Perfluoroalkyl Acids Concentrations Research Articles

Impact of the increasing concentrations of selected perfluoroalkyl acids on the observed concentrations of red blood cell folate among US adults aged ≥20 years.

For the first time (N = 6291), a study was undertaken to estimate associations between the concentratio ns of red blood cell folate (RBCF) and concentration of six perfluoroalkyl acids (PFAAs), namely, perfluorooctanoic acid (PFOA), perfluorooctane sulfonic acid (PFOS), perfluorohexane sulfonic acid (PFHxS), perfluorodecanoic acid (PFDA), perfluorononanoic acid (PFNA), and perfluoroundecanoic acid (PFUnDA) for US adults aged ≥20 years by fitting regression models for the data from National Health and Nutrition Examination Survey for 2007-2014. In almost consistent fashion, increasing concentrations of PFAAs were associated with decreasing concentrations of RBCF. For the total population, for a 10% increase in the concentrations of PFOA, PFOS, PFDA, PFHxS, PFNA, and PFUnDA, percent decreases in RBCF concentrations were found to be 0.33%, 0.66%, 0.83%, 0.16%, 0.89%, and 0.43%, respectively. RBCF concentrations of PFAAs were found to be 1104, 1042, 100, and 936 nmol/L across the four quartiles of PFOS; 112, 1068, 1009, and 948 nmol/L across the four quartiles of PFDA; 1125, 1054, 1005, and 967 nmol/L across the four quartiles of PFNA; and 1099, 1094, 989, and 952 nmol/L across the four quartiles of PFUnDA. Perfluorinated carboxylic acids with carbon chain length > 8 decreased concentrations of RBCF to a greater degree than those carbon chain length ≤ 8. Perfluorinated chemicals with a sulfonic group with carbon chain length > 6 decreased concentrations of RBCF to a greater degree than those carbon chain length ≤ 6. The degree to which concentrations of RBCF decrease varied by age, gender, and race/ethnicity. Non-Hispanic blacks as compared to non-Hispanic whites and Hispanics had the lowest decreases in RBCF concentrations. Mechanisms responsible for negative associations between RBCF and PFAA concentrations are not known and will need to be researched further.

Trends (2005-2016) of perfluoroalkyl acids in top predator fish of the Laurentian Great Lakes.

This work presents the first assessment of temporal trends (2005-2016) for perfluoroalkyl acids (PFAAs) in top predator fish of the Laurentian Great Lakes except Lake Ontario, for which we provide a post-2008 update. Lake trout (Salvelinus namaycush) or walleye (Sander vitreus; Lake Erie only) collected annually from 2005 to 2016 were analyzed for 12 perfluoroalkyl carboxylic acids (PFCAs) and 4 perfluoroalkyl sulfonic acids (PFSAs) with carbon chain lengths between 4 and 16 (C4-C16). Individual analyte concentrations generally decreased in fish basin-wide between 2005 and 2016, including Lake Ontario lake trout previously found to lack declining PFAA concentrations up until 2008. Declining fish PFAA burden reflects a positive response to the industrial phase-outs of these chemicals. Notable exceptions to this general decline included most analytes in lake trout collected from Lake Superior near Keweenaw Point and C6 and C8 PFSAs and C9 PFCAs in Lake Erie lake trout and walleye, which exhibited constant or increasing concentrations in recent years. Recent increases in Lake Superior shoreline development and mobilization from increased sediment resuspension and contamination from biosolids-amended agricultural soils in the Lake Erie watershed are plausible explanations for these cases. However, data scarcity prohibits confirmation of these suspected causes. The lingering lack of declining concentrations noted in this study together with the ongoing evolution of the fluorinated chemical industry emphasize the vigilance needed to better understand how past and future emissions will affect the Great Lakes and global ecosystems.

Associations between perfluoroalkyl acids in serum and lead and mercury in whole blood among US children aged 3-11 years.

