended with 5% w/w R100, individual PFAS relative bioavailability was reduced to 16.1 ± 0.8% to 26.1 ± 0.9% with similar results observed when R300 (5% w/w) was utilised (14.4 ± 1.6% to 24.3 ± 0.8%). Results from this study highlight that soil amendments have the potential to reduce both PFAS leachability and relative bioavailability thereby decreasing mobility and potential exposure to soil-borne contaminants.
Drinking water treatment residuals (DWTRs), solid byproducts of drinking water treatment, are dominated by calcium (Ca), iron (Fe) or aluminum (Al), depending on the coagulant used. DWTRs are often landfilled, but current research is exploring options for beneficial reuse. Previous studies have shown that Al‐ and Fe‐ rich materials have potential to reduce the mobility of per‐ and polyfluoroalkyl substances (PFAS). Here, we investigated how amending biosolids with 5% wt/wt DWTRs affected plant bioavailable PFAS in two different simulated scenarios: (1) agricultural scenario, with Solanum lycopersicum (tomato) grown in soil amended with an agronomically relevant rate of DWTR‐amended biosolids (0.9% w/w, resulting in 0.045% w/w DWTR in the biosolids‐amended soil), and (2) mine reclamation scenario, examining PFAS uptake by Lolium perenne (perennial ryegrass) grown in soil that received DWTR‐amended biosolids amendment at a rate consistent with the mine remediation (13% w/w, resulting in 0.65% w/w DWTR in the biosolids‐amended soil). Amending biosolids with Ca‐DWTR significantly reduced perfluorobutanoic acid (PFBA) uptake in ryegrass and perfluorohexanoic acid (PFHxA) uptake in tomatoes, possibly due to DWTR‐induced pH elevation, while Fe‐DWTR amendment reduced PFBA bioaccumulation in ryegrass. The Al‐DWTR did not induce a significant reduction in accumulated PFAS compared to controls. Although the reasons for this finding are unclear, the relatively low PFAS concentrations in the biosolids and relatively high Al content in the biosolids and soil may be partially responsible.
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Many food contact materials (FCMs) and reusable plastics in the food industry contain poly- and perfluoroalkyl substances (PFAS), a group of synthetic pollutants that are known to be potentially harmful for wildlife, humans, and the environment. PFAS may migrate from FCMs to food consumed by humans. As a replacement for plastics, often paper and other plant-based materials are used in commercial settings. This also applies to drinking straws, where plant-based and other presumably eco-friendly straws are increasingly used to reduce plastic pollution. In order to make these materials water-repellent, PFAS are added during manufacturing but can also already be present early in the supply chain due to the use of contaminated raw materials. In the present study, we examined the PFAS concentrations in 39 different brands of straws, made from five materials (i.e. paper, bamboo, glass, stainless steel, and plastic) commercially available on the Belgian market. We combined both targeted and suspect-screening approaches to evaluate a wide range of PFAS. PFAS were found to be present in almost all types of straws, except for those made of stainless steel. PFAS were more frequently detected in plant-based materials, such as paper and bamboo. We did not observe many differences between the types of materials, or the continents of origin. The presence of PFAS in plant-based straws shows that they are not necessarily biodegradable and that the use of such straws potentially contributes to human and environmental exposure of PFAS.
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.
With the growing development of modern agriculture and industry, groundwater is facing more and more complex contaminants. One such contaminant is per- and polyfluoroalkyl substances (PFASs), which pose a potential risk to human health, particularly for those who rely on groundwater as their primary source of drinking water. In this study, we conducted a comprehensive investigation on the occurrence, spatial distribution, and source apportionment of PFASs in shallow (<60 m) and deep (>80 m) groundwater samples from a reclaimed water irrigation area in Beijing's suburbs. Our results showed that the average total PFAS concentration (∑10PFAS) for all samples was 10.55 ± 7.77 ng/L, ranging from 1.05 to 34.28 ng/L. The dominant congeners were PFBA, PFOA, and PFBS. No significant linear relationship was observed between PFAS concentrations and the well depth. However, the averaged ΣPFASs in groundwater were highest in the uppermost layer and declined sharply to a few ng/L in the deep aquifer below 80 m. PFASs showed elevated concentration in shallow aquifers in 9 out of 11 paired wells, indicating an overall descending trend of PFASs with increasing aquifer depth. The spatial distribution of PFASs was highly heterogeneous and showed different patterns in shallow and deep groundwater, which may be related to the complicated attenuation behavior of PFAS compounds when they transport and diffuse through overlapping aquifer layers. The influence of the landfill on groundwater PFASs was most pronounced within a 5 km radius. Source apportionment results indicated that reclaimed water irrigation is the main non-point source of PFASs in shallow groundwater. In contrast, deep groundwater is primarily subject to point sources and lateral recharge flow. This investigation of PFASs in shallow and deep wells provides a foundation for further exploration of PFASs transportation and risk prevention in regions where groundwater is a major water resource for domestic and industrial development.
Widespread distributions of short-chain perfluoroalkyl substances (PFASs) has been recognized as a crucial environmental issue. However, multiple treatment techniques were ineffective due to their high polarity and mobility, contributing to a never-ending existence in the aquatic environment ubiquitously. The present study revealed potential technique of periodically reversing electrocoagulation (PREC) to perform efficient removal of short-chain PFASs including experimental factors (in the conditions of 9 V for voltage, 600 r/min of stirring speed, 10 s of reversing period, and 2 g/L of NaCl electrolyte), orthogonal experiments, actual application, and removal mechanism. Accordingly, based upon the orthogonal experiments, the removal efficiencies of perfluorobutane sulfonate (PFBS) in simulated solution could achieve 81.0% with the optimal parameters of Fe-Fe electrode materials, addition of 665 μL H2O2 per 10 min, and pH at 3.0. The PREC was further applied for treating the actual groundwater around a fluorochemical facility, consequently the removal efficiencies for typical short-chain perfluorobutanoic acid (PFBA), perfluoropentanoic acid (PFPeA), perfluorohexanoic acid (PFHxA), PFBS, and perfluoropentane sulfonate (PFPeS) were 62.5%, 89.0%, 96.4%, 90.0%, and 97.5%, respectively. The other long-chain PFASs contaminants had superior removal with the removal efficiencies up to 97%-100%. In addition, a comprehensive removal mechanism related to electric attraction adsorption for short-chain PFASs could be verified through the morphological analysis of ultimate flocs composition. The oxidation degradation was further revealed as the other removal mechanism by suspect and nontarget screening of intermediates formed in simulated solution, as well as density functional theory (DFT) calculation theory. Moreover, the degradation pathways about one CF2O molecule or CO2 eliminated with one C atom removed in PFBS by ·OH generated from the PREC oxidation process were further proposed. As a result, the PREC would be a promising technique for the efficient removal of short-chain PFASs from severely contaminated water bodies.
Per- and polyfluoroalkyl substances (PFAS) are persistent organic pollutants (POPs) that pose significant environmental and human health risks. The presence of PFAS in landfill leachate is becoming an increasingly concerning issue. This article presents a comprehensive review of current knowledge and research gaps in monitoring and removing PFAS from landfill leachate. The focus is on evaluating the effectiveness and sustainability of existing removal technologies, and identifying areas where further research is needed. To achieve this goal, the paper examines the existing technologies for monitoring and treating PFAS in landfill leachate. The review emphasizes the importance of sample preparation techniques and quality assurance/quality control measures in ensuring accurate and reliable results. Then, this paper reviewed the existing technologies for removal and remediation of PFAS in landfill leachates, such as adsorption, membrane filtration, photocatalytic oxidation, electrocatalysis, biodegradation, and constructed wetlands. Additionally, the paper summarizes the factors that exhibit the performance of various treatment technologies: reaction time, experimental conditions, and removal rates. Furthermore, the paper evaluates the potential application of different remediation technologies (i.e., adsorption, membrane filtration, photocatalytic oxidation, electrocatalysis, biodegradation, and constructed wetlands, etc.) in treating landfill leachate containing PFAS and its precursors, such as fluorotelomeres like FTOH and FTSs. The review highlights the importance of considering economic, technical, and environmental factors when selecting control measures. Overall, this article aims to provide guidance for promoting environmental protection and sustainable development in the context of PFAS contamination in landfill leachate.
Per- and polyfluoroalkyl substance (PFAS) contamination in aqueous matrices has intensified the search for PFAS adsorbents with elevated capacity, selectivity, and cost effectiveness. A novel surface modified organoclay (SMC) adsorbent was evaluated for PFAS removal performance in parallel with granular activated carbon (GAC) and ion exchange resin (IX) for the treatment of five distinct PFAS impaired waters including groundwater, landfill leachate, membrane concentrate and wastewater effluent. Rapid small scale column tests (RSSCTs) and breakthrough modeling were coupled to provide insight on adsorbent performance and cost for multiple PFAS and water types. IX exhibited the best performance with respect to adsorbent use rates in treatment of all tested waters. IX was nearly four times more effective than GAC and two times more effective than SMC in the treatment of PFOA from water types excluding groundwater. Employed modeling strengthened the comparison of adsorbent performance and water quality to infer adsorption feasibility. Further, evaluation of adsorption was extended beyond PFAS breakthrough with the inclusion of unit adsorbent cost as a decision metric influencing adsorbent selection. An analysis of levelized media cost indicated treatment of landfill leachate and membrane concentrate was at least three times more expensive than groundwaters or wastewaters evaluated.
Perfluoroalkyl carboxylic acids (PFCAs) and perfluorooctyl sulfonic acids (PFSAs), which are the most commonly regulated and most widely concerned per- and polyfluoroalkyl substances (PFAS) have received increasing attention on a global scale due to their amphiphilicity, stability, and long-range transport. Thus, understanding the two types of typical PFAS transport behavior and using models to predict the evolution of PFAS contamination plumes is important for evaluating the potential risks. In this study, the effects of organic matter (OM), minerals, water saturation, and solution chemistry on the transport and retention of PFAS were investigated, and the interaction mechanism between long-chain/short-chain PFAS and the surrounding environment was analyzed. The results revealed that high content of OM/minerals, low saturation, low pH, and divalent cation had a great retardation effect on long-chain PFAS transport. The retention caused by hydrophobic interaction was the prominent mechanism for long-chain PFAS, whereas, the retention caused by electrostatic interaction was more relevant for short-chain PFAS. Additional adsorption at the air-water and nonaqueous-phase liquids (NAPL)-water interface was another potential interaction for retarding PFAS transport in the unsaturated media, which preferred to retard long-chain PFAS. Furthermore, the developing models for describing PFAS transport were investigated and summarized in detail, including the convection-dispersion equation, two-site model (TSM), continuous-distribution multi-rate model, modified-TSM, multi-process mass-transfer (MPMT) model, MPMT-1D model, MPMT-3D model, tempered one-sided stable density transport model, and a comprehensive compartment model. The research revealed PFAS transport mechanisms and provided the model tools, which supported the theoretical basis for the practical prediction of the evolution of PFAS contamination plumes.
