Perfluorotridecanoic Acid Research Articles

A 20-year study reveal decrease in per- and polyfluoroalkyl substances (PFAS) in a pelagic seabird from the Western Mediterranean Sea

Despite the first ban on perfluorooctane sulfonic acid (PFOS) in 2009, it remains unclear whether Europe, a key regulator, has effectively reduced per- and polyfluoroalkyl substances (PFAS) in the environment over the past 20 years. This study investigates the levels and temporal trends of 19 PFAS compounds in the livers of 62 Scopoli's shearwaters (Calonectris diomedea) collected from the Mediterranean basin during 2003–2022. Over the past two decades, PFAS concentrations showed an overall significant decrease of 77%. PFOS was the most frequently and predominantly detected chemical in livers, closely followed by perfluorotridecanoic acid (PFTrDA) and perfluoroundecanoic acid (PFUnDA). However, the contribution of PFTrDA (32.4%) surpassed that of PFOS (30.3%) in 2009–2014, which can be attributed to its increased use as a substitute following the regulation on PFOS in 2009. Perfluoroalkyl carboxylic acids (PFCAs), along with PFOS, showed a general decline over the study periods, with the largest decrease occurring after 2015, corresponding to the regulations on PFCAs. An odd-numbered, long-chain PFCAs accumulation trend was observed in samples. Principal component analysis showed a shift from PFOS to PFCAs in Scopoli's shearwater PFAS patterns over 20 years. Our results offer valuable insights into the environmental behavior of PFAS, the complex interactions between regulations and compounds and their transfer to the marine ecosystems. Despite widespread declines, their persistent detection underscores the need for enhanced international cooperation efforts to comprehensively mitigate PFAS emissions, including those from developing regions and unregulated sources.

Association between exposure to perfluoroalkyl substances (PFAS) and endometriosis in the ENDEA case-control study

BackgroundPerfluoroalkyl substances (PFAS) are environmental contaminants present in a wide range of consumer products and frequently detected in drinking water. They have been linked to adverse reproductive health outcomes in women, but there is limited human evidence on the association of PFAS exposure with endometriosis. Objective/AimTo explore the association between plasma concentrations of several PFAS, considered individually and as a mixture, and the risk of endometriosis in women of childbearing age. MethodsBetween 2018 and 2020, 42 patients with endometriosis and 90 controls undergoing abdominal surgery were recruited at two public hospitals in Granada, Spain. The presence or absence of endometriosis was ascertained by laparoscopic inspection of the pelvis and biopsy of suspected lesions (histological diagnosis). Concentrations of 10 PFAS were quantified in plasma samples from participants. Unconditional logistic regression was employed to examine associations of individual PFAS and summed concentrations of short (∑SC) and long-chain (∑LC) PFAS with odds of endometriosis, and quantile g-computation was used to assess their mixture effect. ResultsIn models adjusted for age, schooling, and parity, perfluorotridecanoic acid (PFTrDA) was associated with higher odds of endometriosis (odds ratio [OR] = 1.74; 95 % CI = 1.11–2.73 per 2-fold increase in plasma concentrations), while marginally significant associations were found for perfluorohexane sulfonate (PFHxS) (OR = 1.45, 95 % CI = 0.94–2.21) and ∑SC PFAS (OR = 1.48; 95 % CI = 0.96–2.30). No associations were found for the remaining PFAS. The PFAS mixture was non-significantly associated with 1.7-fold higher odds of endometriosis (95 % CI = 0.73–3.80), with perfluorononanoic acid (PFNA), PFHxS, and PFTrDA being the major contributors to this effect. ConclusionsThese findings suggest that exposure to certain PFAS may increase the odds of endometriosis. However, given the modest sample size, further studies are warranted to verify these results.

Determination of 13 perfluorinated and polyfluoroalkyl substances in fishes by QuEChERS-ultra-high performance liquid chromatography-tandem mass spectrometry