Data for 639 US children aged 3-11 years who participated in the National Health and Nutrition Examination Survey during 2013-2014 were analyzed by fitting regression models with log10-transformed values of blood lead and methyl and total mercury as dependent variables and log10-transformed values of perfluoroalkyl acids (PFAA) as one of the independent variables. PFAAs considered were 2-(N-methyl-perfluorooctane sulfonamido) acetic acid (MPAH), linear isomer of perfluorooctanoic acid (NPFOA), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluorohexane sulfonic acid (PFHxS), linear isomer of perfluorooctane sulfonic acid (NPFOS), and monomethyl branch isomer of perfluorooctane sulfonic acid (MPFOS). Adjusted regression slopes (β) indicating associations between the concentrations of PFAAs with blood lead and mercury were estimated. Statistically significant associations between concentrations of each PFAA and blood lead were observed. For 10% increases in concentrations of MPAH, NPFOA, PFNA, PFDA, PFHxS, NPFOS, and MPFOS, percent increases in the concentrations of blood lead were 0.45%, 1.59%, 0.78%, 0.32%, 0.65%, 1.32%, and 0.89% respectively. For 10% increases in concentrations of MPAH, PFNA, PFDA, and NPFOS, percent increases in the concentrations of total mercury in the blood were 1.62%, 1.44%, and 3.24% respectively. For 10% increases in concentrations of PFDA and NPFOS, percent increases in the concentrations of methyl mercury in the blood were 2.07% and 4.57% respectively. While concentrations of each of the seven PFAAs were positively associated with the concentrations of blood lead, concentrations of only PFDA and NPFOS were positively associated with increases in total and methyl mercury. PFAAs having positive associations with lead and mercury imply co-exposure and/or co-existence of high concentrations of PFAAs and lead/mercury. Since PFAAs as well as lead/mercury are known to be neurotoxic, nephrotoxic, and endocrine disruptors, their co-existence/co-exposure may lead to neurodevelopmental deficits that are additive/synergistic than neurodevelopmental deficits associated with exposures to PFAAs and lead/mercury alone. Future studies are needed to investigate additive/synergistic neurodevelopmental deficits associated with co-exposures to PFAAs and lead/mercury.

Estimating the Equilibrium Distribution of Perfluoroalkyl Acids and 4 of Their Alternatives in Mammals.

Perfluoroalkyl acids (PFAAs) mostly exist as ionic compounds that are of major concern because of their accumulative behavior. The discussion about their risk is ongoing considering the increasing production of structurally similar alternatives. We conducted model calculations based on equilibrium distribution coefficients that allow studying the distribution of PFAAs and their alternatives in various mammalian organs through comparison to empirical measurements in humans and rats. The calculations rely on experimentally determined distribution coefficients of a series of PFAAs and 4 of their alternatives to physiological matrices such as structural proteins, storage lipids, membrane lipids, albumin, and fatty acid binding protein (FABP). The relative sorption capacities in each organ were calculated from the combination of distribution coefficients and physiological data. The calculated distribution of PFAAs and alternatives within the organs showed that albumin and membrane lipids and, to a lesser extent, structural proteins have the highest relative sorption capacities for the compounds. Sorption to FABP is only relevant in the distribution of short-chain PFAAs. Storage lipids play a minor role in the distribution of all studied compounds. Our calculated distribution of PFAAs was evaluated by comparison to reported PFAA concentrations in various organs. Environ Toxicol Chem 2021;40:910-920. © 2020 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Uptake and translocation of perfluoroalkyl acids with different carbon chain lengths (C2-C8) in wheat (Triticum acstivnm L.) under the effect of copper exposure.

The co-contamination by perfluoroalkyl acids (PFAAs) and heavy metals (HMs) is ubiquitous in the surface environment subjected to sewage irrigation and land application of sludge. However, the joint effects of HMs and PFAAs on plant roots are not well clarified. This study explored the root uptake and acropetal translocation behaviors of C2-C8 PFAAs by wheat (Triticum acstivnm L.) under the co-exposure of copper (Cu). The underlying uptake mechanisms of PFAAs were verified in a defective root system. The results showed that excessive Cu (100-400μmol/L) damaged the cell membrane of wheat root to increase electrolytic leakage. In the defective root system, the root concentrations of PFAAs decreased by 6%-73% and the decrease rates were negatively associated with the carbon chain length of PFAAs. Along with the decrease in root concentrations of PFAAs, the amount of ultrashort-chain (C2-C3) and short-chain (C4-C6) PFAAs translocated to the shoot also decreased by 45%-84%. In contrast, the acropetal translocation of long-chain (C8) PFAAs, perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), was enhanced under Cu exposure due to the increase in root permeability as observed by increased electrolytic leakage. The shoot concentrations of PFOA and PFOS under Cu exposure were up to 5.5 and 11 times higher than those in the control, respectively. These results suggested that PFOA and PFOS could enter wheat root more easily through the breaks caused by Cu exposure and thereby their acropetal transportation to shoot was enhanced. Therefore, the risk of plant accumulation of long-chain PFAAs can be potentially underestimated if without considering the co-contamination with HMs in the environment.

