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Perfluorooctane sulfonate (PFOS) is a ubiquitous pollutant that elicits a wide range of toxic effects in exposed biota. Coastal zones in highly urbanized or industrial areas are particularly vulnerable to PFOS pollution. At present, information is lacking on biomarkers to assess PFOS effects on aquatic wildlife. This study investigated the efficacy of l-carnitine (or carnitine) and fatty acids as biomarkers of PFOS exposure in aquatic biota. The levels of PFOS, total and free carnitine, and 24 fatty acids (measured as fatty acid methyl esters or FAMEs) were measured in the liver, and muscle or blubber, of fish and dolphins sampled from Galveston Bay and the northern Gulf of Mexico (nGoM). Overall, bottlenose dolphins (Tursiops truncatus) had the highest hepatic PFOS levels. Galveston Bay fish, gafftopsail catfish (Bagre marinus), red drum (Sciaenops ocellatus), and spotted seatrout (Cynoscion nebulosus), had hepatic PFOS levels ∼8-13× higher than nGoM pelagic fish species, red snapper (Lutjanus campechanus) and yellowfin tuna (Thunnus albacares). The multivariate analysis of PFOS liver body-burdens and biomarkers found carnitine to be a more modal biomarker of PFOS exposure than FAMEs. Significant positive correlation of hepatic PFOS levels with total carnitine was evident for biota from Galveston Bay (fish only), and a significant correlation between PFOS and total and free carnitine was evident for biota from the nGoM (fish and dolphins). Given the essential role of carnitine in mediating fatty acid ß-oxidation, our results suggest carnitine to be a likely candidate biomarker of environmental PFOS exposure and indicative of potential dyslipidemia effects.

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PFAS are a group of organic chemicals, which some presents environmental persistence, dispersion and potential toxicity. Some of them have been listed in the Stockholm Convention as persistent organic pollutants (POPs) to have its production and use restricted, namely PFOS, its salts and PFOSF and PFOA, its salts and related substances. As a Party, Brazil has to comply with the Convention provisions regarding the control of POPs. In order to develop listed PFAS inventories in the country, the Convention guidance documents were used. Stakeholders were consulted and trade data was assessed. Complementary, a review on listed PFAS occurrence in Brazil was performed. From over 1000 queries sent, only 3 answers were received. International trade data showed an import of 93.7 tonnes of PFOSF from China and export of sulfluramid-base ant bait to other developing countries. Domestic trade data showed that around 28 t per year of EtFOSA is commercialized in Brazil. The EtFOSA sold internally could lead to emissions of up to 616 t of PFOS. With domestic and foreign trade data it was possible to estimate the production of EtFOSA from 2010 to 2018 to 40 t per year. Only 10 studies reported listed PFAS occurrence in Brazilian environmental matrices. All of them reported ubiquitous occurrence of listed PFAS in the country, being PFOS the predominant in terms of occurrence and concentration. Brazil needs to develop strategies to overcome the low engagement of stakeholders and enforce control over listed PFAS foreign trade.

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The biomagnification of per- and polyfluoroalkyl substances (PFASs) was investigated in a tropical mangrove food web from an estuary in Bahia, Brazil. Samples of 44 organisms (21 taxa), along with biofilm, leaves, sediment and suspended particulate matter were analyzed. Sum (∑) PFAS concentrations in biota samples were dominated by perfluorooctane sulfonate (PFOS, 93% detection frequency in tissues; 0.05 to 1.97 ng g-1 ww whole-body (wb)), followed by perfluorotridecanoate (PFTrDA, 57%; 0.01 to 0.28 ng g-1 ww wb). PFOS precursors such as perfluorooctane sulfonamide (FOSA, 54%; 0.01 to 0.32 ng g-1 ww wb) and N-ethyl perfluorooctane sulfonamide (EtFOSA; 30%; 0.01 to 0.21 ng g-1 ww wb) were also detected. PFAS accumulation profiles revealed different routes of exposure among bivalve, crustacean and fish groups. Statistics for left-censored data were used in order to minimize bias on trophic magnification factors (TMFs) calculations. TMFs >1 were observed for PFOS (linear + branched isomers), EtFOSA (linear + branched isomers), and perfluorononanoate (PFNA), and in all cases, dissimilar accumulation patterns were observed among different trophic positions. The apparent biodilution of some long-chain PFCAs through the food chain (TMF < 1) may be due to exposure from multiple PFAS sources. This is the first study investigating bioaccumulation of PFASs in a tropical food web and provides new insight on the behavior of this ubiquitous class of contaminants.

