Accumulation of Per- and Polyfluoroalkyl Substances (PFAS) in Coastal Sharks from Contrasting Marine Environments: The New York Bight and The Bahamas.

Per- and polyfluoroalkyl substances (PFAS) enter the marine food web, accumulate in organisms, and potentially have adverse effects on predators and consumers of seafood. However, evaluations of PFAS in meso-to-apex predators, like sharks, are scarce. This study investigated PFAS occurrence in five shark species from two marine ecosystems with contrasting relative human population densities, the New York Bight (NYB) and the coastal waters of The Bahamas archipelago. The total detected PFAS (∑PFAS) concentrations in muscle tissue ranged from 1.10 to 58.5 ng g-1 wet weight, and perfluorocarboxylic acids (PFCAs) were dominant. Fewer PFAS were detected in Caribbean reef sharks (Carcharhinus perezi) from The Bahamas, and concentrations of those detected were, on average, ∼79% lower than in the NYB sharks. In the NYB, ∑PFAS concentrations followed: common thresher (Alopias vulpinus) > shortfin mako (Isurus oxyrinchus) > sandbar (Carcharhinus plumbeus) > smooth dogfish (Mustelus canis). PFAS precursors/intermediates, such as 2H,2H,3H,3H-perfluorodecanoic acid and perfluorooctanesulfonamide, were only detected in the NYB sharks, suggesting higher ambient concentrations and diversity of PFAS sources in this region. Ultralong-chain PFAS (C ≥ 10) were positively correlated with nitrogen isotope values (δ15N) and total mercury in some species. Our results provide some of the first baseline information on PFAS concentrations in shark species from the northwest Atlantic Ocean, and correlations between PFAS, stable isotopes, and mercury further contextualize the drivers of PFAS occurrence.

Occurrence of a "forever chemical" in the atmosphere above pristine Amazon Forest.

Per- and polyfluoroalkyl substances (PFAS), often referred to as "forever chemicals", are a class of man-made, extremely stable chemicals, which are widely used in industrial and commercial applications. Exposure to some PFAS is now known to be detrimental to human health. By virtue of PFAS long residence times, they are widely detected in the environment, including remote locations such as the Arctics, where the origin of the PFAS is poorly understood. It has been suggested that PFAS may be transported through contaminated waters, leading to accumulation in coastal areas, where they can be aerosolised via sea spray, thereby extending their geographical distribution far beyond their original source regions. The aim of this work is to investigate, for the first time, whether "forever chemicals" could be transported to areas considered to be pristine, far from coastal sites. This study was performed at the Amazonian Tall Tower Observatory (ATTO), a unique remote site situated in the middle of the Amazon rainforest, where a restricted PFAS, perfluorooctanoic acid (PFOA), was observed with concentrations reaching up to 2 pg/m3. A clear trend of increasing concentration with sampling height was observed and air masses from the south over Manaus had the highest concentrations. Atmospheric lifetime estimations, removal mechanisms supported by measurements at two heights (320 and 42 m above the rainforest), and concentration spikes indicated a long-range transport of PFOA to pristine Amazon rainforest. Potential sources, including industrial activities in urban areas, were explored, and historical fire management practices considered. This research presents the first measurements of PFAS in the atmosphere of Amazon rainforest. Remarkably, even in this remote natural environment, appreciable levels of PFAS can be detected. This study provides valuable insights into the long-range transport of the anthropogenic "forever chemical" into a remote natural ecosystem and should raise awareness of potential environmental implications.

Spatial and temporal distribution of perfluoroalkyl substances (PFAS) detected after an aqueous film forming foam (AFFF) spill.

In 2015, > 460,000 L of aqueous film-forming foam (AFFF) and fire suppressors containing per- and polyfluoroalkyl substances (PFAS) were used to combat a fire at a petrochemical fuel storage terminal in the Port of Santos (Brazil). Sediments from seven sites were sampled repeatedly from 2 weeks to 1 year after the fire (n = 30). Æ©15PFAS concentrations ranged from 115 to 15,931 pg g-1 dry weight (dw). Perfluorooctane sulfonic acid (PFOS) was the most frequently detected compound with concentrations ranging from 363 to 4517 (average = 1603) pg g-1dw to <47.1 to 642 (average = 401) pg g-1 dw, followed by perfluorohexanoic acid (PFHxA) (from 38.8 to 219 (average = 162) pg g-1 dw after 15 days and from <20.8 to 161 (average = 101) pg g-1 dw one year later). Together, the hydrodynamics and fire events documented in the region were important features explaining the spread of PFAS.