Linear and branched isomers of per- and polyfluoroalkyl substances (PFASs) are simultaneously present in the environment. However, isomer profiles of PFASs in municipal wastewater treatment plants (WWTPs) are still unknown because of the limitations of standards. Here, influent and effluent samples from 148 municipal WWTPs in China were collected. Ion mobility spectrometry was introduced into high-resolution mass spectrometry-based suspect screening methods to identify the target and suspect PFAS isomers. A total of 38 branched isomers of 14 typical PFASs were identified in wastewater samples. Linear PFASs had higher detection rates (22.3%-100%) than branched isomers (2.0%-98%). Compared to the influents, proportions of branched isomers of most PFASs (except for perfluoropentanoic acid and perfluorohexanoic acid) increased in the effluents. The conventional biological treatment processes (such as anaerobic-anoxic-aerobic and oxidation ditch treatments) had poor removal efficiency for linear PFASs (<21.4%) and branched isomers (<13.4%). No difference on removal efficiency among treatment processes was found. Furthermore, isomer composition in the WWTPs showed obvious differences between East China region and other regions, and the usage of short-chain PFASs (perfluorobutanesulfonic acid and perfluorohexanesulfonic acid) may be a key factor for driving this difference. This study sheds lights on the identification and characterization of PFAS isomers in WWTPs, which would be useful for development of monitoring and control strategies of PFASs.
Uptake and accumulation of per- and polyfluoroalkyl substances (PFAS) in Allium cepa from soils amended with biosolids were investigated. The Ʃ38 PFAS concentrations in soils amended with biosolids ranged from 10.4 to 104 ng g⁻¹ (dry-weight). Among PFAS, perfluorooctanesulfonate (PFOS) concentration was the highest in soils, with a maximum of 48.1 ng g⁻¹, followed by N-ethylperfluoro-1-octanesulfonamidoacetic acid (N-Et-FOSAA) with the maximum of 10.9 ng g⁻¹. The concentration of perfluorooctanoate (PFOA) was higher (0.55 – 1.82 ng g⁻¹) in roots of A. cepa than that of PFOS (0.03 – 0.13 ng g⁻¹). The accumulation of PFAS in A. cepa shoots depended on the carbon chain length, with a more significant accumulation of shorter C-chain PFAS than the longer C-chain derivatives. The concentration of PFAS in shoots correlated positively with corresponding root concentration, suggesting a significant translocation of PFAS from root to shoots. A. cepa showed no considerable cyto-genotoxicity in the meristem root tip cells exposed to soils amended with biosolids. The oxidative stress parameters such as reactive oxygen species (ROS), mitochondrial membrane potential (MMP), and lipid peroxidation (LP) showed no significant increase in A. cepa root cells exposed to soils amended with biosolids. The estimated dietary intake for PFOA and PFOS did not exceed the recommended tolerable daily intake (TDI) even after assuming that onion accounted for 100% of vegetable consumption. This study provides evidence of accumulation and translocation of PFAS from soil to roots and shoots of A. cepa. Also, we assessed the potential risk of PFAS accumulated in A. cepa to humans via the food chain to be insignificant.
Per- and polyfluoroalkyl substances (PFAS) have been widely used in consumer products, some of which inevitably end up as municipal solid waste. Significant knowledge gaps associated with the fate and release of PFAS from the post-consumer products in solid waste management processes exist that limit our current ability to develop appropriate end-of-life management strategies for PFAS. The objectives of this paper are to summarize the current knowledge associated with the fate and release of PFAS from post-consumer products from commonly used waste management processes (including landfilling, recycling, composting, and incineration) and to use that information to identify knowledge gaps and potential exposure pathways for humans and the environment. The current results indicate that landfills are major sinks of PFAS because most PFAS-containing consumer products are landfilled, and PFAS were extensively reported in landfill leachate. More information is needed regarding total influx of PFAS into landfills as well as landfill gas emissions. Recycling and composting also present potential exposure pathways. The reprocessing of carpet and paper packaging was reported to cause direct exposure to on-site workers through PFAS volatilization and dust emissions. Recycling can cause circularity of PFAS in the new product and subsequent release throughout its lifespan. Composted food packaging was found to contain PFAS and could cause contamination during land application of compost. The incineration of waste provides near-complete destruction (~99%) of PFAS. However, some low-temperature regions within the furnace may still result in products of incomplete combustion such as short-chain perfluoroalkyl acids and other stable fluorinated compounds, which may be released in incinerator ash. More information is needed regarding the mechanisms of PFAS thermal destruction. Case studies of PFAS product categories indicated that carpet and cosmetics might contribute to the release of more soluble and volatile PFAS such as perfluoroalkyl acids and fluorotelomer alcohols during landfilling in leachate and gas. The fate of specific PFAS during waste management align well with their physical/chemical properties such as solubility and volatility.
The aim of this critical review is i) to summarize the occurrence of Per- and polyfluoroalkyl substances (PFASs) in landfills; ii) to outline the environmental fate and transport of PFASs in landfills; iii) to compare the treatment technologies of PFASs in landfill leachate and remediation methods of PFASs in surrounding groundwater; iv) to identify the research gaps and suggest future research directions. In recent years, PFASs have been detected in landfills around the world, among which Perfluoroalkyl acids (PFAAs) especially Perfluorooctanoic acid (PFOA) and Perfluorooctane sulfonic acid (PFOS) are mostly studied due to their long-term stability. Short-chain PFASs (<8 carbons) are more common than long-chain PFASs (≧8 carbons) in landfill leachate. PFASs in landfill leachate are eventually transported to the surrounding groundwater, surface water and soil. Some PFASs evaporate from landfills to the ambient air. To avoid the environmental and health risks of PFASs in landfills, new technologies and combined use of existing technologies have been implemented to treat PFASs in landfill leachate. Integrated remediation methods are applied to control the diffusion of PFASs in groundwater surrounding landfills. In future, the mechanisms of PFAAs precursors degradation, the correlation among PFASs in different environmental media around landfills, as well as the environmental behavior and toxic effect of combined pollutants together with PFASs in landfill leachate and surrounding groundwater should be studied.
Observed trends in municipal solid waste landfills reveal a distinct disparity between PFAS composition entering in waste, mostly as diPAP and FTOH, and leaching out as FTCA and PFCA. These patterns are elucidated by compiling PFAS compositions in paper, textiles, and carpet, with known precursor transformations that generate FTCA and PFCA in leachate. Future research must assess the role of precursor PFAS like diPAP and FTOH in landfill mass balances, particularly in leachate, along with the potential release of semi-volatile PFAS to the atmosphere. Closing these knowledge gaps is critical as landfills will increasingly serve as PFAS sources.
Municipal wastewater treatment plants (WWTPs) can reflect the pollution status of per- and polyfluoroalkyl substances (PFASs) pollution. Here, matched influent, effluent, and sludge samples were collected from 58 municipal WWTPs in China, South Sudan, Tanzania, and Kenya. Target and suspect screening of PFASs was performed to explore their profiles in WWTPs and assess removal efficiency and environmental emissions. In total, 155 and 58 PFASs were identified in WWTPs in China and Africa, respectively; 146 and 126 PFASs were identified in wastewater and sludge, respectively. Novel compounds belonging to per- and polyfluoroalkyl ether carboxylic acids (PFECAs) and sulfonic acids (PFESAs), hydrogen-substituted polyfluorocarboxylic acids (H-PFCAs), and perfluoroalkyl sulfonamides (PFSMs) accounted for a considerable proportion of total PFASs (ΣPFASs) in Chinese WWTPs and were also widely detected in African samples. In China, estimated national emissions of ΣPFASs in WWTPs exceeded 16.8 t in 2015, with >60 % originating from emerging PFASs. Notably, current treatment processes are not effective at removing PFASs, with 35 of the 54 WWTPs showing emissions higher than mass loads. PFAS removal was also structure dependent. Based on machine learning models, we found that molecular descriptors (e.g., LogP and molecular weight) may affect adsorption behavior by increasing hydrophobicity, while other factors (e.g., polar surface area and molar refractivity) may play critical roles in PFAS removal and provide novel insights into PFAS pollution control. In conclusion, this study comprehensively screened PFASs in municipal WWTPs and determined the drivers affecting PFAS behavior in WWTPs based on machine learning models.
With the rapid increasing drainage of industrial sewage, the problems arising from sewage containing high-concentration surfactant become more urgent. In order to purify the high-concentration surfactant solution, a novel integrated technology of foam separation and TiO2 photocatalysis was developed. An anionic surfactant of sodium dodecyl benzene sulfonate (SDBS) was used as the model surfactant and its initial concentration in the simulated solution was 0.5 g/L. First, foam separation had been performed to primitively reduce SDBS concentration in the simulated solution. Based on the results of independent factor test, a five-level-three-factor central composite design (CCD) based on response surface design (RSM) was used to predict the optimal experimental conditions. Under above conditions, the enriching proportion and removing percentage of SDBS were 4.69±0.14 and 84.85±0.71%, respectively. The surface tension and foam stability of the residual solution after foam separation had been measured using pulling ring method and bubbling method, respectively. The residual solution after foam separation possessed a higher surface tension and weaker foam stability compared with those of freshly prepared SDBS solution. Extrinsic fluorescence spectra using pyrene showed that interfacial adsorption had led to the generation of hydrophilic SDBS micelles. In order to perform TiO2 photocatalysis, the adsorption capacity of SDBS on TiO2 nanoparticles had been studied. The adsorption of SDBS on TiO2 nanoparticles obeyed Pseudo-second-order dynamics model and Freundlich isotherm model. Based on the unique optical property and particle entrainment capacity of foam, a coupling operation of foam separation and TiO2 photocatalysis was proposed to degrade SDBS in the residual solution. The suitable operating conditions were identified and the maximum degradation percentage of SDBS reached 94.86±1.06%. The total SDBS removing percentage of developed technology was 99.38±0.10%. Total organic carbon (TOC) concentrations of SDBS solution before and after treatment were measured using combustion oxidation coupled nondispersive infrared absorption method. Finally, the economic analysis was carried out to assess the cost effectiveness of the integrated technology of foam separation and TiO2 photocatalysis.
Poly- and perfluoroalkyl substances (PFAS) are a large group of synthetic organofluorine compounds. Over 4700 PFAS compounds have been produced and used in our daily life since the 1940s. PFAS have received considerable interest because of their toxicity, environmental persistence, bioaccumulation and wide existence in the environment. Various treatment methods have been developed to overcome these issues. Thermal treatment such as combustion and pyrolysis/gasification have been employed to treat PFAS contaminated solids and soils. However, short-chain PFAS and/or volatile organic fluorine is produced and emitted via exhaust gas during the thermal treatment. Combustion can achieve complete mineralisation of PFAS at large scale operation using temperatures >1000 °C. Pyrolysis has been used in treatment of biosolids and has demonstrated that it could remove PFAS completely from the generated biochar by evaporation and degradation. Although pyrolysis partially degrades PFAS to short-chain fluorine containing organics in the syngas, it could not efficiently mineralise PFAS. Combustion of PFAS containing syngas at 1000 °C can achieve complete mineralisation of PFAS. Furthermore, the by-product of mineralisation, HF, should also be monitored due to its low regulated atmospheric discharge values. Alkali scrubbing is normally required to lower the HF concentration in the exhaust gas to acceptable discharge concentrations.