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Perfluorooctane sulfonate (PFOS) and perfluorohexane sulfonate (PFHxS) are toxic and bioaccumulative, included in the Stockholm Convention's list as persistent organic pollutants. Due to their toxicity, worldwide distribution, and lack of information in spermatozoa physiology during pre-fertilization processes, the present study seeks to analyze the toxic effects and possible alterations caused by the presence of these compounds in boar sperm during the in vitro capacitation. The spermatozoa capacitation was performed in supplemented TALP-Hepes media and mean lethal concentration values of 460.55 µM for PFOS, and 1930.60 µM for PFHxS were obtained. Results by chlortetracycline staining showed that intracellular Ca2+ patterns bound to membrane proteins were scarcely affected by PFOS. The spontaneous acrosome reaction determined by FITC-PNA was significantly reduced by PFOS and slightly increased by PFHxS. Both toxic compounds significantly alter the normal capacitation process from 30 min of exposure. An increase in ROS production was observed by flow cytometry and considerable DNA fragmentation by the comet assay. The immunocytochemistry showed a decrease of tyrosine phosphorylation in proteins of the equatorial and acrosomal zone of the spermatozoa head. In conclusion, PFOS and PFHxS have toxic effects on the sperm, causing mortality and altering vital parameters for proper sperm capacitation.

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Research pertaining to exposure of humans to per- and polyfluorinated alkyl substances (PFASs) has received considerable public and regulatory attention in recent years. Although several studies have reported exposure to PFASs by populations in North America and western Europe, such information is still scarce in Latin America, including Brazil. In this study, concentrations of thirteen PFASs were determined in whole blood collected during the second trimester from 252 pregnant Brazilian women. This is a nested case-control study within the Brazilian Ribeirao Preto and Sao Luiz Birth Cohort Study (BRISA) with selected birth outcomes cases (n = 63) and matched controls (n = 189). PFASs concentrations were associated with conditions including preeclampsia, birth weight (BW), preterm birth, and intrauterine growth restriction (IUGR). Among PFASs measured, perfluorooctane sulfonate (PFOS) was found at the highest concentration (range: 1.06-106 ng mL-1 with a median value of 3.41 ng mL-1) which was followed by perfluorooctanoic acid (PFOA, range: 0.11-2.77 ng mL-1 with a median value of 0.20 ng mL-1). A significant positive association of PFOS and PFOA concentrations with fetal growth restriction (p < 0.05) was found. This is the first study to assess whole blood concentrations of PFASs and their effect on fetal growth in pregnant Brazilian women.

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Per- and polyfluoroalkyl substances (PFAS) are ubiquitous, synthetic anthropogenic chemicals known to infiltrate and persist in biological systems as a result of their stability and bioaccumulation potential. This study investigated 15 PFAS, including short-chain carboxylic and sulfonic acids, and their presence in a threatened herbivore, the West Indian manatee (Trichechus manatus). Seven of the 15 PFAS examined were detected in manatee plasma. Perfluorooctanesulfonic acid (PFOS) (ranging from 0.13 to 166 ng/g ww) and perfluorononanoic acid (PFNA) (ranging from 0.038 to 3.52 ng/g ww) were detected in every manatee plasma sample examined (n = 69), with differing medians across sampling sites in Florida, Crystal River (n = 39), Brevard County (n = 18), Everglades National Park (n = 8), and four samples (n = 4) from Puerto Rico. With an herbivorous diet and long life-span, the manatee provides a new perspective to monitoring PFAS contamination.

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N-Ethyl perfluorooctane sulfonamide (EtFOSA) is a perfluorooctane sulfonate (PFOS) precursor and the active ingredient in sulfluramid, a pesticide which is used extensively in Brazil for management of leaf cutting ants. Here we investigate the occurrence of EtFOSA, PFOS, and other per- and polyfluoroalkyl substances (PFASs) in soil, eucalyptus leaves, water (ground, riverine, and coastal (estuarine/marine)) and coastal sediment from an agricultural region of Bahia State, Brazil. This area contains a larger number of eucalyptus plantations where sulfluramid is suspected to be applied. Soil, leaves, and coastal water (marine/estuarine) contained ∑PFAS concentrations of up to 5400 pg g-1, 979 pg g-1, and 1020 pg L-1, respectively, with PFAS profiles generally dominated by PFOS and perfluorooctane sulfonamide (FOSA). Coastal sediment contained ∑PFAS concentrations of up to 198 pg g-1, with PFOS, FOSA, and perfluorooctanoic acid (PFOA) being the most frequently observed PFASs. These substances are all potential EtFOSA transformation products, pointing to sulfluramid as a possible source. In riverine water, ∑PFAS concentrations of up to 8930 pg L-1 were observed. PFOS and PFOA were detected in all river water samples. Groundwater also exhibited PFAS contamination (5730 pg L-1 ∑PFASs), likely from sulfluramid use. The observation of other PFASs (e.g. perfluorobutanoic acid) in freshwater suggests that other PFAS sources (in addition to sulfluramid) may be important in this region. Overall, these data support the hypothesis that sulfluramid use contributes to the occurrence of PFASs in the Brazilian environment.