Associations between concentrations of selected perfluoroalkyl acids and concentrations of blood cadmium, lead, and total mercury.

Data (N = 2552) from National Health and Nutrition Examination Survey for US adults aged ≥ 20 years for 2011-2016 were analyzed to estimate the associations between the concentrations of blood cadmium, lead, and total mercury and the concentrations of seven perfluoroalkyl acids (PFAA), namely, 2-(N-Methyl-perfluorooctane sulfonamido) acetic acid (MPAH), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluoroundecanoic acid (PFUnDA), perfluorohexane sulfonic acid (PFHxS), and perfluorooctane sulfonic acid (PFOS). Concentrations of blood cadmium were negatively associated with the concentrations of PFHxS (β = - 0.05428, p < 0.01) and PFOS (β = - 0.0212, p = 0.02). Concentrations of blood lead were positively associated with the concentrations of MPAH (β = 0.03301, p < 0.01), PFOA (β = 0.04783, p = 0.01), PFNA (β = 0.11761, p < 0.01), PFDA (β = 0.08007, p < 0.01), PFUA (β = 0.11382, p < 0.01), and PFOS (β = 0.04996, p = 0.02). Percent increases in the concentration of blood lead were 0.32%, 0.46%, 1.13%, 0.77%, 1.09%, and 0.48% for 10% increases in the concentrations of MPAH, PFOA, PFNA, PFDA, PFUA, and PFOS, respectively. Concentrations of blood total mercury were positively associated with the concentrations of PFNA (β = 0.37105, p < 0.01), PFDA (β = 0.46875, p < 0.01), PFUA (β = 0.56934, p < 0.01), and PFOS (β = 0.17557, p < 0.01). Percent increases in the concentration of blood total mercury were 3.6%, 4.57%, 5.58%, and 1.69% for 10% increases in the concentrations of PFNA, PFDA, PFUA, and PFOS, respectively. Associations between the concentrations of PFAAs with blood total mercury were substantially stronger than the concentrations with blood lead. Higher the carbon chain length for PFAAs, stronger were the associations between PFAAs with lead and mercury.

Influence of perfluoroalkyl acids and other parameters on circulating thyroid hormones and immune-related microRNA expression in free-ranging nestling peregrine falcons

Exposure to certain perfluoroalkyl acids (PFAAs) can have considerable effects on the endocrine and immune systems, although such effects remain largely uncharacterized in wildlife. Using an apex avian predator, we investigated possible relationships of thyroid hormones (THs), specifically free (F) and total (T) thyroxine (FT4; TT4) and triiodothyronine (FT3; TT3), and the expression of an immune-related microRNA biomarker (i.e., miR-155), with the concentrations of 11 PFAAs in nestling peregrine falcons (Falco peregrinus). Nestling peregrines (n = 56; usually two chicks of each sex per nest) were blood sampled when 23 ± 4 days old in urban and rural regions of the Laurentian Great Lakes Basin (Ontario, Canada) in 2016 and 2018. The circulating concentrations of several PFAAs were significantly associated with THs and estimated thyroid gland activity (TT3:TT4; FT3:FT4), including PFHxS (FT3; FT3:FT4), PFDS (TT3; TT3:TT4), PFOA (TT4; FT3:FT4), PFTeDA (TT4; FT3:FT4), PFHxDA (TT4; TT3:TT4) and ΣPFCAs (TT4). Our novel evaluation of miR-155 in peregrine nestlings identified significantly negative relationships of plasma miR-155 counts with PFHxS and PFOA concentrations, indicating potential down-regulation of miR-155 expression and impaired immunity. Several PFAA homologues significantly predicted the variation in THs and miR-155 in conjunction with year (e.g., inter-annual differences in weather, ambient temperature, rainfall), region (urban/rural), nestling age, and/or diet (trophic position; δ15N), which suggests that multiple environmental and biological stressors, including PFAA exposure, influenced thyroid activity and immune function in these nestlings. Further research is warranted to identify the mechanisms and additional impacts of PFAA-related thyroid and immune disruption on the growth, development, and health risks in developing birds.