Per- and polyfluoroalkyl substances (PFAS) are a class of artificially synthetic organic compounds that are hardly degraded in the natural environment. PFAS have been widely used for many decades, and the persistence and potential toxicity of PFAS are an emerging concern in the world. PFAS exposed via diet can be readily absorbed by the intestine and enter the circulatory system or accumulate directly at intestinal sites, which could interact with the intestine and cause the destruction of intestinal barrier. This review summarizes current relationships between PFAS exposure and intestinal barrier damage with a focus on more recent toxicological studies. Exposure to PFAS could cause inflammation in the gut, destruction of the gut epithelium and tight junction structure, reduction of the mucus layer, and induction of the toxicity of immune cells. PFAS accumulation could also induce microbial disorders and metabolic products changes. In addition, there are limited studies currently, and most available studies converge on the health risk of PFAS exposure for human intestinal disease. Therefore, more efforts are deserved to further understand potential associations between PFAS exposure and intestinal dysfunction and enable better assessment of exposomic toxicology and health risks for humans in the future.
To better understand the fate of per- and polyfluoroalkyl substances (PFAS) during conventional and advanced wastewater treatment, 42 PFAS (C3-C14 perfluorocarboxylic acids (PFCAs), C3-C10 perfluorosulfonic acids (PFSAs), per- and polyfluoroethers, and perfluoroalkyl acid (PFAA) precursors) were investigated through the treatment trains at two municipal wastewater treatment plants (WWTPs) using a targeted analysis, the total oxidizable precursor (TOP) assay, and the estimation of partitioning to sludge. Short-chain (C3-C7) PFAAs were found in higher concentrations in wastewater samples, while long-chain (≥C8) PFAAs dominated in sludge samples. PFAA concentrations were elevated by the wastewater treatment processes, particularly after biological treatment (191.3 and 185.1% increases of PFAAs at WWTP-A and B). After TOP oxidation, PFCAs, particularly short-chain ones, increased considerably (up to 311.4 and 409.3% increases of PFCAs at WWTP-A and B). The study results indicated that the transformation of precursors into shorter chain PFAAs by biological treatment and the partitioning of longer chain PFAS into sludge streams are key factors determining the fate of PFAS in WWTPs. With the increasing impact of short-chain PFAS over time, future research should focus on the evaluation of the fate and distribution of historical and emerging PFAS in WWTPs.
Landfills are the main destination of many urban wastes containing per- and polyfluoroalkyl substances (PFAS), and PFAS may leach out from the waste and contaminate the surrounding groundwater. Here we investigated the occurrence of PFAS in leachate and surrounding groundwater from three landfills in Guangzhou, China by using a combined target and non-target approach. Non-target screening showed that a total of 651 PFAS with 96 classes were identified, including 17 legacy PFAS and 637 emerging PFAS. The quantitative target analysis of some PFAS revealed that the average removal rate of PFAS from the raw leachates were ranged between 62 % and 99 %. Statistical analysis and source analysis suggested that landfill leachate was a major source of PFAS in the groundwater within the landfills and downstream sites. The results from the combined target and non-target analyses demonstrated that PFAS in landfills could leach into the surrounding groundwater, and may affect the sustainable use of groundwater as a source of drinking water and pose a potential risk to human health.
Removal of per- and polyfluoroalkyl substances (PFAS) from water use cycles has now become an urgent task due to their wide spread in water environment and associated adverse health effects. Despite the effectiveness of nanofiltration (NF) and reverse osmosis (RO) for PFAS removal, the high cost related to the high pressure operation and membrane replacement mostly limit the application in the actual drinking water treatment. In this study, we investigated the rejection of the two most typical PFAS, perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) by the chlorine treated RO membranes (Dow FILMTEC™ SW30HR) with five different salt rejection ratios from 12% to 66%, which simulated the used membranes upgraded for the permeability. The damaged membranes were further characterized for their contact angle and zeta potential, and elemental composition was analyzed by X-ray photoelectron spectroscopy. The lab-scale cross-flow filtration tests demonstrated that the damaged RO membranes with 39∼66% salt rejection ratios achieved over 85% rejection of both PFOA and PFOS, which was comparable or even superior performance to that previously reported for NF membranes. Characterization of damaged membranes suggested that electrostatic repulsion and size exclusion both played an important role in the rejection of PFOA and PFOS by the damaged membrane. The present study provides new insights into the energy-efficient and material-saving, thereby economically sustainable, membrane process for the removal of the legacy PFAS.
Per‐ and poly‐fluoroalkyl substances (PFAS) are a universe of fluorinated organic substances with very different physical, chemical, and biological properties including polymers and non‐polymers; solids, liquids, and gases. Commercial PFAS‐based products have been used in a wide variety of industrial and consumer applications because they have unique performance properties of significant socioeconomic value. The PFAS definition has evolved and expanded over the years. Numerous lists of PFAS, some with thousands of entries, have been compiled, but none have clearly identified which of the substances are commercially relevant. This study is the first to use a bona‐fide “bottom up” approach to identify how many of the 4,730 PFAS substances listed in a 2018 OECD/UNEP Report are directly connected to commercial products based on input from three major global producers. This study provides new and valuable insight into the 2018 OECD/UNEP Report list of PFAS substances. The results show that 256, less than 6%, of the 4,730 PFAS substances presented in the 2018 OECD/UNEP Report are commercially relevant globally. This study suggests that grouping and categorizing PFAS using fundamental classification criteria based on composition and structure can be used to identify appropriate groups of PFAS substances for risk assessment, thereby dispelling assertions that there are too many PFAS chemistries to conduct proper regulatory risk assessments for the commercially relevant substances. This article is protected by copyright. All rights reserved.
Our knowledge of PFAS fate and transport in the urban water cycle between water treatment plants (WTPs) and wastewater treatment plants (WWTPs) is dependent upon analytical methodology. To conduct a mass balance of PFAS through these engineered systems, environmental analytical chemistry must be leveraged to quantify PFAS in the various media that cycle through these facilities. Although mass balances have been attempted across various unit treatment processes for a small selection of PFAS in WTPs and WWTPs, system-wide mass balances are a daunting challenge that have not been achieved to date. The continued existence of legacy PFAS and the constantly moving target of newly emerging commercial PFAS and transformation products (TPs), in addition to complications resulting from bias-free collection of uncontaminated samples for PFAS in the parts-per-trillion (ppt) range, complicate a mass balance. Further compounding a mass balance is the diverse universe of PFAS which consists of polar/nonpolar, nonvolatile/semi-volatile/volatile, and neutral/anionic/cationic/zwitterionic chemicals. The physicochemical properties of these chemicals, and the media in which they exist, drive the selection of appropriate analytical procedures to provide accurate and precise quantification of these compounds. The current state of analytical science for PFAS is development of methods specific for subgroups of PFAS families in limited matrices. Here, approaches to integrate analytical workflows across types of PFAS and media are proposed. In this evaluation, multi-platform targeted, suspect/non-targeted, and surrogate screening methods combining promulgated standardized methods and emerging procedures are presented. Synthesis of a comprehensive analytical workflow that aspires to achieve a mass balance of PFAS across the gaseous, solid, and aqueous matrices encountered in WTPs and WWTPs is proposed. Finally, research data gaps and future research needs are also discussed.
Mt. Everest, one of the most coveted climbing mountains on earth, also contains the highest altitude chemical contamination on land. For the first time, meltwater and snow samples from Mt. Everest's Khumbu Glacier were analyzed for "forever chemicals" per-and polyfluoroalkyl substances (PFAS). Our research team utilized solid-phase extraction (SPE) and liquid chromatography-tandem mass spectrometry (LC-MS/MS) to identify pollutants sampled from Everest Base Camp, Camp 1, Camp 2, and Everest Balcony. From the 14 PFAS compounds tested for, we found perfluorooctanesulfonic acid (PFOS), perfluorooctanoic acid (PFOA), and perfluorohexa-noic acid (PFHxA) in Mt. Everest snow and meltwater. The highest concentrations found were 26.14 ng/L and 10.34 ng/L PFOS at Base Camp and Camp 2, respectively. However, PFAS species were seen within 1-2 orders of magnitude in all sampling sites with detection, potentially suggesting a widespread presence on the mountain. Our samples are the highest altitude PFAS samples ever retrieved and indicate the need for further sampling both on Mt. Everest and in the below-glacier watershed.
The need for remediation of poly‐ and perfluoroalkyl substances (PFASs) is growing as a result of more regulatory attention to this new class of contaminants with diminishing water quality standards being promulgated, commonly in the parts per trillion range. PFASs comprise >3,000 individual compounds, but the focus of analyses and regulations has generally been PFASs termed perfluoroalkyl acids (PFAAs), which are all extremely persistent, can be highly mobile, and are increasingly being reported to bioaccumulate, with understanding of their toxicology evolving. However, there are thousands of polyfluorinated “PFAA precursors”, which can transform in the environment and in higher organisms to create PFAAs as persistent daughter products.
Some PFASs can travel miles from their point of release, as they are mobile and persistent, potentially creating large plumes. The use of a conceptual site model (CSM) to define risks posed by specific PFASs to potential receptors is considered essential. Granular activated carbon (GAC) is commonly used as part of interim remedial measures to treat PFASs present in water. Many alternative treatment technologies are being adapted for PFASs or ingenious solutions developed. The diversity of PFASs commonly associated with use of multiple PFASs in commercial products is not commonly assessed. Remedial technologies, which are adsorptive or destructive, are considered for both soils and waters with challenges to their commercial application outlined. Biological approaches to treat PFASs report biotransformation which creates persistent PFAAs, no PFASs can biodegrade. Water treatment technologies applied ex situ could be used in a treatment train approach, for example, to concentrate PFASs and then destroy them on‐site. Dynamic groundwater recirculation can greatly enhance contaminant mass removal via groundwater pumping. This review of technologies for remediation of PFASs describes that:
GAC may be effective for removal of long‐chain PFAAs, but does not perform well on short‐chain PFAAs and its use for removal of precursors is reported to be less effective;
Anion‐exchange resins can remove a wider array of long‐ and short‐chain PFAAs, but struggle to treat the shortest chain PFAAs and removal of most PFAA precursors has not been evaluated;
Ozofractionation has been applied for PFASs at full scale and shown to be effective for removal of total PFASs;
Chemical oxidation has been demonstrated to be potentially applicable for some PFAAs, but when applied in situ there is concern over the formation of shorter chain PFAAs and ongoing rebound from sorbed precursors;
Electrochemical oxidation is evolving as a destructive technology for many PFASs, but can create undesirable by‐products such as perchlorate and bromate;
Sonolysis has been demonstrated as a potential destructive technology in the laboratory but there are significant challenges when considering scale up;
Soils stabilization approaches are evolving and have been used at full scale but performance need to be assessed using appropriate testing regimes;
Thermal technologies to treat PFAS‐impacted soils show promise but elevated temperatures (potentially >500 °C) may be required for treatment.
There are a plethora of technologies evolving to manage PFASs but development is in its early stage, so there are opportunities for much ingenuity.