Perfluorinated and polyfluoroalkyl substances (PFASs) are compounds characterized by at least one perfluorinated carbon atom in an alkyl chain linked to side-chain groups. Owing to their unique chemical properties, these compounds are widely used in industrial production and daily life. However, owing to anthropogenic activities, sewage discharge, surface runoff, and atmospheric deposition, PFASs have gradually infiltrated the environment and aquatic resources. With their gradual accumulation in environmental waters, PFASs have been detected in fishes and several fish-feeding species, suggesting that they are bioconcentrated and even amplified in aquatic organisms. PFASs exhibit high intestinal absorption efficiencies, and they bioaccumulate at higher trophic levels in the food chain. They can be bioconcentrated in the human body via food (e. g., fish) and thus threaten human health. Therefore, establishing an efficient analytical technique for use in analyzing PFASs in typical fish samples and providing technical support for the safety regulation and risk assessment of fish products is necessary. In this study, by combining solvent extraction and magnetic dispersion-solid phase extraction (d-SPE), an improved QuEChERS method with ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) was developed for the determination of 13 PFASs in fish samples. Fe3O4-TiO2 can be used as an ideal adsorbent in the removal of sample matrix interference and a separation medium for the rapid encapsulation of other solids to be isolated from the solution. Based on the matrix characteristics of the fish products and structural properties of the target PFASs, Fe3O4-TiO2 and N-propyl ethylenediamine (PSA) were employed as adsorbents in dispersive purification. The internal standard method was used in the quantitative analyses of the PFASs. To optimize the sample pretreatment conditions of analyzing PFASs, the selection of the extraction solvent and amounts of Fe3O4-TiO2 and PSA were optimized. Several PFASs contain acidic groups that are non-dissociated in acidic environments, thus favoring their entry into the organic phase. In addition, acidified acetonitrile can denature and precipitate the proteins within the sample matrix, facilitating their removal. Finally, 2% formic acid acetonitrile was used as the extraction solvent, and 20 mg Fe3O4-TiO2, 20 mg PSA and 120 mg anhydrous MgSO4 were used as purification adsorbents. Under the optimized conditions, the developed method exhibited an excellent linearity (R≥0.9973) in the range of 0.01-50 μg/L, and the limits of detection (LODs) and quantification (LOQs) ranged from 0.001-0.023 and 0.003-0.078 μg/L, respectively. The recoveries of the 13 PFASs at low, medium, and high spiked levels (0.5, 10, and 100 μg/kg) were 78.1%-118%, with the intra- and inter-day precisions of 0.2%-11.1% and 0.8%-8.7%, respectively. This method was applied in analyzing real samples, and PFASs including perfluorooctanesulfonic acid, perfluorooctanoic acid, perfluoroundecanoic acid, perfluorododecanoic acid, and perfluorotridecanoic acid, were detected in all 11 samples evaluated. This method is simple, sensitive, and suitable for use in analyzing PFASs in fish samples.

Associations between prenatal exposure to per- and polyfluoroalkyl substances and plasma immune molecules in three-year-old children in China

BackgroundMany studies have reported that prenatal exposure to Per- and Polyfluoroalkyl Substances (PFASs) can disrupt immune function. However, little is known about the effects of PFASs on immune molecules. The study analyzed the association between prenatal exposure to mixed and single PFASs and plasma immune molecules in three-year-old children. MethodsTen PFASs were measured in umbilical cord serum, while peripheral blood samples were collected at age three to measure immune molecules. Associations between exposure to individual and combined PFASs and immune molecules were analyzed using Generalized Linear Models and Weighted Quantile Sum (WQS) regression. Results(1) Interleukin-4 (IL-4) increased by 23.85% (95% CI:2.99,48.94) with each doubling of Perfluorooctanoic Acid (PFOA), and Interleukin-6 (IL-6) increased by 39.07% (95%CI:4.06,85.86) with Perfluorotridecanoic Acid (PFTrDA). Elevated PFOA and Perfluorononanoic Acid (PFNA) were correlated with increases of 34.06% (95% CI: 6.41, 70.28) and 24.41% (95% CI: 0.99, 53.27) in Eotaxin-3, respectively. Additionally, the doubling of Perfluorohexane Sulfonic Acid (PFHxS) was associated with a 9.51% decrease in Periostin (95% CI: −17.84, −0.33). (2) The WQS analysis revealed that mixed PFASs were associated with increased IL-6 (β = 0.37, 95%CI:0.04,0.69), mainly driven by PFTrDA, PFNA, and 8:2 Chlorinated Perfluoroethyl Sulfonamide (8:2 Cl-PFESA). Moreover, mixed PFASs were linked to an increase in Eotaxin-3 (β = 0.32, 95% CI: 0.09,0.55), primarily influenced by PFOA, PFTrDA, and Perfluorododecanoic Acid (PFDoDA). ConclusionsPrenatal PFASs exposure significantly alters the levels of immune molecules in three-year-old children, highlighting the importance of understanding environmental impacts on early immune development.

Species-specific profiles of per- and polyfluoroalkyl substances (PFAS) in small coastal sharks along the South Atlantic Bight of the United States

Per- and polyfluoroalkyl substances (PFAS) have gained widespread commercial use across the globe in various industrial and consumer products, such as textiles, firefighting foams, and surface coating materials. Studies have shown that PFAS exhibit a strong tendency to accumulate within aquatic food webs, primarily due to their high bioaccumulation potential and resistance to degradation. Despite such concerns, their impact on marine predators like sharks remains underexplored. This study aimed to investigate the presence of 34 PFAS in the plasma (n = 315) of four small coastal sharks inhabiting the South Atlantic Bight of the United States (U.S). Among the sharks studied, bonnetheads (Sphyrna tiburo) had the highest ∑PFAS concentration (3031 ± 1674 pg g − 1 plasma, n = 103), followed by the Atlantic sharpnose shark (Rhizoprionodon terraenovae, 2407 ± 969 pg g − 1, n = 101), blacknose shark (Carcharhinus acronotus, 1713 ± 662 pg g − 1, n = 83) and finetooth shark (Carcharhinus isodon, 1431 ± 891 pg g − 1, n = 28). Despite declines in the manufacturing of perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA), the long-chain (C8 – C13) perfluoroalkyl acids (PFAAs) were frequently detected, with PFOS, perfluorodecanoic acid (PFDA), and perfluorotridecanoic acid (PFTrDA) present as the most dominant PFAS. Furthermore, males exhibited significantly higher ∑PFAS concentrations than females in bonnetheads (p < 0.01), suggesting possible sex-specific PFAS accumulation or maternal offloading in some species. The results of this study underscore the urgency for more extensive biomonitoring of PFAS in aquatic/marine environments to obtain a comprehensive understanding of the impact and fate of these emerging pollutants on marine fauna.