Distribution behavior and risk assessment of emerging perfluoroalkyl acids in multiple environmental media at Luoma Lake, East China

Perfluoroalkyl acids (PFAAs) are ubiquitous in various environments. This has caused great public concern, particularly in the shallow freshwater lake region, where the lake, rivers, and estuaries form a highly interconnected continuum. However, little is known about the environmental behaviors of PFAAs in the continuum. For the first time, a high-resolution monitoring framework covering the river-estuary-lake continuum of Luoma Lake was built, and the concentrations, sources, and environmental fates of PFAAs were identified and analyzed. The results revealed that the total concentration of PFAAs was at a moderate level in the water and at a high level in the sediment compared to global levels respectively. Perfluorooctanesulfonate (PFOS) was the most abundant PFAA in the continuum. In particular, the ∑PFAA concentration in the particle phase was much higher than that in the sediment phase. Distinct spatial heterogeneities were observed in the behaviors of distribution and the multiphase fate of PFAAs in the continuum, mainly driven by the turbulent mixing during transport, dilution of lake water, and spatial differences of hydrodynamic features and sedimentary properties among the sub-regions. Interestingly, the pH of the sediment and water had significant effects on the water-sediment portioning of PFAAs in contrasting ways. Furthermore, based on the composition of the sediments, four possible migration paths for PFAAs were deduced and the main sources of PFAAs were identified as sewage, domestic, and industrial effluents using the positive matrix factorization model. During the human health assessment, no risk was found under the median exposure scenario; however, under the high exposure scenario, PFAAs posed uncertain risks to human health, which cannot be ignored. This study provides basic information for simulating the fate and transport of PFAAs in the continuum and is significant for developing cost-effective control and remediation strategies in the near future.

Urine concentrations of perfluoroalkyl acids in children and contributions of dietary factors: a cross-sectional study from Shanghai, China.

The production and emission of short-chain perfluoroalkyl acids (PFAAs) has increased over the years to replace long-chain PFAAs, leading to frequent detection in the environment and raising global concerns about the potential impacts on human health. In this study, the specific urine levels of 10 PFAAs were obtained from 189 children (age 8-12years) from two primary schools located in urban and suburban areas of Shanghai in 2019, and the contributions of dietary factors were investigated. Perfluorohexanoic acid (PFHxA), perfluoroheptanoic acid (PFHpA), and perfluorobutane sulfonate (PFBS) were detected in 100%, 99.5%, and 87.3% of the samples, with median concentrations of 20.20ng/L, 46.50ng/L, and 20.95ng/L, respectively. The most abundant PFAA was perfluorooctanoic acid (PFOA), with a median concentration of 78.90ng/L. The concentration of ∑PFAAs ranged from 61.10 to 4108.93ng/L, with a median concentration of 253.12ng/L. Children aged 8-9years had higher median levels of PFBS, perfluorohexane sulfonate (PFHxS), and perfluorooctane sulfonate (PFOS) than children aged 10-12years. Obese/overweight children had lower levels of PFHpA, PFBS, and PFOS. The intake of red meats, tubers, sugared beverages, fish and seafood, and eggs contributed to higher concentrations of PFAAs, while frequent intake of poultry and soy milk was associated with lower PFAA concentrations.

Understanding PFAAs exposure in a generalist seabird species breeding in the vicinity of a fluorochemical plant: Influence of maternal transfer and diet.