A critical review of existing publications is presented i) to summarize the occurrence of various classes of per- and polyfluoroalkyl substances (PFASs) and their sources in landfills, ii) to identify temporal and geographical trends of PFASs in landfills; iii) to delineate the factors affecting PFASs in landfills; and iv) to identify research gaps and future research directions. Studies have shown that perfluoroalkyl acids (PFAAs) are routinely detected in landfill leachate, with short chain (C4-C7) PFAAs being most abundant, possibly indicating their greater mobility, and reflecting the industrial shift towards shorter-chain compounds. Despite its restricted use, perfluorooctanoic acid (PFOA) remains one of the most abundant PFAAs in landfill leachates. Recent studies have also documented the presence of PFAA-precursors (e.g., saturated and unsaturated fluorotelomer carboxylic acids) in landfill leachates at concentrations comparable to, or higher than, the most frequently detected PFAAs. Landfill ambient air also contains elevated concentrations of PFASs, primarily semi-volatile precursors (e.g., fluorotelomer alcohols) compared to upwind control sites, suggesting that landfills are potential sources of atmospheric PFASs. The fate of PFASs inside landfills is controlled by a combination of biological and abiotic processes, with biodegradation releasing most of the PFASs from landfilled waste to leachate. Biodegradation in simulated anaerobic reactors has been found to be closely related to the methanogenic phase. The methane-yielding stage also results in higher pH (>7) of leachates, correlated with higher mobility of PFAAs. Little information exists regarding PFAA-precursors in landfills. To avoid significant underestimation of the total PFAS released from landfills, PFAA-precursors and their degradation products should be determined in future studies. Owing to the semi-volatile nature of some precursor compounds and their degradation products, future studies also need to include landfill gas to clarify degradation pathways and the overall fate of PFASs.
More than 3000 per-and polyfluoroalkyl substances (PFASs) are, or have been, on the global market, yet most research and regulation continues to focus on a limited selection of rather well-known long-chain PFASs, particularly perfluorooctanesulfonate (PFOS), per-fluorooctanoic acid (PFOA) and their precursors. Continuing to overlook the vast majority of other PFASs is a major concern for society. We provide recommendations for how to proceed with research and cooperation to tackle the vast number of PFASs on the market and in the environment.
Perfluoroalkyl and polyfluoroalkyl substances (PFAS) are used in a wide range of products of all day life. Due to their toxicological potential, an emerging focus is directed towards their exposure to humans. This study investigated the PFAS load of consumer products in a broad perspective. Perfluoroalkyl sulfonic acids (C4, C6–C8, C10-PFSA), carboxylic acids (C4–C14-PFCA) and fluorotelomer alcohols (4:2, 6:2; 8:2 and 10:2 FTOH) were analysed in 115 random samples of consumer products including textiles (outdoor materials), carpets, cleaning and impregnating agents, leather samples, baking and sandwich papers, paper baking forms and ski waxes. PFCA and PFSA were analysed by HPLC-MS/MS, whereas FTOH were detected by GC/CI-MS. Consumer products such as cleaning agents or some baking and sandwich papers show low or negligible PFSA and PFCA contents. On the other hand, high PFAS levels were identified in ski waxes (up to about 2000 μg/kg PFOA), leather samples (up to about 200 μg/kg PFBA and 120 μg/kg PFBS), outdoor textiles (up to 19 μg/m2 PFOA) and some other baking papers (up to 15 μg/m2 PFOA). Moreover, some test samples like carpet and leather samples and outdoor materials exceeded the EU regulatory threshold value for PFOS (1 μg/m2). A diverse mixture of PFASs can be found in consumer products for all fields of daily use in varying concentrations. This study proves the importance of screening and monitoring of consumer products for PFAS loads and the necessity for an action to regulate the use of PFASs, especially PFOA, in consumer products.
Electronic supplementary material
The online version of this article (doi:10.1007/s11356-015-4202-7) contains supplementary material, which is available to authorized users.
In this discussion paper, the transition from long-chain poly- and perfluorinated alkyl substances (PFASs) to fluorinated alternatives is addressed. Long-chain PFASs include perfluoroalkyl carboxylic acids (PFCAs) with 7 or more perfluorinated carbons, perfluoroalkyl sulfonic acids (PFSAs) with 6 or more perfluorinated carbons, and their precursors. Because long-chain PFASs have been found to be persistent, bioaccumulative and toxic, they are being replaced by a wide range of fluorinated alternatives. We summarize key concerns about the potential impacts of fluorinated alternatives on human health and the environment in order to provide concise information for different stakeholders and the public. These concerns include, amongst others, the likelihood of fluorinated alternatives or their transformation products becoming ubiquitously present in the global environment; the need for more information on uses, properties and effects of fluorinated alternatives; the formation of persistent terminal transformation products including PFCAs and PFSAs; increasing environmental and human exposure and potential of adverse effects as a consequence of the high ultimate persistence and increasing usage of fluorinated alternatives; the high societal costs that would be caused if the uses, environmental fate, and adverse effects of fluorinated alternatives had to be investigated by publicly funded research; and the lack of consideration of non-persistent alternatives to long-chain PFASs.
Several classes of polyfluorinated chemicals that are potential precursors to the perfluorinated carboxylates and sulfonates are present in aqueous film-forming foams (AFFF). To assess the persistence of these AFFF-derived precursors, groundwater, soil, and aquifer solids were obtained in 2011 from an unlined firefighter training area at a U.S. Air Force Base where AFFF was regularly used between 1970 and 1990. To measure the total concentration of perfluorinated carboxylate and sulfonate precursors in archived AFFF formulations and AFFF-impacted environmental samples, a previously developed assay that uses hydroxyl radical to oxidize precursors to perfluorinated carboxylates was adapted for these media. This assay was employed along with direct measurement of 22 precursors found in AFFF and a suite of other poly- and perfluoroalkyl substances (PFASs). On a molar basis, precursors accounted for 41-100% of the total concentration of PFASs in archived AFFF formulations. In the training area, precursors measured by the oxidation assay accounted for an average of 23% and 28% of total PFASs (i.e., precursors and perfluorinated carboxylates and sulfonates) in groundwater and solids samples, respectively. One precursor in AFFF, perfluorohexane sulfonamide amine, was observed on several highly contaminated soil and aquifer solids samples, but no other precursors present in AFFF formulations were detected in any samples at this field site. Suspected intermediate transformation products of precursors in AFFF that were directly measured accounted for approximately half of the total precursor concentration in samples from the training site. The fraction of PFASs consisting of perfluorinated carboxylates and sulfonates was greater in groundwater and solid samples than in any archived AFFF formulations, suggesting that much of the mass of precursors released at the site was converted to perfluorinated carboxylates and sulfonates. The precursors that have persisted at this site may generate significant amounts of additional perfluorinated carboxylates and sulfonates upon remediation of contaminated groundwater or aquifer solids.
The distribution of polyfluoroalkyl compounds (PFCs) in the dissolved and particulate phase and their discharge from the river
Elbe into the North Sea were studied. The PFCs quantified included C4-C8 perfluorinated sulfonates (PFSAs), 6:2 fluorotelomer sulfonate (6:2 FTS), C6 and C8 perfluorinated sulfinates (PFSiAs), C4-C12 perfluorinated carboxylic acids (PFCAs), perfluoro-3,7-dimethyl-octanoic acid (3,7m2-PFOA), perfluorooctane sulfonamide (FOSA), and n-ethyl perfluroctane sulfonamidoethanol (EtFOSE). PFCs were mostly distributed
in the dissolved phase, where perfluorooctanoic acid (PFOA) dominated with 2.9–12.5 ng/L. In the suspended particulate matter
FOSA and perfluorooctane sulfonate (PFOS) showed the highest concentrations (4.0 ng/L and 2.3 ng/L, respectively). The total
flux of ΣPFCs from the river Elbe was estimated to be 802 kg/year for the dissolved phase and 152 kg/year for the particulate
phase. This indicates that the river Elbe acts as a source of PFCs into the North Sea. However, the concentrations of perfluorobutane
sulfonate (PFBS) and perfluorobutanoic acid (PFBA) in the North Sea were higher than that in the river Elbe, thus an alternative
source must exist for these compounds.
The primary aim of this article is to provide an overview of perfluoroalkyl and polyfluoroalkyl substances (PFASs) detected in the environment, wildlife, and humans, and recommend clear, specific, and descriptive terminology, names, and acronyms for PFASs. The overarching objective is to unify and harmonize communication on PFASs by offering terminology for use by the global scientific, regulatory, and industrial communities. A particular emphasis is placed on long-chain perfluoroalkyl acids, substances related to the long-chain perfluoroalkyl acids, and substances intended as alternatives to the use of the long-chain perfluoroalkyl acids or their precursors. First, we define PFASs, classify them into various families, and recommend a pragmatic set of common names and acronyms for both the families and their individual members. Terminology related to fluorinated polymers is an important aspect of our classification. Second, we provide a brief description of the 2 main production processes, electrochemical fluorination and telomerization, used for introducing perfluoroalkyl moieties into organic compounds, and we specify the types of byproducts (isomers and homologues) likely to arise in these processes. Third, we show how the principal families of PFASs are interrelated as industrial, environmental, or metabolic precursors or transformation products of one another. We pay particular attention to those PFASs that have the potential to be converted, by abiotic or biotic environmental processes or by human metabolism, into long-chain perfluoroalkyl carboxylic or sulfonic acids, which are currently the focus of regulatory action. The Supplemental Data lists 42 families and subfamilies of PFASs and 268 selected individual compounds, providing recommended names and acronyms, and structural formulas, as well as Chemical Abstracts Service registry numbers.
In most countries, sanitary landfilling is nowadays the most common way to eliminate municipal solid wastes (MSW). In spite of many advantages, generation of heavily polluted leachates, presenting significant variations in both volumetric flow and chemical composition, constitutes a major drawback. Year after year, the recognition of landfill leachate impact on environment has forced authorities to fix more and more stringent requirements for pollution control. This paper is a review of landfill leachate treatments. After the state of art, a discussion put in light an opportunity and some results of the treatment process performances are given. Advantages and drawbacks of the various treatments are discussed under the items: (a) leachate transfer, (b) biodegradation, (c) chemical and physical methods and (d) membrane processes. Several tables permit to review and summarize each treatment efficiency depending on operating conditions. Finally, considering the hardening of the standards of rejection, conventional landfill leachate treatment plants appear under-dimensioned or do not allow to reach the specifications required by the legislator. So that, new technologies or conventional ones improvements have been developed and tried to be financially attractive. Today, the use of membrane technologies, more especially reverse osmosis (RO), either as a main step in a landfill leachate treatment chain or as single post-treatment step has shown to be an indispensable means of achieving purification.
Per- and polyfluoroalkyl substances (PFAS) are compounds of emerging concern due to their persistence in the global water cycle and detection in drinking water sources. However, PFAS have been poorly studied in bottled water, especially in the United States. This study investigated the occurrence of PFAS and related factors in 101 uniquely labelled bottled water products for sale in the U.S. Products were screened for 32 target PFAS by solid phase extraction-liquid chromatography-tandem mass spectrometry (SPE-LC-MS/MS). Fifteen of 32 measured analytes were detected, consisting primarily of C3-C10 perfluorocarboxylic acids (PFCA) and C3-C6 and C8 perfluorosulfonic acids (PFSA). PFAS were detected above method detection limits in 39/101 tested products. The ∑32PFAS concentrations detected were 0.17-18.87 ng/L with a median of 0.98 ng/L; 97% of samples were below 5 ng/L. PFCA (83%) and short-chain perfluoroalkyl acids (PFAA) containing 5 or less CF2 groups (67%) were more prevalent on a mass basis than PFSA and longer-chain PFAA, respectively. Ultrashort-chain PFPrA, measured for the first time in bottled water, accounted for the greatest individual fraction of detected PFAS mass (42%) and was found almost exclusively in products labeled as Spring water. Purified water products contained significantly less PFAS than Spring water products, which was attributed to the use of reverse osmosis (RO) treatment in the majority of Purified waters (25/35) compared to Spring waters (1/45). RO-treated products contained significantly lower ∑32PFAS, long-chain, short-chain, and PFPrA concentrations than products without RO. Although no enforceable PFAS regulations exist for bottled water in the U.S., the finding that some products approach levels of concern justify a framework for monitoring PFAS in bottled water production.