Associations between serum per- and polyfluoroalkyl substances as mixtures and lipid levels: A cross-sectional study in Jinan

Per- and polyfluoroalkyl substances (PFASs) are known to be linked with dyslipidemia. Between March and June 2022, we collected 575 fasting serum samples from individuals without occupational exposure in Jinan, China. Eighteen PFASs were analyzed using UHPLC-Orbitrap MS. Multiple linear regression (MLR), Bayesian kernel machine regression (BKMR), and Quantile g-computation (QGC) models were utilized to assess the effects of both individual PFAS and PFAS mixtures on serum lipid levels, including triglycerides (TG), cholesterol (CHO), high-density lipoprotein (HDL), and low-density lipoprotein (LDL). The PFAS mixture, composed of perfluoroheptanoic acid (PFHpA), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluoroundecanoic acid (PFUnDA), perfluorododecanoic acid (PFDoDA), perfluorotridecanoic acid (PFTrDA), perfluorohexane sulfonate (PFHxS), perfluoroheptane sulfonic acid (PFHpS), perfluorooctane sulfonate (PFOS), and 6:2 chlorinated polyfluoroalkyl ether sulfonate (6:2 Cl-PFESA), showed a positive association with CHO and LDL levels, while no distinct trend was noted in HDL and TG levels about changes in PFAS mixtures levels in BKMR and QGC models, adjusted for gender, age, BMI, occupation, and educational level. The effects of individual PFASs on lipid levels were in general consistent across MLR, BKMR and QGC models. PFUnDA and PFTrDA demonstrated greater impacts on blood lipid levels compared to other PFAS, albeit with varied directional effects. Age-stratified analysis revealed PFAS mixture effect was more pronounced in participants aged higher than 40. No obvious trend in lipid levels with changes in PFAS mixture levels in participants with age ranged from 18 to 40, while positive association between PFAS mixture and CHO and LDL was detected in participants aged higher than 40.

Per/Polyfluoroalkyl Substances (PFASs) in a Marine Apex Predator (White Shark, Carcharodon carcharias) in the Northwest Atlantic Ocean.

Per/polyfluoroalkyl substances (PFASs) are ubiquitous, highly persistent anthropogenic chemicals that bioaccumulate and biomagnify in aquatic food webs and are associated with adverse health effects, including liver and kidney diseases, cancers, and immunosuppression. We investigated the accumulation of PFASs in a marine apex predator, the white shark (Carcharodon carcharias). Muscle (N = 12) and blood plasma (N = 27) samples were collected from 27 sharks during 2018-2021 OCEARCH expeditions along the eastern coast of North America from Nova Scotia to Florida. Samples were analyzed for 47 (plasma) and 43 (muscle) targeted PFASs and screened for >2600 known and novel PFASs using liquid chromatography coupled to high-resolution mass spectrometry (LC-HRMS). Perfluoroalkyl carboxylates with carbon chain-length C11 to C14 were frequently detected above the method reporting limits in plasma samples, along with perfluorooctanesulfonate and perfluorodecanesulfonate. Perfluoropentadecanoate was also detected in 100% of plasma samples and concentrations were estimated semiquantitatively as no analytical standard was available. Total concentrations of frequently detected PFASs in plasma ranged from 0.56 to 2.9 ng mL-1 (median of 1.4 ng mL-1). In muscle tissue, nine targeted PFASs were frequently detected, with total concentration ranging from 0.20 to 0.84 ng g-1 ww. For all frequently detected PFASs, concentrations were greater in plasma than in muscle collected from the same organism. In both matrices, perfluorotridecanoic acid was the most abundant PFAS, consistent with several other studies. PFASs with similar chain-lengths correlated significantly among the plasma samples, suggesting similar sources. Total concentrations of PFASs in plasma were significantly greater in sharks sampled off of Nova Scotia than all sharks from other locations, potentially due to differences in diet. HRMS suspect screening tentatively identified 13 additional PFASs in plasma, though identification confidence was low, as no MS/MS fragmentation was collected due to low intensities. The widespread detection of long-chain PFASs in plasma and muscle of white sharks highlights the prevalence and potential biomagnification of these compounds in marine apex predators.

The Association between Prenatal Exposure to Per- and Polyfluoroalkyl Substances and Respiratory Tract Infections in Preschool Children: A Wuhan Cohort Study.