Perfluoroalkyl acids (PFAAs) are a focus of scientific and regulatory attention nowadays. However, PFAAs dynamics in the environment and the factors that determine wildlife exposure are still not well understood. In this study we examined PFAAs exposure in chicks of a generalist seabird species, the lesser black-backed gull (Larus fuscus), breeding 49km away of a PFAAs hotspot (a fluorochemical plant in Antwerp, Belgium). In order to study the pathways of PFAAs exposure, we measured how chicks' PFAAs burden varied with age, sex, and body condition. In addition, we related PFAA concentrations to chicks' diet using stable isotope signatures. For this purpose, we studied plasma PFAA concentrations in 1-week and 4-week-old gull chicks. Only 4 (PFOS, PFOA, PFDA and PFNA) out of the 13 target PFAA compounds were detected. Measured concentrations of PFOS and PFOA were generally high compared to other seabird species but were highly variable between individuals. Furthermore, our results suggest that maternal transfer plays a significant role in determining chicks' PFAAs burden, and that there are variable sources of exposure for PFOS and PFOA during post-hatching development. The association between PFOS and specific stable isotopes (i.e. δ15N and δ13C) suggests a higher exposure to PFOS in birds with a predominantly marine diet. We also found that males' condition was positively associated with PFOS plasmatic concentration, probably due to the indirect effect of being fed a high quality (marine) diet which appears PFOS rich. Yet, exact exposure source(s) for PFOA remain(s) unclear. Given that PFOS concentrations measured in some chicks surpassed the toxicity reference value calculated for top avian predators, continued monitoring of exposure and health of this gull population, and other wildlife populations inhabiting the area, is highly recommended.

The Impact of Smoking on the Association between Perfluoroalkyl Acids (PFAS) and Thyroid Hormones: A National Health and Nutrition Examination Survey Analysis.

Perfluoroalkyl acids (PFAS) are known endocrine disrupting chemicals, potentially affecting thyroid function. Smoking has been associated with PFAS levels as well as with thyroid function. The impact of smoking on the association between PFAS and thyroid function remains to be elucidated, so the objective was to assess the effect of PFAS exposure on thyroid function in the general population, stratified by smoking status, using the National Health and Nutrition Examination Survey (NHANES). NHANES adult participants who were part of the 2011–2012 laboratory subsample and had PFAS and thyroid function measured were included (n = 1325). Adjusted linear regression models and stratified analyses were performed. There was a significant positive association between perfluorooctanesulfonic acid (PFOS) (p = 0.003), perfluorononanoic acid (PFNA) (p = 0.014), total PFAS (p = 0.004) concentrations and free T4 (FT4). No significant associations were found between perfluorooctanoic acid (PFOA), PFOS, perfluorohexane sulfonate (PFHxS), PFNA, total PFAS and total T4 (TT4) or thyroid stimulating hormone (TSH). In non-smokers, a significant positive association was found between PFOS (p = 0.003), PFHxS (p = 0.034), PFNA (p = 0.012), total PFAS (p = 0.003) and FT4 while no significant associations were found in smokers. The present study showed that increased PFAS exposure was associated with increased FT4 in non-smokers, while no association was found in smokers. These results confirm that smoking modifies the association between PFAS exposure and thyroid function.

Bioaccumulation, trophic transfer and biomagnification of perfluoroalkyl acids (PFAAs) in the marine food web of the South China Sea

Knowledge about bioaccumulation and trophic transfer in food webs is of tremendous importance in contaminant hazards evaluation. Perfluoroalkyl acids (PFAAs) are widely distributed, and its emissions to coastal areas have posed a threat to the health of marine organisms and consumers. In this study, 15 species were sampled from Qinzhou Bay of the South China Sea. The concentrations of PFAAs in organisms were detected by liquid chromatography-mass spectrometry, and the trophic positions of organisms were constructed based on nitrogen isotope analysis. PFAAs were found in all organisms. The contents of PFOS in all organisms were higher than of PFOA, and the proportions of short-chain PFAAs were higher in the low trophic positioned organisms, while long-chain PFAAs were higher in the high trophic positioned organisms. Moreover, the bioaccumulation factors (BAFs) increased with the increasing number of fluorocarbon atoms. The trophic magnification factor (TMF) and the biomagnification factors (BMFs), calculated from the constructed food webs, together suggested potential biomagnification effects of PFOS, while less clear results were found for PFOA. Our results further indicate that previously banned long-chain PFAAs had persistent residuals in this coastal marine ecosystem, and that emerging short-chain PFAAs had high concentrations in some species but showed no biomagnification.