Poly- and perfluoroalkyl substances (PFAS) comprise more than 4,000 anthropogenically manufactured compounds with widescale consumer and industrial applications. This critical review compiles the latest information on the worldwide distribution of PFAS and evaluates their fate in wastewater treatment plants (WWTPs). A large proportion (>30%) of monitoring studies in WWTPs were conducted in China, followed by Europe (30%) and North America (16%), whereas information is generally lacking for other parts of the world, including most of the developing countries. Short and long-chain perfluoroalkyl acids (PFAAs) were widely detected in both the influents (up to 1,000 ng/L) and effluents (15 to >1,500 ng/L) of WWTPs. To date, limited data is available regarding levels of PFAS precursors and ultra-short chain PFAS in WWTPs. Most WWTPs exhibited low removal efficiencies for PFAS, and many studies reported an increase in the levels of PFAAs after wastewater treatment. The analysis of the fate of various classes of PFAS at different wastewater treatment stages (aerobic and/aerobic biodegradation, photodegradation, and chemical degradation) revealed biodegradation as the primary mechanism responsible for the transformation of PFAS precursors to PFAAs in WWTPs. Remediation studies at full scale and laboratory scale suggest advanced processes such as adsorption using ion exchange resins, electrochemical degradation, and nanofiltration are more effective in removing PFAS (~95–100%) than conventional processes. However, the applicability of such treatments for real-world WWTPs faces significant challenges due to the scaling-up requirements, mass-transfer limitations, and management of treatment by-products and wastes. Combining more than one technique for effective removal of PFAS, while addressing limitations of the individual treatments, could be beneficial. Considering environmental concentrations of PFAS, cost-effectiveness, and ease of operation, nanofiltration followed by adsorption using wood-derived biochar and/or activated carbons could be a viable option if introduced to conventional treatment systems. However, the large-scale applicability of the same needs to be further verified.
Here we synthesize current understanding of the magnitudes and methods for assessing human and wildlife exposures to poly‐ and perfluoroalkyl substances (PFAS). Most human exposure assessments have focused on two to five legacy PFAS and wildlife assessments are typically limited to targeted PFAS (up to ~30 substances). However, shifts in chemical production are occurring rapidly and targeted methods for detecting PFAS have not kept pace with these changes. Total fluorine (TF) measurements complemented by suspect screening using high resolution mass spectrometry are thus emerging as essential tools for PFAS exposure assessment. Such methods enable researchers to better understand contributions from precursor compounds that degrade into terminal perfluoroalkyl acids (PFAA). Available data suggest that diet is the major human exposure pathway for some PFAS but there is large variability across populations and PFAS compounds. Additional data on TF in exposure media and the fraction of unidentified organofluorine are needed. Drinking water has been established as the major exposure source in contaminated communities. As water supplies are remediated, and for the general population, exposures from dust, personal care products, indoor environments and other sources may be more important. A major challenge for exposure assessments is the lack of statistically representative population surveys. For wildlife, bioaccumulation processes differ substantially between PFAS and neutral lipophilic organic compounds, prompting a revaluation of traditional bioaccumulation metrics. There is evidence that both phospholipids and proteins are important for the tissue partitioning and accumulation of PFAS. New mechanistic models for PFAS bioaccumulation are being developed that will assist in wildlife risk evaluations. This article is protected by copyright. All rights reserved.
Municipal solid waste contain diverse and significant amounts of per-and polyfluoroalkyl substances (PFAS), and these compounds may transform throughout the "landfilling" process from transport through landfill degradation. Fresh vehicle leachates, from commercial and residential waste collection vehicles at a transfer station, were measured for 51 PFAS. Results were compared to PFAS levels obtained from aged landfill leachate at the disposal facility. The landfill leachate was dominated by perfluoroalkyl acids (PFAAs, including perfluoroalkyl carboxylic acids (PFCAs) and perfluoroalkyl sulfonic acids (PFSAs); 86% of the total PFAS, by median mass concentration), while the majority of PFAS present in commercial and residential waste vehicle leachate were PFAA-precursors (70% and 56% of the total PFAS, by median mass concentration, respectively), suggesting precursor transformation to PFAAs during the course of landfill disposal. In addition, several PFAS, which are not routinely monitoredperfluoropropane sulfonic acid (PFPrS), 8-chloro-perfluoro-1-octane sulfonic acid (8Cl-PFOS), chlorinated polyfluoroether sulfonic acids (6:2, 8:2 Cl-PFESAs), sodium dodecafluoro-3H-4,8-dioxanonanoate (NaDONA), and perfluoro-4-ethylcyclohexanesulfonate (PFECHS)were detected. Potential degradation pathways were proposed based on published studies: transformation of polyfluoroalkyl phosphate diester (diPAPs) and fluorotelomer sulfonic acids (FTS) to form PFCAs via formation of intermediate products such as fluorotelomer carboxylic acids (FTCAs).
Large volumes of PFAS-contaminated wastewaters, such as municipal solid waste landfill leachates, pose a challenge for PFAS treatment technologies in practice today. In this study, the surfactant properties of PFAS were exploited to concentrate the compounds in foam produced via the bubble aeration of landfill leachate. The effectiveness of the foaming technique for concentrating PFAS varied by compound, with a mean removal percentage (the percent difference between PFAS in leachate before and after foam removal) of 68% and a median removal percentage of 92 % among the ten replicate foaming experiments. This technique appears to be similarly effective at sequestering sulfonates and carboxylate PFAS compounds, and is less effective at concentrating the smallest and largest PFAS molecules. The results of this study suggest that for the pretreatment or preconcentration of landfill leachates, foaming to sequester PFAS may provide a practical approach that could be strategically coupled to high energy PFAS-destructive treatment technologies. The process described herein is simple and could feasibly be applied at a relatively low cost at most landfills, where leachate aeration is already commonplace.
Contamination of soils with poly- and perfluoroalkyl substances (PFAS) has become a challenging issue due to the adverse effects of these substances on both the environment and public health. PFAS have strong chemical structures and their bonding with soil makes them challenging to eliminate from soil environments. Traditional methods of soil remediation have not been successful in their reduction or removal from the environment. This paper provides a comprehensive evaluation of existing and emerging technologies for remediating PFAS contaminated soils with guidance on which approach to use in different contexts. The functions of all remediation technologies, their suitability, limitations, and the scale applied from laboratory to the field are presented as a baseline for understanding the research need for treatment in soil environments. To date, the immobilization method has been a significant part of the remediation solution for PFAS contaminated soils, although its long-term efficiency still needs further investigation. Soil washing and thermal treatment techniques have been tested at the field scale, but they are expensive and energy-intensive due to the use of a large volume of washing solvent and the high melting point of PFAS, respectively; both methods need a large initial investment for their installation. Other remediation technologies, such as chemical oxidation, ball milling, and electron beams, have been progressed in the laboratory. However, additional research is needed to make them feasible, cost-effective and applicable in the field.
Poly- and perfluoroalkyl substances (PFAS) are a wide group of environmentally persistent organic compounds of industrial origin, which are of great concern due to their harmful impact on human health and ecosystems. Amongst long-chain PFAS, perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) are the most detected in the aquatic environment, even though their use has been limited by recent regulations. Recently, more attention has been posed on the short-chain compounds, due to their use as an alternative to long-chain ones, and to their high mobility in the water bodies. Therefore, short-chain PFAS have been increasingly detected in the environmental compartments. The main process investigated and implemented for PFAS removal is adsorption. However, to date, most adsorption studies have focused on synthetic water. The main objective of this article is to provide a critical review of the recent peer-reviewed studies on the removal of long- and short-chain PFAS by adsorption. Specific objectives are to review 1) the performance of different adsorbents for both long- and short-chain PFAS, 2) the effect of organic matter, and 3) the adsorbent regeneration techniques. Strong anion-exchange resins seem to better remove both long- and short-chain PFAS. However, the adsorption capacity of short-chain PFAS is lower than that observed for long-chain PFAS. Therefore, short-chain PFAS removal is more challenging. Furthermore, the effect of organic matter on PFAS adsorption in water or wastewater under real environmental conditions is overlooked. In most studies high PFAS levels have been often investigated without organic matter presence. The rapid breakthrough of PFAS is also a limiting factor and the regeneration of PFAS exhausted adsorbents is very challenging and needs more research.
Per- and polyfluoroalkyl substances (PFAS) are found ubiquitously in wastewater treatment plants (WWTPs) due to their multiple sources in industry and consumer products. In Australia, limited spatial data are available on PFAS levels in WWTPs influent, while no temporal data have been reported. The aim of this study was to investigate the occurrence and temporal trend of PFAS in the influent of two large WWTPs in Australia (WWTP A and B) over a four-year period. Daily influent samples were collected over one week at different seasons from 2014 to 2017. Eleven perfluoroalkyl acids (PFAA) (i.e. seven perfluoroalkyl carboxylic acids (PFCAs) and four perfluoroalkyl sulfonic acids (PFSA)) were detected with mean Σ11PFAA concentrations of 57 ± 3.3–94 ± 17 ng/L at WWTP A, and 31 ± 6.1–142 ± 73 ng/L at WWTP B. The highest mean concentrations were observed for perfluorohexanoate (PFHxA) (20 ± 2 ng/L) in WWTP A, and perfluorooctane sulfonate (PFOS) (17 ± 13 ng/L) in WWTP B. The precursor 6:2 fluorotelomer sulfonate was detected over five sampling periods from Aug 2016 to Oct 2017, with mean concentrations of 37 ± 18–138 ± 51 ng/L for WWTP A and 8.8 ± 4.5–29 ± 5.1 ng/L for WWTP B. Higher concentration of 6:2 FTS (1.8–11 folds) than those of PFOA and PFOS in WWTP A indicate a likely substitution of C8 PFAA by fluorotelomer-based PFAS in this catchment. Temporal trends (annual and seasonal) in per-capita mass load were observed for some PFAA, increasing for PFPeA, PFHxA, PFHpA, PFNA, and PFHxS, while decreasing for PFBS and PFOS in either WWTPs. Notably, elevated levels of PFOS in October 2017 were observed at both WWTPs with the highest per capita mass load of up to 67 μg/day/inhabitant. For some PFAS release trends, longer sampling periods would be required to achieve acceptable statistical power. Keywords: Per- and polyfluoroalkyl substances (PFAS), 6:2 fluorotelomer sulfonate (6:2 FTS), Temporal trends, Wastewater treatment plant (WWTP), Influent, Power, Effect size
The extent of per- and polyfluoroalkyl substances (PFAS) in groundwater surrounding legacy landfills is currently poorly constrained. Seventeen PFAS were analysed in groundwater surrounding legacy landfills in a major Australian urban re-development precinct. Sampling locations (n = 13) included sites installed directly in waste material and down-gradient from landfills, some of which exhibited evidence of leachate contamination including elevated concentrations of ammonia-N (≤106 mg/L), bicarbonate (≤1,740 mg/L) and dissolved methane (≤10.4 mg/L). Between one and fourteen PFAS were detected at all sites and PFOS, PFHxS, PFOA and PFBS were detected in all samples. The sum of detected PFAS (∑ 14 PFAS) varied from 26 ng/L at an ambient background site to 5,200 ng/L near a potential industrial point-source. PFHxS had the highest median concentration (34 ng/L; range: 2.6–280 ng/L) followed by PFOS (26 ng/L; range: 1.3–4,800 ng/L), PFHxA (19 ng/L; range: <LOQ – 46 ng/L) and PFOA (12 ng/L; range: 1.7–74 ng/L). Positive correlations between ∑ 14 PFAS, PFOA and other perfluoroalkyl carboxylic acids (PFCAs) (e.g. PFHxA) with typical leachate indicators including ammonia-N and bicarbonate were observed. In contrast, no such correlations were found with perfluoroalkyl sulfonic acids (PFSAs) (e.g., PFOS and PFHxS). In addition, a strong positive linear correlation (R ² = 0.69) was found between the proportion of PFOA in the sum of detected perfluorinated alkylated acids (PFOA/∑PFAA) and ammonia-N concentrations in groundwater. This is consistent with previous research showing relatively high PFOA/∑PFAA in municipal landfill leachates, and more conservative behaviour (e.g. less sorption and reactivity) of PFCAs during subsurface transport compared to PFSAs. PFOA/∑PFAA in groundwater may therefore be a useful indicator of municipal landfill-derived PFAA. One site with significantly elevated PFOS and PFHxS concentrations (4,800 and 280 ng/L, respectively) appears to be affected by point-source industrial contamination, as landfill leachate indicators were absent. PFAS have been analysed in groundwater surrounding legacy landfills in a major urban re-development precinct in Australia, to better understand their sources, fate and transport.