This study investigates the association between prenatal exposure to per- and polyfluoroalkyl substances (PFASs) and the incidence and frequency of respiratory tract infections (RTIs) in preschool children. We selected 527 mother-infant pairs from Wuhan Healthy Baby Cohort (WHBC), China. Ten PFASs were measured in umbilical cord serum, and we collected data on common RTIs in preschool children aged 4 years through a questionnaire. Associations of single PFASs with the incidence and frequency of RTIs were analyzed via Logistic regression and Poisson regression, while the collective effect was assessed by weighted quantile sum (WQS) regression. Furthermore, stratified and interaction analyses were performed to evaluate if there were sex-specific associations. We found a positive correlation between perfluorododecanoic acid (PFDoDA) and the incidence of tonsillitis, with several PFASs also showing positive associations with its frequency. Moreover, perfluorotridecanoic acid (PFTrDA) showed a positive link with the frequency of common cold. The results of WQS regression revealed that after adjusting for other covariates, PFASs mixture showed a positive association with the incidence of tonsillitis, the frequency of common cold, and episodes. In particular, perfluoroundecanoic acid (PFUnDA), PFDoDA, PFTrDA, perfluorodecanoic acid (PFDA) and 8:2 chlorinated polyfluorinated ether sulfonic acid (8:2 Cl-PFESA) had the most significant impact on this combined effect. The results suggest that both single and mixed exposures to PFASs may cause RTIs in preschool children. However, there was no statistically significant interaction between different PFASs and sex.

Biomagnification and temporal trends (1990–2021) of perfluoroalkyl substances in striped dolphins (Stenella coeruleoalba) from the NW Mediterranean sea

Poly- and Perfluoroalkyl Substances (PFAS) are a well-known class of pollutants which can bioaccumulate and biomagnify with a vast majority being highly persistent. This study aims to determine the biomagnification rates of PFAS in sexually mature striped dolphins and to assess temporal trends on PFAS concentrations over the past three decades (1990–2021) in the North-Western Mediterranean Sea. Thirteen and 17 of the 19 targeted PFAS were detected in the samples of the dolphins’ digestive content and liver, respectively, at concentrations ranging between 43 and 1609 ng/g wet weight, and 254 and 7010 ng/g wet weight, respectively. The most abundant compounds in both types of samples were linear perfluorooctanesulfonic acid (n-PFOS) and perfluorooctanesulfonamide (FOSA), which were present in all samples, followed by perfluoroundecanoic acid (PFUnDA), perfluorotridecanoic acid (PFTrDA) and perfluorononanoic acid (PFNA). Long-chain PFAS (i.e., PFCAs C ≥ 7 and PFSAs C ≥ 6) biomagnified to a greater extent than short-chain PFAS, suggesting a potential effect on the health of striped dolphins. Environmental Quality Standards concentrations set in 2014 by the European Union were exceeded in half of the samples of digestive content, suggesting that polluted prey may pose potential health risks for striped dolphins. Concentrations of most long-chain PFAS increased from 1990 to 2004–2009, then stabilized during 2014–2021, possibly following country regulations and industrial initiatives. The current study highlights the persistent presence of banned PFAS and may contribute to future ecological risk assessments and the design of management strategies to mitigate PFAS pollution in marine ecosystems.

Trimester-specific hemodynamics of per- and polyfluoroalkyl substances and its relation to lipid profile in pregnant women

Per- and polyfluoroalkyl substances (PFAS) are persistent organic pollutants widely detected in blood from pregnant women, yet limited study evaluated the trimester-specific variance of serum PFAS, and even less is known for the window of vulnerability to lipids metabolism interrupting effects of PFAS during pregnancy. We quantified 16 legacy, 3 emerging PFAS, and lipid biomarkers in 286 serum samples from 118 pregnant women. All target PFAS, except perfluorotridecanoic acid (PFTrDA), in maternal serum showed moderate to low temporal irregular variability across gestation (average intraclass correlation coefficients ≥ 0.57), while the generalized estimating equations showed a significant declining trend in the serum levels during pregnancy (p for trend < 0.05). The decline of 6:2 chlorinated polyfluorinated ether sulfonate in maternal serum was the greatest with a change of − 21.63% from 1st to 2nd trimester, which indicated a possible higher accumulation of this emerging PFAS in fetal compartment. Multiple linear regression, multiple informant model and Bayesian kernel machine regression showed a higher vulnerability in the 1st trimester to effects of PFAS exposure on serum lipids of pregnant women. The results highlighted the importance of the study timing of PFAS exposure during pregnancy.