Extraordinary levels of per- and polyfluoroalkyl substances (PFAS) in vertebrate animals at a New Mexico desert oasis: Multiple pathways for wildlife and human exposure.

Per- and polyfluoroalkyl substances (PFAS) in the environment pose persistent and complex threats to human and wildlife health. Around the world, PFAS point sources such as military bases expose thousands of populations of wildlife and game species, with potentially far-reaching implications for population and ecosystem health. But few studies shed light on the extent to which PFAS permeate food webs, particularly ecologically and taxonomically diverse communities of primary and secondary consumers. Here we conducted >2000 assays to measure tissue-concentrations of 17 PFAS in 23 species of mammals and migratory birds at Holloman Air Force Base (AFB), New Mexico, USA, where wastewater catchment lakes form biodiverse oases. PFAS concentrations were among the highest reported in animal tissues, and high levels have persisted for at least three decades. Twenty of 23 species sampled at Holloman AFB were heavily contaminated, representing middle trophic levels and wetland to desert microhabitats, implicating pathways for PFAS uptake: ingestion of surface water, sediments, and soil; foraging on aquatic invertebrates and plants; and preying upon birds or mammals. The hazardous long carbon-chain form, perfluorooctanosulfonic acid (PFOS), was most abundant, with liver concentrations averaging >10,000 ng/g wet weight (ww) in birds and mammals, respectively, and reaching as high 97,000 ng/g ww in a 1994 specimen. Perfluorohexanesulfonic acid (PFHxS) averaged thousands of ng/g ww in the livers of aquatic birds and littoral-zone house mice, but one order of magnitude lower in the livers of upland desert rodent species. Piscivores and upland desert songbirds were relatively uncontaminated. At control sites, PFAS levels were strikingly lower on average and different in composition. In sum, legacy PFAS at this desert oasis have permeated local aquatic and terrestrial food webs across decades, severely contaminating populations of resident and migrant animals, and exposing people via game meat consumption and outdoor recreation.

Profile of per- and polyfluoroalkyl substances, source appointment, and determinants in Argentinean postpartum women.

BACKGROUND: Per- and polyfluoroalkyl substances (PFAS) are a group of synthetic chemicals with potential adverse health effects. Information concerning PFAS concentrations in relation to pregnancy is scarce in South America and non-existent in Argentina. AIM: We aimed to investigate an extended maternal PFAS profile herein serum concentrations in a regional and global view, source appointment, and determinants in Argentinean women. METHODS: A cross-sectional study with a sampling period from 2011 to 2012 included 689 women from Ushuaia and Salta in Argentina. Serum samples collected two days postpartum were analyzed by ultra-high pressure liquid chromatography coupled to electrospray negative ionisation tandem-quadrupole mass-spectrometry. Principal Component Analysis (PCA) following absolute principal component score-multiple linear regression (APCS-MLR) was used for PFAS source appointments. Determinants of PFAS were explored through a MLR approach. A review of previous studies within the same period was conducted to compare with present levels. RESULTS: Argentinean PFAS concentrations were the lowest worldwide, with PFOS (0.74 ng/mL) and PFOA (0.11 ng/mL) as the dominant substances. Detection frequencies largely aligned with the compared studies, indicating the worldwide PFAS distribution considering the restrictions. The PCA revealed region-specific loading patterns of two component groups of PFAS, a mixture of replaced and legacy substances in Ushuaia and long-chain in Salta. This might relate to a mix of non-diet and diet exposure in Ushuaia and diet in Salta. Region, age, lactation, parity, household members, migration, bottled water, and freshwater fish were among the determinants of various PFAS. CONCLUSION: This is the first study to monitor human PFAS exposure in Argentina. Maternal PFAS concentrations were the lowest observed worldwide in the same period. Exposure contributions are suggested to be affected by restrictions and substitutions. Given the limited population-based studies and the emergence of PFAS, it is essential to conduct further monitoring of PFAS in Argentina and South America.