The concentrations and spatial occurrences of 17 legacy per- and polyfluoroalkyl substances (PFAS) and 4 emerging PFAS in the coastal water-dissolved phase, surface sediment phase and suspended particulate matter (SPM) in the coastal areas of Bohai Bay were investigated. In addition, the partition behaviors of PFAS in the water-SPM system and water-sediment system and the potential sources of PFAS in the marine environment were revealed. The total concentrations of PFAS (∑PFAS) in the water-dissolved phase, surface sediment and SPM were 20.5–684 ng/L, 2.69–25.0 ng/g dry weight (dw) and 4.39–527 ng/g dw, respectively. The level of PFAS contamination in the coastal areas of Shandong Province was higher than that in other areas. The average partition coefficients (log Kd) of PFAS in the water-SPM system and water-sediment system were 1.56–3.57 and 0.72–2.95, respectively. Long-chain PFAS and PFECHS (perfluoroethylcyclohexane sulfonate) have a higher log Kd than that of short-chain PFAS. PFAS with short carbon chains were mainly detected in the water-dissolved phase, but long-chain PFAS mainly occurred in the surface sediment and SPM phases. Source analysis based on the positive matrix factorization (PMF) model found that erosion inhibitor factories, aqueous film-forming foam factories, metal plating plants, fluoropolymer chemical manufacture and food contact materials were the main sources of PFAS in Bohai Bay. These results improved our understanding of the partitioning behavior and sources of PFAS in aquatic environments.
Here, we review present understanding of sources and trends in human exposure to poly- and perfluoroalkyl substances (PFASs) and epidemiologic evidence for impacts on cancer, immune function, metabolic outcomes, and neurodevelopment. More than 4000 PFASs have been manufactured by humans and hundreds have been detected in environmental samples. Direct exposures due to use in products can be quickly phased out by shifts in chemical production but exposures driven by PFAS accumulation in the ocean and marine food chains and contamination of groundwater persist over long timescales. Serum concentrations of legacy PFASs in humans are declining globally but total exposures to newer PFASs and precursor compounds have not been well characterized. Human exposures to legacy PFASs from seafood and drinking water are stable or increasing in many regions, suggesting observed declines reflect phase-outs in legacy PFAS use in consumer products. Many regions globally are continuing to discover PFAS contaminated sites from aqueous film forming foam (AFFF) use, particularly next to airports and military bases. Exposures from food packaging and indoor environments are uncertain due to a rapidly changing chemical landscape where legacy PFASs have been replaced by diverse precursors and custom molecules that are difficult to detect. Multiple studies find significant associations between PFAS exposure and adverse immune outcomes in children. Dyslipidemia is the strongest metabolic outcome associated with PFAS exposure. Evidence for cancer is limited to manufacturing locations with extremely high exposures and insufficient data are available to characterize impacts of PFAS exposures on neurodevelopment. Preliminary evidence suggests significant health effects associated with exposures to emerging PFASs. Lessons learned from legacy PFASs indicate that limited data should not be used as a justification to delay risk mitigation actions for replacement PFASs.
Landfills are the final stage in the life cycle of many products containing per- and polyfluoroalkyl substances (PFASs) and their presence has been reported in landfill leachate. The concentrations of 70 PFASs in 95 samples of leachate were measured in a survey of U.S. landfills of varying climates and waste ages. National release of PFASs was estimated by coupling measured concentrations for the 19 PFASs where more than 50% of samples had quantifiable concentrations, with climate-specific estimates of annual leachate volumes. For 2013, the total volume of leachate generated in the U.S. was estimated to be 61.1 million m3, with 79% of this volume coming from landfills in wet climates (> 75 cm/yr precipitation) that contain 47% of U.S. solid waste. The mass of measured PFASs from U.S. landfill leachate to wastewater treatment plants was estimated to be between 563 and 638 kg for 2013. In the majority of landfill leachate samples, 5:3 fluorotelomer carboxylic acid (FTCA) was dominant and variations in concentrations with waste age affected total estimated mass. There were six PFASs that demonstrated significantly higher concentrations in leachate from younger waste compared to older waste, while no PFAS demonstrated significant variation with climate.
Discarded carpet and clothing are potential sources of per- and polyfluoroalkyl substances (PFASs) in landfill leachate, but little is known about their release when disposed in landfills. The concentrations of 70 PFASs in the aqueous phase of anaerobic model landfill reactors filled with carpet or clothing were monitored under biologically-active and abiotic conditions. For carpet, total PFAS release was greater in live than abiotic reactors, with an average of 8.5 nmol/L and 0.62 nmol/L after 552 days, respectively. Release in live carpet reactors was primarily due to 5:3 fluorotelomer carboxylic acid (FTCA - 3.9 nmol/L) and perfluorohexanoic carboxylic acid (PFHxA - 2.9 nmol/L). For clothing, release was more dependent on sample heterogeneity than the presence of biological activity, with 0.63, 21.7, 2.6, and 6.3 nmol/L for two live and two abiotic reactors after 519 days, respectively. Release in the clothing reactors was largely due to perfluorooctatonic carboxylic acid (PFOA), with low relative concentrations of measured biotransformation precursors (FTCAs). For carpet and clothing reactors, the majority of PFAS release was not measured until after day 100. Results demonstrate that carpet and clothing are likely sources of PFASs in landfill leachate.
A wide variety of consumer products that are treated with poly- and perfluoroalkyl substances (PFASs) and related formulations are disposed in landfills. Landfill leachate has significant concentrations of PFASs and acts as secondary point sources to surface water. Here, we model how PFASs enter leachate using four lab-scale anaerobic bioreactors filled with municipal solid waste (MSW) and operated over 273 days. Duplicate reactors were monitored under live and abiotic conditions to evaluate influences attributable to biological activity. The biologically-active reactors simulated the methanogenic conditions that develop in all landfills, producing ~140 mL CH4/dry g refuse. The average total PFAS leaching measured in live reactors (16.7 nmol/kg dry-refuse) was greater than the average for abiotic reactors (2.83 nmol/kg dry-refuse), indicating biological processes were primarily responsible for leaching. The low level leaching in the abiotic reactors was primarily due to PFCAs ≤C8 (2.48 nmol/kg dry-refuse). Concentrations of known biodegradation intermediates, including methylperfluorobutane sulfonamide acetic acid and the n:2 and n:3 fluorotelomer carboxylates, increased steadily in concentration after the onset of methanogenesis, with the 5:3 fluorotelomer carboxylate becoming the single most concentrated PFAS observed in live reactors (9.53 nmol/kg dry-refuse).
Concentrations and isomer profiles for 24 per- and polyfluoroalkyl substances (PFASs) were monitored over 5 months (February-June, 2010) in municipal landfill leachate. These data were used to assess the role of perfluoroalkyl acid (PFAA) precursor degradation on changes in PFAA concentrations over time. The influence of total organic carbon, total suspended solids, pH, electrical conductivity (EC), leachate flow rates, and meteorological data (precipitation, air temperature) on leachate PFAS concentrations was also investigated. Perfluoropentanoate and perfluorohexanoate were typically the dominant PFASs in leachate, except for March-April, when concentrations of perfluorooctane sulfonate, perfluorooctanoate, and numerous PFAA-precursors (i.e., (N-alkyl) perfluorooctane sulfonamides and fluorotelomer carboxylic acids) increased by a factor of 2-10 (∼4 μg/L to ∼36 μg/L ΣPFASs). During this time, isomer profiles of PFOA became increasingly dominated by the linear isomer, likely from transformation of linear, telomer-manufactured precursors. While ΣPFAA-precursors accounted for up to 71% of ΣPFASs (molar basis) in leachate from this site, leachate from a second landfill displayed only low concentrations of precursors (<1% of ΣPFASs). Overall, degradation of PFAA-precursors and changes in leachate pH, EC, and 24-h precipitation were important factors controlling PFAS occurrence in leachate. Finally, 8.5-25 kg/yr (mean 16 kg/yr) of ΣPFASs was estimated to leave the landfill via leachate for subsequent treatment at a wastewater treatment plant.
Individual whole body homogenates of 4 year old lake trout (Salvelinus namaycush) samples collected in 2001 from each of the Great Lakes were extracted using a novel fluorophilicity cleanup step and analyzed for perfluoroalkyl compounds (PFCs). Standard addition and internal standardization were used for quantification. Results were reported (+/- SE) for perfluorinated carboxylates (PFCAs), perfluorinated sulfonates (PFSAs), and unsaturated fluorotelomer carboxylates (8:2 and 10:2 FTUCA). The lowest average concentration of sigmaPFC was found in samples from Lake Superior (13+/-1 ng g(-1)), while the highest average concentration was found in samples from Lake Erie (152+/-14 ng g(-1)). Samples from Lake Ontario (60+/-5 ng g(-1)) and Lake Huron (58 +/-10 ng g(-1)) showed similar average sigmaPFC concentrations, although the perfluorinated sulfonate/carboxylate ratios were different. The major perfluoroalkyl contaminant observed was perfluorooctane sulfonate (PFOS) with the highest concentration found in samples from Lake Erie (121+/-14 ng g(-1)), followed by samples from Lake Ontario (46+/-5 ng g(-1)), Lake Huron (39 +/-10 ng g(-1)), Lake Michigan (16+/-3 ng g(-1)), and Lake Superior (5+/-1 ng g(-1)). Perfluorodecane sulfonate (PFDS) was detected in 89% of the samples, with the highest concentration in Lake Erie samples (9.8+/-1.6 ng g(-1)), and lowest concentration in samples from Lake Superior (0.7 +/- 0.1 ng g(-1)). Statistically significant correlations were observed between PFOS and PFDS concentrations, and PFOS concentration and body weight, respectively. The PFCAs were detected in all samples, with the highest total average concentration in samples from Lake Erie (19 ng g(-1)), followed by samples from Lake Huron (16 ng g(-1)), Lake Ontario (10 ng g(-1)), Lake Michigan (9 ng g(-1)) and Lake Superior (7 ng g(-1)). The compounds with significant contributions to the sigmaPFCA concentrations were PFOA and C9-C13-PFCAs. The 8:2 FTUCA was detected at concentrations ranging between 0.1 and 0.2 ng g-1, with the highest level in samples showing also elevated concentrations of PFOA (4.4 ng g(-1) for Lake Michigan vs 1.5 ng g(-1) for all other samples). The 10:2 FTUCA was detected only in 9% of all samples (nd, 45 pg g(-1)). For those PFCs where we determined lake water concentrations, the highest log BAFs were calculated for PFOS (4.1), PFDA (3.9), and PFOSA (3.8).