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In 2010 an oil terminal next to nature reservation Saliña Goto (Bonaire) caught fire. Firefighting resulted in elevated per- and polyfluoroalkyl substances (PFAS) concentrations in the salt lake. Within months flamingo abundance in Goto dropped to near complete absence. After statistical analysis, rainfall was deemed an unlikely cause for this decline. Toxicological effects on abundance of prey are likely the main cause for the flamingo absence. This reduced PFAS exposure via food and thus risk towards flamingos during the first years after the fires. Although the sediment is still polluted with persistent PFAS, flamingos returned, and started to feed on organisms with PFAS levels that exceed safety thresholds, placing the birds and other wildlife at risk. Monitoring bird populations is advised to assess potential toxic effects on birds and their offspring. This case suggests that applying persistent chemicals to reduce incident impacts may be more harmful than the incident itself.

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The distribution of 32 per/polyfluoroalkyl substances (PFASs) in surface soils was determined at 62 locations representing all continents (North America n = 33, Europe n = 10, Asia n = 6, Africa n = 5, Australia n = 4, South America n = 3 and Antarctica n = 1) using ultra performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) systems. Quantifiable levels of perfluoroalkyl carboxylates (PFCAs: PFHxA-PFTeDA) were observed in all samples with total concentrations ranging from 29 to 14,300 pg/g (dry weight), while perfluoroalkane sulfonates (PFSAs: PFHxS, PFOS and PFDS) were detected in all samples but one, ranging from

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This study assessed the levels of 21 perfluoroalkyl substances (PFASs) in 283 food items (38 from Brazil, 35 from Saudi Arabia, 174 from Spain and 36 from Serbia) among the most widely consumed foodstuffs in these geographical areas. These countries were chosen as representatives of the diet in South America, Western Asia, Mediterranean countries and South-Eastern Europe. The analysis of foodstuffs was carried out by turbulent flow chromatography (TFC) combined with liquid chromatography with triple quadrupole mass spectrometry (LC-QqQ-MS) using electrospray ionization (ESI) in negative mode. The analytical method was validated for the analysis of different foodstuff classes (cereals, fish, fruit, milk, ready-to-eat foods, oil and meat). The analytical parameters of the method fulfill the requirements specified in the Commission Recommendation 2010/161/EU. Recovery rates were in the range between 70% and 120%. For all the selected matrices, the method limits of detection (MLOD) and the method limits of quantification (MLOQ) were in the range of 5 to 650 pg/g and 17 to 2000 pg/g, respectively. In general trends, the concentrations of PFASs were in the pg/g or pg/mL levels. The more frequently detected compounds were perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA) and perfluorobutanoic acid (PFBA). The prevalence of the eight-carbon chain compounds in biota indicates the high stability and bioaccumulation potential of these compounds. But, at the same time, the high frequency of the shorter chain compounds is also an indication of the use of replacement compounds in the new fluorinated materials. When comparing the compounds profile and their relative abundances in the samples from diverse origin, differences were identified. However, in absolute amounts of total PFASs no large differences were found between the studied countries. Fish and seafood were identified as the major PFASs contributors to the diet in all the countries. The total sum of PFASs in fresh fish and seafood was in the range from the MLOQ to 28ng/g ww. According to the FAO-WHO diets composition, the daily intake (DI) of PFASs was calculated for various age and gender groups in the different diets. The total PFASs food intake was estimated to be between 2300 and 3800 ng /person per day for the different diets. Finally, the risk intake (RI) was calculated for selected relevant compounds. The results have indicated that by far in no case the tolerable daily intake (TDI) (150, 1500, 50,000, 1,000,000, 150, 1500 ng/kg body weight, for perfluorohexanesulfonate (PFHxS), fluorotelomer alcohol (FTOH), perfluorobutanesulfonic acid (PFBS), perfluorobutanoic acid (PFBA), PFOS and PFOA, respectively) was exceeded.

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Perfluorooctanesulfonate (PFOS) is a compound of global concern because of its persistence and bioaccumulation in the environment. Nevertheless, little is known of the potential for PFOS biodegradation, even though the importance of characterizing the function and activity of microbial populations detected in the environment has been discussed. This study focused on the biodegradation of PFOS by a specific microorganism. Through this study, we have identified the aerobic microorganism for the specific decomposition of PFOS from wastewater treatment sludge, as a well-known sink for environmental PFOS. This species was Pseudomonas aeruginosa strain HJ4 with a 99% similarity, a mesophilic rod type bacteria (30-37°C). A pH range of 7-9 was determined to be optimal for the growth of strain HJ4. In this study approximately 67% over a range of concentrations (1400-1800µgL(-)(1)) for PFOS was biologically decomposed by P. aeruginosa after 48h incubation. This result is reported here for the first time, which strongly pertains to the efficient biodegradation of PFOS. Therefore, our study is considered a major advancement in sustainable PFOS treatment.

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