Uncovering the impact of agricultural activities and urbanization on rivers from the Piracicaba, Capivari, and Jundiaí basin in São Paulo, Brazil: A survey of pesticides, hormones, pharmaceuticals, industrial chemicals, and PFAS.

Rivers in Southeast Brazil are essential as sources of drinking water, energy production, irrigation, and industrial processes. The Piracicaba, Capivari, and Jundiaí rivers basin, known as the PCJ basin, comprises major cities, industrial hubs, and large agricultural areas, which have impacted the water quality in the region. Emerging contaminants such as pesticides, hormones, pharmaceuticals, industrial chemicals, and per- and polyfluoroalkyl substances (PFAS) are likely to be released into the rivers in the PCJ basin; however, the current Brazilian legislation does not require monitoring of most of these chemicals. Thus, the extent of emerging contaminants pollution and their risks to aquatic and human life in the basin are largely unknown. In this study, we investigated the occurrence of several pesticides, hormones, pharmaceuticals, and personal care products in 15 sampling points across the PCJ basin, while industrial chemicals and PFAS were assessed in 11 sampling points. The results show that agriculture and industrial activities are indeed causing the pollution of most rivers. Multivariate analysis indicates that some sampling points, such as Jundiaí, Capivari, and Piracicaba rivers, are largely impacted by pesticides used in agriculture. In addition, to the best of our knowledge, this is the first study reporting the presence of PFAS in rivers in São Paulo, the most populous state in Brazil. Four out of eight species of PFAS assessed in our study were detected in at least 5 sampling points at concentrations ranging from 2.0 to 50.0 ng L-1. The preliminary risk assessment indicates that various pesticides, caffeine, industrial chemicals, and PFAS were present at concentrations that could threaten aquatic life. Notably, risk quotients of 414, 340, and 178 were obtained for diuron, atrazine, and imidacloprid, respectively, in the Jundiaí River. Our study suggests that establishing a comprehensive monitoring program is needed to ensure the protection of aquatic life and human health.

PFAS in fish from AFFF-impacted environments: Analytical method development and field application at a Canadian international civilian airport.

Methods targeting anionic per- and polyfluoroalkyl substances (PFAS) in aquatic biota are well established, but commonly overlook many PFAS classes present in aqueous film-forming foams (AFFFs). Here, we developed an analytical method for the expanded analysis of negative and positive ion mode PFAS in fish tissues. Eight variations of extraction solvents and clean-up protocols were first tested to recover 70 AFFF-derived PFAS from the fish matrix. Anionic, zwitterionic, and cationic PFAS displayed the best responses with methanol-based ultrasonication methods. The response of long-chain PFAS was improved for extracts submitted to graphite filtration alone compared with those involving solid-phase extraction. The validation included an assessment of linearity, absolute recovery, matrix effects, accuracy, intraday/interday precision, and trueness. The method was applied to a set of freshwater fish samples collected in 2020 in the immediate vicinity (creek, n = 15) and downstream (river, n = 15) of an active fire-training area at an international civilian airport in Ontario, Canada. While zwitterionic fluorotelomer betaines were major components of the subsurface AFFF source zone, they were rarely detected in fish, suggesting limited bioaccumulation potential. PFOS largely dominated the PFAS profile, with record-high concentrations in brook sticklebacks (Culaea inconstans) from the creek (16000-110,000 ng/g wet weight whole-body). These levels exceeded the Canadian Federal Environmental Quality Guidelines (FEQG) for PFOS pertaining to the Federal Fish Tissue Guideline (FFTG) for fish protection and Federal Wildlife Diet Guidelines (FWiDG) for the protection of mammalian and avian consumers of aquatic biota. Perfluorohexane sulfonamide and 6:2 fluorotelomer sulfonate were among the precursors detected at the highest levels (maximum of ∼340 ng/g and ∼1100 ng/g, respectively), likely reflecting extensive degradation and/or biotransformation of C6 precursors originally present in AFFF formulations.

Occurrence and distribution of per-and polyfluoroalkyl substances (PFAS) in surface and groundwaters in an urbanized and agricultural area, Southern Brazil.