Perfluorinated chemicals (PFCs) such as perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) have been produced and used in a wide range of industrial and consumer products for many decades. Their resistance to degradation has led to their widespread distribution in the environment, but little is known about how humans become exposed. Recent studies have demonstrated that the application of PFC contaminated biosolids can have important effects on local environments, ultimately leading to demonstrable human exposures. This manuscript describes a situation in Decatur, Alabama where PFC contaminated biosolids from a local municipal wastewater treatment facility that had received waste from local fluorochemical facilities were used as a soil amendment in local agricultural fields for as many as twelve years. Ten target PFCs were measured in surface and groundwater samples. Results show that surface and well water in the vicinity of these fields had elevated PFC concentrations, with 22% of the samples exceeding the U.S. Environmental Protection Agency's Provisional Health Advisory level for PFOA in drinking water of 400 ng/L. Water/soil concentration ratios as high as 0.34 for perfluorohexanoic acid, 0.17 for perfluoroheptanoic acid, and 0.04 for PFOA verify decreasing mobility from soils with increasing chain length while indicating that relatively high transport from soils to surface and well water is possible.
The recent implementation of soil and drinking water screening guidance values for two perfluorochemicals (PFCs), perfluorooctanoate (PFOA) and perfluorooctane sulfonate (PFOS) by the U.S. Environmental Protection Agency (EPA), reflects the growing concerns regarding the presence of these persistent and bioaccumulative chemicals in the natural environment. Previous work has established the potential risk to the environment from the land application of industrially contaminated biosolids, but studies focusing on environmental risk from land application of typical municipal biosolids are lacking. Thus, the present study investigated the occurrence and fate of PFCs from land-applied municipal biosolids by evaluating the levels, mass balance, desorption, and transport of PFCs in soils receiving application of municipal biosolids at various loading rates. This study is the first to report levels of PFCs in agricultural soils amended with typical municipal biosolids. PFOS was the dominant PFC in both biosolids (80-219 ng/g) and biosolids-amended soil (2-483 ng/g). Concentrations of all PFCs in soil increased linearly with increasing biosolids loading rate. These data were used to develop a model for predicting PFC soil concentrations in soils amended with typical municipal biosolids using cumulative biosolids loading rates. Mass balance calculations comparing PFCs applied vs those recovered in the surface soil interval indicated the potential transformation of PFC precursors. Laboratory desorption experiments indicated that the leaching potential of PFCs decreases with increasing chain length and that previously derived organic-carbon normalized partition coefficients may not be accurate predictors of the desorption of long-chain PFCs from biosolids-amended soils. Trace levels of PFCs were also detected in soil cores from biosolids-amended soils to depths of 120 cm, suggesting potential movement of these compounds within the soil profile over time and confirming the higher transport potential for short-chain PFCs in soils amended with municipal biosolids.
Perfluorooctanoic acid (PFOA) has been detected in environmental samples in Ohio and West Virginia near the Washington Works Plant in Parkersburg, West Virginia. This paper describes retrospective fate and transport modeling of PFOA concentrations in local air, surface water, groundwater, and six municipal water systems based on estimates of historic emission rates from the facility, physicochemical properties of PFOA, and local geologic and meteorological data beginning in 1951. We linked several environmental fate and transport modeling systems to model PFOA air dispersion, transit through the vadose zone, surface water transport, and groundwater flow and transport. These include AERMOD, PRZM-3, BreZo, MODFLOW, and MT3DMS. Several thousand PFOA measurements in municipal well water have been collected in this region since 1998. Our linked modeling system performs better than expected, predicting water concentrations within a factor of 2.1 of the average observed water concentration for each of the six municipal water districts after adjusting the organic carbon partition coefficient to fit the observed data. After model calibration, the Spearman's rank correlation coefficient for predicted versus observed water concentrations is 0.87. These models may be useful for estimating past and future public well water PFOA concentrations in this region.
Poly- and perfluorinated organic compounds (PFCs) are ubiquitous in the Arctic environment. Several modeling studies have been conducted in attempt to resolve the dominant transport pathway of PFCs to the arctic-atmospheric transport of precursors versus direct transport via ocean currents. These studies are generally limited by their focus on perfluorooctanoate (PFOA) fluxes to arctic seawater and thus far have only used fluorotelomer alcohols (FTOHs) and sulfonamide alcohols as inputs for volatile precursors. There have been many monitoring studies from the North American and European Arctic, however, almost nothing is known about PFC levels from the Russian Arctic. In general, there are very few measurements of PFCs from the abiotic environment. Atmospheric measurements show the widespread occurrence of PFC precursors, FTOHs and perfluorinated sulfonamide alcohols. Further, PFCAs and PFSAs have been detected on atmospheric particles. The detection of PFCAs and PFSAs in snow deposition is consistent with the volatile precursor transport hypothesis. There are very limited measurements of PFCs in seawater. PFOA is generally detected in the greatest concentrations. Additional seawater measurements are needed to validate existing model predications. The bulk of the monitoring efforts in biological samples have focused on the perfluorinated carboxylates (PFCAs) and sulfonates (PFSAs), although there are very few measurements of PFC precursors. The marine food web has been well studied, particularly the top predators. In contrast, freshwater and terrestrial ecosystems have been poorly studied. Studies show that in wildlife perfluorooctane sulfonate (PFOS) is generally measured in the highest concentration, followed by either perfluorononanoate (PFNA) or perfluoroundecanoate (PFUnA). However, some whale species show relatively high levels of perfluorooctane sulfonamide (PFOSA) and seabirds are typically characterized by high proportions of the C(11)-C(15) PFCAs. PFOA is generally infrequently detected and is present in low concentrations in arctic biota. Food web studies show high bioaccumulation in the upper trophic-level animals, although the mechanism of PFC biomagnification is not understood. Spatial trend studies show some differences between populations, although there are inconsistencies between PFC trends. The majority of temporal trend studies are from the Northern American Arctic and Greenland. Studies show generally increasing levels of PFCs from the 1970s, although some studies from the Canadian Arctic show recent declines in PFOS levels. In contrast, ringed seals and polar bears from Greenland continue to show increasing PFOS concentrations. The inconsistent temporal trends between regions may be representative of differences in emissions from source regions.
PFOA is a peroxisome proliferator (PPAR agonist) and exerts morphological and biochemical effects characteristic of PPAR agonists. These effects include increased beta-oxidation of fatty acids, increases in several cytochrome P-450 (CYP450)-mediated reactions, and inhibition of the secretion of very low-density lipoproteins and cholesterol from the liver. These effects on lipid metabolism and transport result in a reduction of cholesterol and triglycerides in serum and an accumulation of lipids in the liver. The triad of tumors observed (liver, Leydig cell, and pancreatic acinar-cell) is typical of many PPAR agonists and is believed to involve nongenotoxic mechanisms. The hepatocellular tumors observed in rats are likely to have been the result of the activation of the peroxisome proliferator activated receptor alpha (PPARalpha). The tumors observed in the testis (Leydig-cell) have been hypothesized to be associated with an increased level of serum estradiol in concert with testicular growth factors. The mechanism responsible for the acinar-cell tumors of the pancreas in rats remains the subject of active investigation. The mechanism resulting in the hepatocellular tumors in rats (PPARalpha activation) is not likely to be relevant to humans. Similarly, the proposed mechanism for Leydig-cell tumor formation is of questionable relevance to humans. Acinar tumors of the pancreas are rare in humans, and the relevance of the these tumors, as found in rats, to humans is uncertain. Epidemiological investigations and medical surveillance of occupationally exposed workers have not found consistent associations between PFOA exposure and adverse health effects.
Perfluorooctane sulfonate (PFOS) is a persistent and bioaccumulative perfluorinated acid detectable in humans and wildlife worldwide that has alerted scientists to examine the environmental fate of other fluorinated organic contaminants. Recently a homologous series of perfluoroalkyl carboxylates (PFCAs) was detected in the Arctic, yet little is known about their sources, breadth of contamination, or environmental distribution. In this study we analyzed for PFOS, the homologous series of PFCAs ranging from 8 to 15 carbons in chain length, and the PFOS-precursor heptadecafluorooctane sulfonamide (FOSA) in various organisms from a food web of Lake Ontario. The sampled organisms included a top predator fish, lake trout (Salvelinus namaycush), three forage fish species including rainbow smelt (Osmerus mordax), slimy sculpin (Cottus cognatus), and alewife (Alosa pseudoharengus), and two invertebrates Diporeia (Diporeia hoyi) and Mysis (Mysis relicta). A striking finding was that the highest mean concentration for each fluorinated contaminantwas detected in the benthic macroinvertebrate Diporeia, which occupies the lowest trophic level of all organisms analyzed. Perfluorinated acid concentrations in Diporeia were often 10-fold higher than in Mysis, a predominantly pelagic feeder, suggesting that a major source of perfluoroalkyl contaminants to this food web was the sediment, not the water. PFOS was the dominant acid in all samples, but long-chain PFCAs, ranging in length from 8 to 15 carbons, were also detected in most samples between <0.5 and 90 ng/ g. Among Mysis and the more pelagic fish species (e.g. excluding Diporeia and sculpin) there was evidence for biomagnification, but the influence of foraging on highly contaminated Diporeia and sculpin by these fish may have overestimated trophic magnification factors (TMFs), which ranged from 0.51 for FOSA to 5.88 for PFOS. By accounting for the known diet composition of lake trout, it was shown that bioaccumulation was indeed occurring at the top of the food web for all perfluoroalkyl compounds except PFOA. Future monitoring at other locations in Lake Ontario, and in other aquatic environments, is necessary to determine if these food web dynamics are widespread. Archived lake trout samples collected between 1980 and 2001 showed that mean whole body PFOS concentrations increased from 43 to 180 ng/g over this period, but not linearly, and may have been indirectly influenced by the invasion and proliferation of zebra mussels (Dreissena polymorpha) through effects on the population and ecology of forage fishes.