Formation and partitioning behaviour of perfluoroalkyl acids (PFAAs) in waste activated sludge during anaerobic digestion

The formation and fate of perfluoroalkyl acids (PFAAs) in sludge during anaerobic digestion (AD) is of global importance since the sludge is a significant source of PFAAs to the environment. The formation of PFAAs from polyfluorinated compounds, namely PFAA precursors, is poorly understood in AD. This study aims to investigate the formation of PFAAs from precursors and their partitioning behaviour in waste activated sludge (WAS) during AD process. To achieve this, three isotope-labelled PFAAs were spiked and monitored along with indigenous PFAAs and precursors over eight weeks in a laboratory-scale anaerobic digester, fed with sludge from a local wastewater treatment plant and operated with a hydraulic retention time of 12 days under 35 ℃. In addition to isotope-labelled PFAAs, twelve native PFAAs and eight polyfluorinated compounds were detected in the feed and digested sludges. A mass-balance model, validated by the spiking experiment, was applied to predict the concentrations of PFAAs and precursors assuming no formation/degradation in AD. The measured concentrations of short-chain PFAAs (perfluoroalkyl carboxylates (PFCAs): C < 8; perfluoroalkane sulfonates (PFSAs): C < 6) in the AD sludge were significantly (p < 0.05) higher than the model-predicted concentrations, indicating the formation of these PFAAs from precursors in AD. In contrast, the formation of long-chain PFAAs (PFCAs: C ≥ 8; PFSAs: C ≥ 6) was not observed. Moreover, the degradation of two polyfluoroalkyl phosphates (PAPs) (6:2 PAP and 6:2/8:2 diPAP) occurred, evidenced by their measured concentrations that were statistically lower than the mass-balance predictions. Further, the AD process reduced the amount of PFAAs absorbed/adsorbed to sludge, particularly for the long-chain ones, due to the breakdown of solids.

Pre- and post-diagnostic blood profiles of perfluoroalkyl acids in type 2 diabetes mellitus cases and controls

BackgroundStudies exploring the associations between perfluoroalkyl acids (PFAAs) and type 2 diabetes mellitus (T2DM) are rather limited and have reported conflicting results. All studies to date, including prospective ones, have relied on a single blood sample to study this association. Similarly, studies investigating how T2DM status may influence the longitudinal changes in PFAA concentrations have not been previously performed. As PFAA concentrations in humans have changed considerably over the last two decades, and as individuals diagnosed with T2DM usually undergo lifestyle changes that could influence these concentrations, a single blood sample may not necessarily reflect the life-time exposure to PFAA concentrations. Hence, repeated measurements from the same individuals will extend our understanding of how PFAAs are associated with T2DM. The present study, therefore, aimed to explore associations between pre- and post-diagnostic PFAA blood profiles and T2DM and assess factors associated with longitudinal changes in PFAAs in T2DM cases and controls. MethodsQuestionnaire data and blood samples from women participating in the Norwegian Women and Cancer study were used to conduct a nested case-control study among 46 T2DM cases matched to 85 non-diabetic controls. PFAAs were measured in blood samples collected prior to (2001/02) and after (2005/6) T2DM diagnosis. We investigated the association between PFAAs and incident and prevalent T2DM using conditional logistic regression. We assessed the longitudinal changes in PFAA concentrations within and between matched cases and controls using t-tests and linear regression models. ResultsWe observed no significant associations between pre-diagnostic PFAA concentrations and T2DM incidence. Similar results were observed for the post-diagnostic PFAA concentrations and T2DM prevalence. Decrease over time in PFAA concentrations were observed for PFOA and ∑PFOS concentrations, whereas increase over time were observed for PFNA, PFDA and PFUnDA concentrations. Longitudinal trends in PFAA concentrations among T2DM cases were similar to the changes observed in controls. ConclusionsThe study did not find evidence of association between PFAAs and incident or prevalent T2DM. The longitudinal changes in PFAAs concentrations were not influenced by T2DM status.