Per- and poly-fluoroalkyl substances in Tawny Owl (Strix aluco) feathers from Trøndelag, Norway

Per- and polyfluoroalkyl substances (PFASs) are contaminants of global concern due to their ubiquitous occurrence in the environment, bioaccumulation and the adverse effects on organisms. Tawny Owls (Strix aluco) are documented to be exposed to increasing concentrations of perfluoroalkyl carboxylic acids (PFCAs), and have been suggested in literature as a key raptor monitoring species. Therefore, non-destructive biomonitoring efforts are of high interest. Thus far, the use of feathers for biomonitoring PFASs in Tawny Owls has not been investigated. In this study, 32 PFASs were analyzed in 49 Tawny Owl body feather samples collected from 2017 to 2020 in Trøndelag, Norway. There were 30 PFASs detected in at least one feather, with the sum concentrations ranging from 31 to 203 ng/g (w.w.). Perfluoroheptanoic acid (PFHpA) (median: 33 ng/g) and perfluorooctane sulfonamidoacetic acid (FOSAA) (median: 18 ng/g) were the two compounds with the highest concentrations. Perfluorooctane sulfonic acid (PFOS), which is banned for production and use in Norway since 2007, was found in all samples (median: 4.14 ng/g), indicating its high persistence. 8 PFASs were detected in at least 50 % of the samples: FOSAA (11–127 ng/g), PFHpA (<0.04–115 ng/g), perfluorobutanesulfonic acid (PFBS) (<0.28–21 ng/g), PFOS (0.23–13 ng/g), perfluorotridecanoic acid (PFTrDA) (0.24–5.15 ng/g), perfluorododecanoic acid (PFDoDA) (<0.28–4.45 ng/g), perfluoroundecanoic acid (PFUnDA) (<0.28–2.33 ng/g), and 1H,1H,2H,2H-perfluorooctanesulfonic acid (6:2 FTSA) (0.07–1.01 ng/g). No significant differences were found for the concentrations of PFASs between calendar years and locations, but a slight increase could be observed in the sum concentration of PFASs (Ʃ32PFASs) over the sampling years. As Tawny Owls are residential owls that usually do not cover great distances, their feathers can be used as a potential alternative matrix for future biomonitoring studies. To our knowledge, this is the first study on the occurrence of 32 PFASs investigated in feathers of a Tawny Owl population.

Perfluoroalkyl Substances in Seabird Eggs from Canada's Pacific Coast: Temporal Trends (1973-2019) and Interspecific Patterns.

Whether perfluoroalkyl sulfonates (PFSAs) and perfluoroalkyl carboxylates (PFCAs) are responding to legislative restrictions and showing decreasing trends in top marine predators that range across the eastern North Pacific Ocean is unclear. Here, we examined longer-term temporal trends (1973-2019) of 4 PFSAs and 13 PFCAs, as well stable isotopes of δ13C and δ15N, in the eggs of 4 seabird species sampled along a nearshore-offshore gradient; double-crested cormorants (Nannopterum auritum), pelagic cormorants (Urile pelagicus), rhinoceros auklets (Cerorhinca monocerata), and Leach's storm-petrels (Hydrobates leucorhous) from the Pacific coast of British Columbia, Canada. PFOS was the most abundant PFSA (79-94%) detected in all eggs regardless of colony and year, with the highest concentrations, on average, measured in auklet eggs (mean = 58 ng g-1, range = 11-286 ng g-1 ww). Perfluoroundecanoic acid (PFUdA) and perfluorotridecanoic acid (PFTriDA) were the dominant long-chain PFCAs (≥30% combined). The majority of PFSAs (including PFOS) are statistically declining (p < 0.001) in the eggs of all 4 species with PFOS half-lives ranging from 2.6 to 7.8 years. Concentrations of long-chain PFCAs exhibited a trajectory comprised of linear increases and second-order declines, suggesting that the rate of uptake of PFCAs is slowing or leveling off. These trends are consistent with the voluntarily ceased production of PFSAs by 3M circa 2000-2003 and are among the first from the northeast Pacific to indicate a positive response to several regulations and restrictions on PFCAs from facility emissions and product content.

Evidence of large-scale deposition of airborne emissions of per- and polyfluoroalkyl substances (PFASs) near a fluoropolymer production plant in an urban area

Airborne emissions of per- and polyfluoroalkyl substances (PFASs) from fluoropolymer manufacturing facilities—especially those producing polyvinylidene (PVDF)—have rarely been investigated. Once PFASs are released into the air from the facility stacks, they settle in the surrounding environment, contaminating all surfaces. Human beings living in close proximity to these facilities can be exposed through air inhalation and ingestion of contaminated vegetables, drinking water or dust. In this study, we collected nine surface soil and five outdoor settled dust samples within 200 m of the fence line of a PVDF and fluoroelastomer production site near Lyon (France). Samples were collected in an urban area including a sports field. High concentrations of long-chain perfluoroalkyl carboxylic acids (PFCAs) (C ≥ 9) were found at sampling points downwind of the facility. Perfluoroundecanoic acid (PFUnDA) was the predominant PFAS in surface soil (12–245 ng/g dw), whereas perfluorotridecanoic acid (PFTrDA) was in outdoor dust (<0.5–59 ng/g dw). The PFAS profiles observed in soil and dust samples very likely originate from the processing aids used for PVDF and fluoroelastomer production. To our knowledge, long-chain PFCA concentrations as high as reported herein have never been found outside the perimeter fencing of a fluoropolymer plant. PFAS concentrations in other environmental compartments (such as air, vegetables or groundwater) should be monitored to assess all potential pathways to exposure of nearby residents before carrying out human biomonitoring.