This review describes the sources, fate, and transport of perfluorocarboxylates (PFCAs) in the environment, with a specific focus on perfluorooctanoate (PFO). The global historical industry-wide emissions of total PFCAs from direct (manufacture, use, consumer products) and indirect (PFCA impurities and/or precursors) sources were estimated to be 3200-7300 tonnes. It was estimated that the majority (approximately 80%) of PFCAs have been released to the environment from fluoropolymer manufacture and use. Although indirect sources were estimated to be much less importantthan direct sources, there were larger uncertainties associated with the calculations for indirect sources. The physical-chemical properties of PFO (negligible vapor pressure, high solubility in water, and moderate sorption to solids) suggested that PFO would accumulate in surface waters. Estimated mass inventories of PFO in various environmental compartments confirmed that surface waters, especially oceans, contain the majority of PFO. The only environmental sinks for PFO were identified to be sediment burial and transport to the deep oceans, implying a long environmental residence time. Transport pathways for PFCAs in the environment were reviewed, and it was concluded that, in addition to atmospheric transport/degradation of precursors, atmospheric and ocean water transport of the PFCAs themselves could significantly contribute to their long-range transport. It was estimated that 2-12 tonnes/ year of PFO are transported to the Artic by oceanic transport, which is greater than the amount estimated to result from atmospheric transport/degradation of precursors.
Wastewater treatment plants have recently been identified as a significant pathway for the introduction of perfluoroalkyl surfactants (PASs) to natural waters. In this study, we measured concentrations and fate of several PASs in six wastewater treatment plants (WWTPs) in New York State. We also monitored and measured matrix effects (ionization suppression and enhancement) by postcolumn infusion and standard additions. Concentrations of perfluorooctanoate (PFOA) in effluents of the six WWTPs ranged from 58 to 1050 ng/L. Perfluorooctanesulfonate (PFOS) was also ubiquitous in effluents of these WWTPs, albeit at much lower concentrations (3-68 ng/L). Two of these WWTPs employed identical treatment processes, with similar hydraulic retentions, but differed only in that Plant B treated domestic and commercial waste, whereas Plant A had an additional industrial influence. We found that this industrial influence resulted in significantly greater mass flows of all of the PASs analyzed. Primary treatment was found to have no effect on the mass flows of PASs. Secondary treatment by activated sludge in Plant A significantly increased (p < 0.05) the mass flows of PFOS, PFOA, perfluorononanoate (PFNA), perfluorodecanoate (PFDA), and perfluoroundecanoate (PFUnDA). However, in Plant B, only the mass flow of PFOA was significantly increased. The observed increase in mass flow of several PASs may have resulted from biodegradation of precursor compounds such as fluorotelomer alcohols, which is supported by significant correlations in the mass flow of PFOA/PFNA and PFDA/PFUnDA. Furthermore, the masses of PFDA and PFUnDA were significantly correlated only after the secondary treatment. In Plant A, concentrations of odd-number PFCAs were greater than those of even-number PFCAs, and concentration decreased with increasing chain length (from C8 to C12). A different pattern was observed in sludge samples, in which the dominance of PFOA decreased, and PFDA and PFUnDA increased, suggesting preferential partitioning of longer-chain PFCAs to sludge.
The sorption of anionic perfluorochemical (PFC) surfactants of varying chain lengths to sediments was investigated using natural sediments of varying iron oxide and organic carbon content. Three classes of PFC surfactants were evaluated for sorptive potential: perfluorocarboxylates, perfluorosulfonates, and perfluorooctyl sulfonamide acetic acids. PFC surfactant sorption was influenced by both sediment-specific and solution-specific parameters. Sediment organic carbon, rather than sediment iron oxide content, was the dominant sediment-parameter affecting sorption, indicating the importance of hydrophobic interactions. However, sorption also increased with increasing solution [Ca2+] and decreasing pH, suggesting that electrostatic interactions play a role. Perfluorocarbon chain length was the dominant structural feature influencing sorption, with each CF2 moiety contributing 0.50-0.60 log units to the measured distribution coefficients. The sulfonate moiety contributed an additional 0.23 log units to the measured distribution coefficient, when compared to carboxylate analogs. In addition, the perfluorooctyl sulfonamide acetic acids demonstrated substantially stronger sorption than perfluorooctane sulfonate (PFOS). These data should prove useful for modeling the environmental fate of this class of contaminants.
Discharge of effluents from municipal wastewater treatment plants (WWTPs) is a route for the introduction of certain organic contaminants into aquatic environments. Earlier studies have reported the occurrence of perfluorochemicals in effluents from WWTPs. In this study, contamination profiles of perfluorinated compounds (PFCs), including perfluoroalkyl sulfonates (PFASs; PFOS, PFOSA, PFHxS) and perfluoroalkyl carboxylates (PFACs; PFOA, PFNA, PFDA, PFDoDA, PFUnDA), were determined in samples collected at various stages of wastewater treatment during different seasons. The two WWTPs selected for this study represent rural (Plant A, Kentucky) and urban (Plant B, Georgia) areas. PFOS was a major contaminant in samples from Plant A (8.2-990 ng/g dry wt in solid samples and 7.0-149 ng/L in aqueous samples), followed by PFOA (8.3-219 ng/g dry wt in solid samples and 22-334 ng/L in aqueous samples). PFOA was the predominant contaminant in samples from Plant B (7.0-130 ng/g dry wt in solid samples and 1-227 ng/L in aqueous samples), followed by PFOS (<2.5-77 ng/g dry wt in solid samples and 1.8-22 ng/L in aqueous samples). PFHxS, PFNA, PFDA, and PFOSA were detected in most of the samples, whereas PFUnDA and PFDoDA were detected in very few samples. Concentrations of some PFCs, particularly PFOA, were slightly higher in effluent than in influent, suggesting that biodegradation of some precursors contributes to the increase in PFOA concentrations in wastewater treatment processes. No large-magnitude seasonal variations in concentrations were found, although mass flow of PFCs was higher in winter than in summer. In general, samples from the rural plant in Kentucky contained greater concentrations of PFCs than did those from the urban plant in Georgia. Incineration of sludge reduced the PFC levels significantly. The mass flows of PFCs in these two plants were several hundreds of mg/day, comparable to flow values reported earlier.
This study reports the results of a screening survey of perfluoroalkyl compounds (PFCs) in the Danish environment. The study included point sources (municipal and industrial wastewater treatment plants and landfill sites) and the marine and freshwater environments. Effluent and influent water and sewage sludge were analysed for point sources. Sediment, blue mussels (Mytilus edulis) and liver from plaice (Pleuronectes platessa), flounder (Platichthys flesus) and eel (Anguilla anguilla) were analysed for the freshwater and marine environments. The results obtained show a diffuse PFCs contamination of the Danish environment with concentrations similar to those measured in other countries with the absence of primary contamination sources such as fluorochemical production. PFOS and PFOA were generally the most dominating PFCs measured in both point sources and the aquatic environments. PFCs were found in both inflow and outflow water and sewage sludge from municipal and industrial wastewater treatment plants (WWTPs), indicating that WWTPs can be significant sources to PFCs in the environment. This is also reflected in the locally elevated PFCs concentrations found in fish like eels from shallow freshwater and marine areas. However, the highest PFCs concentrations found in fish in this study was in plaice from the Skagerrak (156 ng/g wet weight PFOS), but it is unknown if this can be related to significant sources in the North Sea region or to differences between species. The concentrations of PFCs were below the detection limit in all analysed freshwater and marine samples of sediment and mussels. Despite the relatively low PFCs concentrations measured in marine fish, the high bioaccumulation potential of PFCs, particularly PFOS, may lead to high concentrations of PFCs in marine mammals as shown by previous investigations.
Fluorine is the most electronegative element in the periodic table. When bound to carbon it forms the strongest bonds in organic chemistry and this makes fluorine substitution attractive for the development of pharmaceuticals and a wide range of speciality materials. Although highly polarised, the C-F bond gains stability from the resultant electrostatic attraction between the polarised C delta+ and F delta- atoms. This polarity suppresses lone pair donation from fluorine and in general fluorine is a weak coordinator. However, the C-F bond has interesting properties which can be understood either in terms of electrostatic/dipole interactions or by considering stereoelectronic interactions with neighbouring bonds or lone pairs. In this tutorial review these fundamental aspects of the C-F bond are explored to rationalise the geometry, conformation and reactivity of individual organofluorine compounds.
Perfluorinated acids, including perfluorinated carboxylates (PFCAs), and perfluorinated sulfonates (PFASs), are environmentally persistent and have been detected in a variety of wildlife across the globe. The most commonly detected PFAS, perfluorooctane sulfonate (PFOS), has been classified as a persistent and bioaccumulative substance. Similarities in chemical structure and environmental behavior of PFOS and the PFCAs that have been detected in wildlife have generated concerns about the bioaccumulation potential of PFCAs. Differences between partitioning behavior of perfluorinated acids and persistent lipophilic compounds complicate the understanding of PFCA bioaccumulation and the subsequent classification of the bioaccumulation potential of PFCAs according to existing regulatory criteria. Based on available research on the bioaccumulation of perfluorinated acids, five key points are highlighted in this review: (1) bioconcentration and bioaccumulation of perfluorinated acids are directly related to the length of each compound's fluorinated carbon chain; (2) PFASs are more bioaccumulative than PFCAs of the same fluorinated carbon chain length; (3) PFCAs with seven fluorinated carbons or less (perfluorooctanoate (PFO) and shorter PFCAs) are not considered bioaccumulative according to the range of promulgated bioaccumulation,"B", regulatory criteria of 1000-5000 L/kg; (4) PFCAs with seven fluorinated carbons or less have low biomagnification potential in food webs, and (5) more research is necessary to fully characterize the bioaccumulation potential of PFCAs with longer fluorinated carbon chains (>7 fluorinated carbons), as PFCAs with longer fluorinated carbon chains may exhibit partitioning behavior similar to or greater than PFOS. The bioaccumulation potential of perfluorinated acids with seven fluorinated carbons or less appears to be several orders of magnitude lower than "legacy" persistent lipophilic compounds classified as bioaccumulative. Thus, although many PFCAs are environmentally persistent and can be present at detectable concentrations in wildlife, it is clear that PFCAs with seven fluorinated carbons or less (including PFO) are not bioaccumulative according to regulatory criteria.
Perfluorinated compounds have been used for more than 50 years as process aids, surfactants, and for surface protection. This study is a comprehensive assessment of consumer exposure to perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) from a variety of environmental and product-related sources. To identify relevant pathways leading to consumer exposure to PFOS and PFOA a scenario-based approach has been applied. Scenarios represent realistic situations where age- and gender-specific exposure occurs in the everyday life of consumers. We find that North American and European consumers are likely to experience ubiquitous and long-term uptake doses of PFOS and PFOA in the range of 3 to 220 ng per kg body weight per day (ng/kg(bw)/day) and 1 to 130 ng/kg(bw)/day, respectively. The greatest portion of the chronic exposure to PFOS and PFOA is likely to result from the intake of contaminated foods, including drinking water. Consumer products cause a minor portion of the consumer exposure to PFOS and PFOA. Of these, it is mainly impregnation sprays, treated carpets in homes, and coated food contact materials that may lead to consumer exposure to PFOS and PFOA. Children tend to experience higher total uptake doses (on a body weight basis) than teenagers and adults because of higher relative uptake via food consumption and hand-to-mouth transfer of chemical from treated carpets and ingestion of dust. The uptake estimates based on scenarios are within the range of values derived from blood serum data by applying a one-compartment pharmacokinetic model.
Recycling Association Statewide Study on Landfill Leachate PFOA and PFOS Impact on Water Resource Recovery Facility Influent
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Toxicological Profile for Perfluoroalkyls
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