Multiphase distribution and spatial patterns of perfluoroalkyl acids (PFAAs) associated with catchment characteristics in a plain river network

Perfluoroalkyl acids (PFAAs) have emerged as global concerning contaminants because of their persistence, bioaccumulation, and toxicological effects. The transport and fate of PFAAs on dimension of plain river networks (PRNs) are difficult to model due to the unique regional characteristics (i.e., undirectional flows, low slope, complicated structure and connectivity) and the lack of data on PFAAs concentrations and compositions. A typical PRN (Taihu Basin, China) was selected to elucidate the spatial patterns of PFAAs in multi-matrices, including colloidal phase, soluble phase, suspended particles, and sediment. PFAAs were ubiquitously detected in plain rivers with total concentrations of 18.48–1220 ng/L in colloids, 139.07–721.37 ng/L in soluble phase, 97.69–2247 ng/g dw in suspended particles, and <72.04–178.12 ng/g dw in sediment. PFAAs were more likely to transport via dissolved phase and accumulate into sediment. Colloids carried 45.46–62.59% of ∑PFAAs in overlying water, while suspended particles contained <36.63% of ∑PFAAs, suggesting the important role of colloids in preloading PFAAs. Moreover, PFAAs variability was correlated with indicators of the structure and connectivity of river network by gray relational analysis. The mean gray relational degrees can be sorted as edge-node ratio (0.7609) > network connectivity (0.7191) > river density (0.7012) > water surface ratio (0.6887) > river development coefficient (0.6504) > functional connectivity (0.4780). These results suggested that the effects of catchment characteristics should be taken into account in understanding PFAAs fate in the PRNs.

Within- and Among-Clutch Variation of Yolk Perfluoroalkyl Acids in a Seabird from the Northern Adriatic Sea.

Perfluoroalkyl substances (PFAS) are surface-active agents used in diverse industrial and commercial applications. They contaminate both freshwater and marine ecosystems, are highly persistent, and accumulate through trophic transfer. Seabirds are exposed to environmental contaminants due to their high trophic position in food webs and relatively long lifespan. We measured levels of 10 perfluoroalkyl acids (PFAAs) in egg yolks of yellow-legged gulls (Larus michahellis) breeding in the northern Adriatic Sea (Northeast Italy). We examined variations in PFAAs within clutches (between eggs of different laying order) and among clutches. Perfluorooctane sulfonate (PFOS) was the most abundant yolk PFAA (mean = 42.0 ng/g wet wt), followed by perfluorooctanoic acid (PFOA; 3.8 ng/g wet wt) and perfluorododecanoic acid (PFDoDa; 2.8 ng/g wet wt). The ∑PFAAs averaged 57.4 ng/g wet weight, ranging between 26.5 and 115.0 ng/g wet weight. The PFAA levels varied substantially among clutches (0.29-0.79 of the total variation), whereas the effects of laying order were considerably weaker (0.01-0.13). Egg-laying order effects were detected for ∑PFAAs, PFOS, perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluoroundecanoic acid (PFUnA), and PFDoDa, whereby the last-laid eggs exhibited lower PFAA concentrations than early-laid eggs. Our results indicate that seagulls from the northern Adriatic basin deposit measurable amounts of PFAAs in their eggs. The large among-clutches differences in PFAAs suggest that exposure of yellow-legged gull females to these compounds is highly variable. Environ Toxicol Chem 2021;40:744-753. © 2020 SETAC.

Influence of Water Concentrations of Perfluoroalkyl Acids (PFAAs) on Their Size-Resolved Enrichment in Nascent Sea Spray Aerosols

Perfluoroalkyl acids (PFAAs) are persistent organic substances that have been widely detected in the global oceans. Previous laboratory experiments have demonstrated effective enrichment of PFAAs in nascent sea spray aerosols (SSA), suggesting that SSA are an important source of PFAAs to the atmosphere. In the present study, the effects of the water concentration of PFAAs on their size-resolved enrichment in SSA were examined using a sea spray simulation chamber. Aerosolization of the target compounds in almost all sizes of SSA revealed a strong linear relationship with their water concentrations (p < 0.05, r2 > 0.9). The enrichment factors (EF) of the target compounds showed no correlation with their concentrations in the chamber water, despite the concentrations varying by a factor of 500 (∼0.3 to ∼150 ng L–1). The particle surface-area-to-volume ratio appeared to be a key predictor of the enrichment of perfluoroalkyl carboxylic acids (PFCAs) with ≥7 perfluorinated carbons and perfluoroalkanesulfonic acids (PFSAs) with ≥6 perfluorinated carbons in supermicron particles (p < 0.05, r2 > 0.8), but not in submicron particles. The different enrichment behaviors of PFAAs in submicron and supermicron particles might be a result of the different production mechanisms of film droplets and jet droplets. The results suggest that the variability in seawater concentrations of PFAAs has little influence on EFs and that modeling studies designed to quantify the source of PFAAs via SSA emissions do not need to consider this factor.