Occurrence and tissue distribution of 33 legacy and novel per- and polyfluoroalkyl substances (PFASs) in Baikal seals (Phoca sibirica)

Per- and polyfluoroalkyl substances (PFASs) are bioaccumulative and associated with adverse effects in both wildlife and humans. The occurrence of 33 PFASs was assessed in the plasma, liver, blubber, and brain of 18 Baikal seals (Phoca sibirica) (16 pups and 2 adult females) from Lake Baikal, Russia (in 2011). Of the 33 congeners analysed for: perfluorooctanosulfonic acid (PFOS), 7 long chain perfluoroalkyl carboxylic acids (C8–C14 PFCAs) and 1 branched PFCA (perfluoro-3,7-dimethyloctanoic acid; P37DMOA) were most frequently detected. The PFASs in plasma and liver with the highest median concentrations were legacy congeners: perfluoroundecanoic acid (PFUnA; plasma: 11.2 ng/g w.w.; liver: 7.36 ng/g w.w.), PFOS (plasma: 8.67 ng/g w.w.; liver: 9.86 ng/g w.w.), perfluorodecanoic acid (PFDA; plasma: 5.13 ng/g w.w.; liver: 6.69 ng/g w.w.), perfluorononanoic acid (PFNA; plasma: 4.65 ng/g w.w.; liver: 5.83 ng/g w.w.) and perfluorotridecanoic acid (PFTriDA; plasma: 4.29 ng/g w.w.; liver: 2.55 ng/g w.w.). PFASs were detected in the brain of Baikal seals, indicating that PFASs cross through the blood–brain barrier. In blubber, the majority of PFASs were detected in low abundance and concentrations. In contrast to legacy PFASs, novel congeners (e.g., Gen X) were either detected infrequently or not found in Baikal seals. The worldwide occurrence of PFASs in pinnipeds was compared and lower median concentrations of PFOS were observed in Baikal seals relative to other pinnipeds. Conversely, similar concentrations of long chain PFCAs were found in Baikal seals compared to other pinnipeds. Furthermore, human exposure was assessed by estimating weekly intakes (EWI) of PFASs through Baikal seal consumption. Although PFASs concentrations were comparatively low relative to other pinnipeds, consumption of Baikal seal could exceed current regulatory guidelines.

Plasma eicosapentaenoic acid, a biomarker of fish consumption, is associated with perfluoroalkyl carboxylic acid exposure in residents of Kyoto, Japan: a cross-sectional study.

Per- and polyfluoroalkyl substances (PFASs) are highly fluorinated organic compounds that have been widely used in industry during the past few decades. The main exposure routes for PFASs are thought to be the diet, drinking water, and dust. In this study, we aimed to evaluate the relationship between perfluoroalkyl carboxylic acids (PFCAs, members of the PFAS family) and the plasma eicosapentaenoic acid-to-arachidonic acid ratio (EPA/AA), a biological indicator of seafood intake, to determine whether seafood intake may represent a means of exposure to PFASs in the Japanese population. We performed a cross-sectional study using 131 plasma samples collected from residents of Kyoto, Japan in 2013 and held in the Kyoto University biological sample bank. The concentrations of perfluoroheptanoic acid (PFHpA), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluoroundecanoic acid (PFDA), perfluoroundecanoic acid (PFUnDA), perfluorododecanoic acid (PFDoDA), perfluorotridecanoic acid (PFTrDA), EPA, and AA were quantified by gas chromatography-mass spectrometry, and multiple linear regression was used to analyze the results. In multiple linear regression analyses with age and eGFR, PFOA showed a significant positive linear association with age (p = 0.0005); PFHpA showed a significant negative linear association with estimated glomerular filtration rate (eGFR; p = 0.0338); and PFHpA, PFOA, PFNA, PFUnDA, and PFDoDA exhibited significant positive linear associations with EPA/AA (p = 0.0358, 0.0056, 0.0242, <0.0001, and <0.0001, respectively). Because only PFHpA and PFOA were associated with smoking, their concentrations were examined again with smoking variable included and neither showed an association with smoking habit. PFOA showed a significant linear association with EPA/AA ratio (p = 0.0072), but PFHpA did not (p = 0.051). The plasma concentrations of PFOA, PFNA, PFUnDA and PFDoDA significantly associated with the EPA/AA ratio in residents of Kyoto.