Per- and polyfluoroalkyl substances, known as PFAS, are emerging contaminants detected in surface water, groundwater, drinking water, air, and food. Due to its chemical stability and high hydrophobicity, these compounds are used as surfactants, surface protectors, flame retardants, textile impregnation, fire-fighting foam, and pesticides and may be a risk for human health in the long-term exposure. Currently, a little research has been carried out for these compounds in Brazil. In this study, the concentration and distribution of 23 PFAS were analyzed in groundwater samples collected from water wells in urbanized areas and in surface water samples from Porto Alegre, one of the biggest cities in Brazil. The total concentrations of PFAS (ΣPFAS) in a groundwater sample varied between 22 and 718 ng L-1. Eleven PFAS species were detected in groundwater, including PFOA, PFHxA, PFPeA, PFBA, PFDA, PFNA, and PFOS. Most of PFAS were quantified in samples located in the aquifer formed by medium to coarse sands intercalated with silty-sandy lenses and low organic matter content that could facilitate the percolation of these compounds. The total concentrations of PFAS (ΣPFAS) in a surface water sample varied between 11 and 17 ng L-1. Ten species were founded in surface water being PFOA, PFOS, and PFHpA the most dominant. Considering all the samples, PFOA was the predominant species in the study. In addition, tributary water bodies had higher concentrations of PFAS than the main water body (Guaiba Lake) probably due dilution process.

Commentary: cumulative risk assessment of perfluoroalkyl carboxylic acids and perfluoralkyl sulfonic acids: what is the scientific support for deriving tolerable exposures by assembling 27 PFAS into 1 common assessment group?

This commentary proposes an approach to risk assessment of mixtures of per- and polyfluorinated alkyl substances (PFAS) as EFSA was tasked to derive a tolerable intake for a group of 27 PFAS. The 27 PFAS to be considered contain different functional groups and have widely variable physicochemical (PC) properties and toxicokinetics and thus should not treated as one group based on regulatory guidance for risk assessment of mixtures. The proposed approach to grouping is to split the 27 PFAS into two groups, perfluoroalkyl carboxylates and perfluoroalkyl sulfonates, and apply a relative potency factor approach (as proposed by RIVM) to obtain two separate group TDIs based on liver toxicity in rodents since liver toxicity is a sensitive response of rodents to PFAS. Short chain PFAS and other PFAS structures should not be included in the groups due to their low potency and rapid elimination. This approach is in better agreement with scientific and regulatory guidance for mixture risk assessment.

Using large amounts of firefighting foams releases per- and polyfluoroalkyl substances (PFAS) into estuarine environments: A baseline study in Latin America.

We analyzed per- and polyfluoroalkyl substances (PFAS) in aqueous film-forming foams (AFFFs) used to extinguish a major fire in a petrochemical terminal from the Port of Santos (Brazil). Eight AFFFs from seven known commercial brands and one unknown sample (AFFF-1 to AFFF-8) were evaluated. 17 PFAS were identified and quantified using high performance liquid chromatography (LC/MS). The concentrations of Σ17 PFAS in the AFFFs ranged from 500 to 9000 ng/g, with prevalence of short chain PFAS (~85 %), followed by long chain PFAS. Perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA), included in the global treaty of the Stockholm Convention, were also detected. We estimated that at least 635.96 g of PFAS were introduced in the estuary, representing a massive input of these substances. This investigation reports the PFAS composition of AFFFs used in firefighting in the GRULAC Region (Group of Latin American and Caribbean countries).

A Participatory Science Approach to Evaluating Factors Associated with the Occurrence of Metals and PFAS in Guatemala City Tap Water.

Limited information is available regarding chemical water quality at the tap in Guatemala City, preventing individuals, water utilities, and public health authorities from making data-driven decisions related to water quality. To address this need, 113 participants among households served by a range of water providers across the Guatemala City metropolitan area were recruited as participatory scientists to collect first-draw and flushed tap water samples at their residence. Samples were transported to the U.S. and analyzed for 20 metals and 25 per- and polyfluoroalkyl substances (PFAS). At least one metal exceeded the Guatemalan Maximum Permissible Limit (MPL) for drinking water in 63% of households (n = 71). Arsenic and lead exceeded the MPL in 33.6% (n = 38) and 8.9% (n = 10) of samples, respectively. Arsenic was strongly associated with groundwater while lead occurrence was not associated with location, water source, or provider. One or more PFAS were detected in 19% of samples (n = 21, range 2.1-64.2 ppt). PFAS were significantly associated with the use of plastic water storage tanks but not with location, water source, or provider. Overall, the high prevalence of arsenic above the MPL in Guatemala City tap water represents a potential health risk that current water treatment processes are not optimized to remove. Furthermore, potential contaminants from premise plumbing and storage, including lead and PFAS, represent additional risks requiring further investigation and public engagement.