Influence of soil on the uptake of perfluoroalkyl acids by lettuce: A comparison between a hydroponic study and a field study

This study explores whether mechanistic understanding of plant uptake of perfluoroalkyl acids (PFAAs) derived from hydroponic experiments can be applied to soil systems. Lettuces (Lactuca sativa) were grown in outdoor lysimeters in soil spiked with 4 different concentrations of 13 PFAAs. PFAA concentrations were measured in soil, soil pore water, lettuce roots, and foliage. The PFAA uptake by the lettuce was compared with uptake measured in a hydroponic study. The foliage:pore water concentration ratios in the lysimeter were similar to the foliage:water concentration ratios from the hydroponic experiment. In contrast, the root:pore water concentration ratios in the lysimeter were 1–2 orders of magnitude lower than in the hydroponic study for PFAAs with 6 or more perfluorinated carbons. Hence, hydroponic studies can be expected to provide a good quantitative measure of PFAA transfer from soil to foliage if one accounts for soil:pore water partitioning and differences in transpiration rate. However, hydroponic studies will be of little value for estimating PFAA transfer from soil to roots because sorption to the root surface is greatly enhanced under hydroponic conditions.

The Effects of Soil Organic Carbon Content on Plant Uptake of Soil Perfluoro Alkyl Acids (PFAAs) and the Potential Regulatory Implications

Perfluoro alkyl acids (PFAAs) are known to bioconcentrate in plants grown in contaminated soils; the potential risk from consuming these plants is currently less understood. We determined that the current daily reference doses (RfDs) of the US Environmental Protection Agency (USEPA) could be met by consuming a single radish grown in soils with a perfluorooctanoic acid (PFOA) concentration of 9.7 ng/g or a perfluorooctane sulfonate (PFOS) concentration of 90.5 ng/g. Using a combination of our own research and literature data on plant uptake of PFAAs from soil, we developed equations for predicting PFAA bioconcentration factors (BCFs) for plant shoot and root tissues grown in soils with a known percentage of organic carbon. This calculated BCF was then applied to 6 scenarios with measured soil PFAA concentrations to estimate PFAA concentrations in plants and potential exposure to humans and animals consuming harvested vegetation. Five of the 6 scenarios showed potential for surpassing USEPA PFAA RfDs at soil concentrations as low as 24 ng/g PFOA and 28 ng/g PFOS. Environ Toxicol Chem 2021;40:832-845. © 2020 SETAC.

Are Feathers of a Songbird Model Species (The Great Tit, Parus major) Suitable for Monitoring Perfluoroalkyl Acids (PFAAs) in Blood Plasma?

Feathers have been shown to be useful in the biomonitoring of environmental contaminants, such as metals and persistent organic pollutants. However, little is known regarding the levels of perfluoroalkyl acids (PFAAs) in feathers and the applicability of these structures for the biomonitoring of these compounds. In the present study, we report the extent to which feathers are suitable for monitoring PFAA concentrations in the blood plasma of an insectivorous songbird model species, the great tit (Parus major), settled at and in the vicinity of a fluorochemical plant in Antwerp, Belgium. For most of the target analytes (out of the 15 investigated), the feather PFAA concentrations near the plant are the highest ever reported in free-living birds. As PFAA concentrations did not differ in the adjacent sites, no pollution gradient with distance from the plant was observed. In addition, the PFAA concentrations were not associated with the age and sex of the birds. Perfluorooctanoic acid (PFOA) concentrations were significantly higher in P. major feathers than in blood plasma, but for most other PFAAs, these differences were not observed. The concentrations of perfluorooctanesulfonate (PFOS) and PFOA in P. major feathers and plasma were significantly and positively correlated when combining data from all sites but often not at individual sites. This result was likely caused by lower sample sizes at the individual sites and the use of matrices that represent different time periods. Our results suggest that P. major feathers cannot be used to estimate PFOA and PFOS concentrations in blood plasma, except when there is a great deal of variation in pollutant concentrations among sites/individual birds. Both matrices represent different time frames, providing complementary information on environmental PFAA concentrations, as illustrated by the observation that more PFAA compounds could be detected in P. major feathers than in blood plasma.