Brominated flame retardants (PBDEs and HBCDs) and perfluoroalkyl substances (PFASs) in wild boars (Sus scrofa) from Central Italy

Twenty-six samples of wild boar liver and muscle from the Central Apennine Mountain (Italy) were analysed for 19 perfluoro-alkyl substances (PFASs), 10 polybrominated diphenylethers (PBDEs) and 3 hexabromocyclododecanes (HBCDs). All samples were analysed by gas chromatography–tandem mass spectrometry for PBDEs and liquid chromatography–tandem mass spectrometry for PFASs and HBCDs, using an in-house developed analytical procedure. The brominated flame retardants (BFR) levels in livers were negligible: Σ10PBDEs reached a maximum value of 0.079 μg/kg, whereas HBCDs were not quantified in almost all of the samples analysed. BFR concentrations in muscles were higher, but not significantly therefore, for Σ10PBDEs lower bound, a mean value of 0.045 μg/kg (0.005–0.155 μg/kg range) was measured, while α-HBCD was quantified with a maximum of 0.084 μg/kg in 9 of the samples. Only two muscles contained all 3 HBCD isomers at concentrations of approximately 0.200 μg/kg. Σ19PFAS in the 26 wild boar livers was in the range 31.9–228 μg/kg, with a mean value of 87.7 μg/kg, reaching levels significantly higher than in muscles, which exhibited a mean concentration of 3.08 μg/kg (0.59–9.12 μg/kg range). Perfluorooctanesulfonic acid (PFOS) was the most prevalent compound in all liver samples, accounting for more than half of the total PFASs contamination, confirming that the liver is the primary target organ for PFOS exposure Perfluorotridecanoic acid (PFTrDA), which accounts for 25–30-% of the total contamination, was the most abundant compound in the muscle, followed by PFOS.The estimated daily intake (EDIs) of BFRs remained below the estimated chronic human daily dietary intake (Dr,h) defined from European Food Safety Authority (EFSA). Furthermore, the exposure to PFASs in muscle was 7.7 times lower than the EFSA's tolerable daily intake (TDI).In contrast, exposure due to liver consumption was significant: the EDI exceeded the EFSA's 2020 TDI by approximately 7 times.

Spatiotemporal and life history related trends of per- and polyfluoroalkyl substances in Indo-Pacific finless porpoises from south China sea (2007–2020)

Per- and polyfluoroalkyl substances (PFASs) levels in Indo-Pacific finless porpoises (Neophocaena phocaenoides) in the Pearl River Estuary (PRE), near the most economically developed region in China, have not been characterized. We measured the hepatic concentrations of twelve PFASs, including nine perfluoroalkyl carboxylic acids (PFCAs) and three perfluoroalkane sulfonic acids (PFSAs) in the finless porpoises (n = 21) collected from the PRE between 2007 and 2020. The average level of PFSAs was more than 2-times higher than that of PFCAs. The order of six dominant PFASs was perfluorooctane sulfonate (PFOS) > perfluoroundecanoic acid (PFUdA) > perfluorodecanoic acid (PFDA) > perfluorotridecanoic acid (PFTrDA) > perfluorononanoic acid (PFNA) > perfluorododecanoic acid (PFDoDA). The levels of Hepatic PFOS of 29% samples exceeded the no observable adverse effect level (NOAEL) values. The concentration of PFASs in males was significant higher than in females. PFASs levels were significantly negatively correlated with body length in males and positively correlated in females. PFASs levels in the PRE finless porpoises were lower than in humpback dolphins possibly due to different foraging habitat toward the coast and the consumption of less fish. PFCAs levels in finless porpoises from the western PRE were higher compared to Hong Kong, possibly due to the high-intensity sources of terrestrial anthropogenic pollutants. Significant increasing spatiotemporal trends of PFSAs, PFCAs and PFASs were found in finless porpoises from 2007 to 2020, suggesting a continuously increased risk of PFASs exposure for PRE cetaceans in the last decade.

Association between prenatal exposure to perfluoroalkyl substances and anogenital distance in female neonates

BackgroundPerfluoroalkyl substances (PFASs) have been reported to exert reproductive toxicity. Anogenital distance (AGD) is a biomarker of intrauterine androgen exposure and an indicator of genital development. An animal study reported that female neonatal rats exposed to perfluorooctanoic acid or perfluorooctane sulfonate (PFOS) during postnatal days 1–5 exhibited a longer AGD, while epidemiological studies have shown inconsistent results. This study aimed to examine the effects of prenatal exposure to PFASs on the AGD in female neonates. MethodsPFAS levels were measured in plasma samples obtained from pregnant women at 12–16 gestational weeks using high-performance liquid chromatography/mass spectrometry. The AGD of each female neonate was measured within 3 days after delivery. The anogenital index (AGI), calculated as AGD divided by weight, was also determined. A total of 362 motherinfant pairs were included in this study. A multivariate linear regression model was used to examine the association between prenatal ln-transformed concentrations of PFASs and AGD/AGI. In addition, weighted quantile sum regression (WQSR) and Bayesian kernel machine regression (BKMR) models were used to assess the overall effects of a mixture of PFASs on the AGD/AGI and to identify important contributors to the overall effect. ResultsThere was a consistent pattern of association between maternal PFAS concentrations and increased AGDanus to posterior fourchette (AF), AGDanus to clitoris (AC), and AGIAF lengths at birth. Statistical significance was found between maternal ln-transformed concentrations of perfluorohexane sulfonate (PFHxS), perfluorododecanoic acid, and perfluorotridecanoic acid and AGDAF, with β values (95% confidence interval [CI]) of 0.83 (0.16, 1.51), 0.32 (0.05, 0.59), and 0.25 (0.00, 0.51) mm, respectively; between PFOS and AGDAC, with a β value (95% CI) of 0.63 (0.04, 1.21) mm; and between PFHxS and AGIAF, with a β value (95% CI) of 0.22 (0.02, 0.43) mm/kg. Similarly, the WQSR and BKMR models showed that an increase in the AGDAF/AGIAF at birth was associated with co-exposure to a mixture of PFASs. ConclusionHigh maternal concentrations of PFASs were associated with increased AGD in female neonates, indicating that PFASs may impair reproductive development in female offspring in early life.

