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Per- and Polyfluorinated Alkyl Substances (PFAS) Cycling within Michigan: Contaminated Sites, Landfills and Wastewater Treatment Plants

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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.

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... 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. ...
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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.
Article
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
Article
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.
Article
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.
Article
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.
Article
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.
Article
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.
Article
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).
Article
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.
Article
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).
Article
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.
Article
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.
Article
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.
Article
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.
Article
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.
Article
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.
Article
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.
Article
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.
Article
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.
Article
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.
Article
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.
Article
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.
Article
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.
Article
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
  • Michigan Mwra
  • Waste
Toxicological Profile for Perfluoroalkyls
  • Chou
Policy analysis: a framework for regulation of new and existing PFAS by EPA
  • Dean
Dean, W.I., Adejumo, H., Caiati, A., Garay, P., Harmata, A., Li, L., Rodriguez, E., Sundar, S., 2020. Policy analysis: a framework for regulation of new and existing PFAS by EPA. J. Sci. Policy Governance 16, 1.
Method 537.1: determination of selected per- and Polyfluorinated Alkyl substances in drinking water by solid phase extraction and liquid Chromatography/Tandem Mass Spectrometry
  • J A Shoemaker
  • D R Tettenhorst
  • O Development
Shoemaker, J.A.; Tettenhorst, D.R. Development O.o.R.a (Ed.), Method 537.1: determination of selected per-and Polyfluorinated Alkyl substances in drinking water by solid phase extraction and liquid Chromatography/Tandem Mass Spectrometry (LC/MS/MS) 2018.