Biodegradation of PFOA in microbial electrolysis cells by Acidimicrobiaceae sp. strain A6.

Acidimicrobiaceae sp. strain A6 (A6), is an anaerobic autotrophic bacterium capable of oxidizing ammonium (NH4+) while reducing ferric iron and is also able to defluorinate PFAS under these growth conditions. A6 is exoelectrogenic and can grow in microbial electrolysis cells (MECs) by using the anode as the electron acceptor in lieu of ferric iron. Therefore, cultures of A6 amended with perfluorooctanoic acid (PFOA) were incubated in MECs to investigate its ability to defluorinate PFAS in such reactors. Results show a significant decrease in PFOA concentration after 18 days of operation, while producing current and removing NH4+. The buildup of fluoride and shorter chain perfluorinated products was detected only in MECs with applied potential, active A6, and amended with PFOA, confirming the biodegradation of PFOA in these systems. This work sets the stage for further studies on the application of A6-based per- and polyfluorinated alkyl substances (PFAS) bioremediation in microbial electrochemical systems for water treatment.

Occurrence of perfluoroalkyl substances (PFASs) in marine plastic litter from coastal areas of Central Chile.

Perfluorinated alkyl substances (PFASs) were determined in marine plastic litter (MPL) on six beaches of central Chile. MPL was characterized physically and chemically, showing an abundance of macroplastic (size >2.5 cm). The polypropylene (PP) (47%) was the predominant polymer found. The Desembocadura beach, located at the mouth of the Biobio River, recorded the highest abundance of MPL (3.7 items m-2). PFAS detected (n = 15/21) ranged from 279 to 1211 pg g-1 and accounted for MeFOSE (46%) > PFHxS (14%) > PFPA (11%) > PFBS (6%) > PFOA (4%) and > PFOS (4%). Long-chain PFAS were prevalent, which can be metabolically degraded into PFOS (new POPs). This study i) highlights the need to further investigate the occurrence of chemicals in the MPL to reduce their impact on the environment; and ii) points out the need to improve future coastal management strategies for the elimination of solid waste along the coast of the country.

Pilot-scale expanded assessment of inorganic and organic tapwater exposures and predicted effects in Puerto Rico, USA.

A pilot-scale expanded target assessment of mixtures of inorganic and organic contaminants in point-of-consumption drinking water (tapwater, TW) was conducted in Puerto Rico (PR) to continue to inform TW exposures and corresponding estimations of cumulative human-health risks across the US. In August 2018, a spatial synoptic pilot assessment of than 524 organic and 37 inorganic chemicals was conducted in 14 locations (7 home; 7 commercial) across PR. A follow-up 3-day temporal assessment of TW variability was conducted in December 2018 at two of the synoptic locations (1 home, 1 commercial) and included daily pre- and post-flush samples. Concentrations of regulated and unregulated TW contaminants were used to calculate cumulative in vitro bioactivity ratios and Hazard Indices (HI) based on existing human-health benchmarks. Synoptic results confirmed that human exposures to inorganic and organic contaminant mixtures, which are rarely monitored together in drinking water at the point of consumption, occurred across PR and consisted of elevated concentrations of inorganic contaminants (e.g., lead, copper), disinfection byproducts (DBP), and to a lesser extent per/polyfluoroalkyl substances (PFAS) and phthalates. Exceedances of human-health benchmarks in every synoptic TW sample support further investigation of the potential cumulative risk to vulnerable populations in PR and emphasize the importance of continued broad characterization of drinking-water exposures at the tap with analytical capabilities that better represent the complexity of both inorganic and organic contaminant mixtures known to occur in ambient source waters. Such health-based monitoring data are essential to support public engagement in source water sustainability and treatment and to inform consumer point-of-use treatment decision making in PR and throughout the US.

Per- and polyfluoroalkyl substances (PFAS) in plasma of the West Indian manatee (Trichechus manatus).

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.

The toxic exposure of flamingos to per- and Polyfluoroalkyl substances (PFAS) from firefighting foam applications in Bonaire.

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.