Bioaccumulation and trophic transfer of perfluorinated alkyl substances (PFAS) in marine biota from the Belgian North Sea: Distribution and human health risk implications

Per- and polyfluorinated alkyl substances (PFAS) are highly persistent chemicals, which pose a potential risk for aquatic wildlife due to their bioaccumulative behaviour and toxicological effects. Although the distribution of PFAS in marine environments has been studied worldwide, little is known on the contamination of PFAS in the southern North Sea. In the present study, the bioaccumulation and trophic transfer of Perfluoroalkyl acids (PFAAs) was studied in liver and muscle tissue of seven fish species and in whole-body tissue of two crustacean species, collected at 10 sites in the Belgian North Sea. Furthermore, the human and ecological health risks were examined.Overall, perfluorooctane sulfonate (PFOS) was predominant in all matrices and other long-chain PFAS were frequently detected. Mean PFOS concentrations ranged from <LOQ to 107 ng/g (ww) in fish liver, from <LOQ to 24 ng/g ww in fish muscle and from 0.29 to 5.6 ng/g ww in crustaceans. Elevated perfluorotridecanoic acid (PFTrDA) concentrations were detected in fish liver from the estuarine and coastal region (<LOQ-116 ng/g ww), indicating a specific point source of this compound. Based on stable isotope analysis, no distinctive trophic transfer patterns of PFAS could be identified which implies that the bioconcentration of PFAS from the surrounding abiotic environment is most likely dominating over the biomagnification in the studied biota. The consumption of commercially important species such as the brown shrimp (Crangon crangon), plaice (Pleuronecta platessa), sole (Solea solea) and whiting (Merlangus merlangus) might pose potential health risks if it exceeds 17 g/day, 18 g/day, 26 g/day and 43 g/day respectively. Most PFOS measurements did not exceed the QSbiota,hh of 9.1 ng/g ww, however, the benchmark of 33 ng/g ww targeting the protection of wildlife from secondary poisoning was exceeded for 43% and 28% of the samples in plaice and sole.

Temporal Trends of Organochlorine and Perfluorinated Contaminants in a Terrestrial Raptor in Northern Europe Over 34 years (1986–2019)

Fourteen legacy organochlorine (OC) contaminants and 12 perfluoroalkyl substances (PFASs) were measured in eggs of tawny owls (Strix alueco) in central Norway (1986–2019). We expected OCs to have reached stable equilibrium levels due to bans, and that recent phase‐out of some PFASs would have slowed the increase of these compounds. ∑OC comprised on average approximately 92% of the measured compounds, whereas ∑PFAS accounted for approximately 8%. However, whereas the ∑OC to ∑PFAS ratio was approximately 60 in the first 5 years of the study, it was only approximately 11 in the last 5 years. Both OC pesticides and polychlorinated biphenyls (PCBs) showed substantial declines over the study period (~85%–98%): hexachlorocyclohexanes and chlordanes seemed to be levelling off, whereas p,p′‐dichlorodiphenyldichloroethylene (p,p′‐DDE) and hexachlororbenzene (HCB), and most PCB congeners still seemed to decline at a more or less constant rate. While the concentration of perfluorooctane sulfonic acid (PFOS), the dominating PFAS, was reduced by approximately 43%, other perfluorinated sulfonates (PFSAs) showed only minor changes. Moreover, the median concentrations of seven perfluorinated carboxylic acids (PFCAs) increased approximately five‐fold over the study period. Perfluorononanoic acid and perfluoroundecanoate acid, however, seemed to be levelling off in recent years. In contrast, perfluorododecanoic acid, perfluorodecanoate acid, perfluorotridecanoic acid, and perfluorotetradecanoic acid seemed to increase more or less linearily. Finally, perfluorooctanoic acid (PFOA) was increasingly likely to be detected over the study period. Hence, most legacy OCs and PFOS have not reached a lower threshold with stable background levels, and voluntary elimination of perfluoroalkyl carboxylates still has not resulted in declining levels in tawny owls in central Norway. Environ Toxicol Chem 2022;41:1508–1519. © 2022 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.