Determination of Toxicity at Different Trophic Levels of Aqueous Film-Forming Foams (AFFF) Used in Fire Fighting.

Aqueous film-forming foams (AFFF), containing perfluorinated surfactants, can reach the environment. The objective of this study was to determine the ecotoxicity of AFFF, according to the type of fire to be fought (A1: 1.05 g.L- 1, A2: 3.15 g.L- 1 and A3: 6.30 g.L- 1), to bioindicators of different trophic levels. For Artemia salina a toxic effect was observed at sample A1 (at concentrations of 100%), A2 (at concentrations above 25%) and A3 (at concentrations above 12.5%). For Lactuca sativa all samples affected the number of germinated seeds, speed and percentage of germination and root length. To the Eisenia fetida earthworm, samples A2 and A3 were considered toxic due to the percent avoidance being 70% and 100%, respectively. In Macaca mullata renal cell culture test, none of the samples were toxic by the MTT test. Therefore, it is necessary to develop methods for the safe use of AFFF by professionals.

Occurrence and potential ecological risks of PFAS in Pampulha Lake, Brazil, a UNESCO world heritage site.

Per- and polyfluoroalkyl substances (PFAS) comprise >4000 synthetic substances used in industrial applications and consumer products. PFAS used daily in households and manufacturing plants end up in domestic sewage, and industrial effluents can be discharged to surface water. Urban watersheds located in low and middle-income countries (LMIC), which lack sanitation infrastructure, are potential recipients of waste containing PFAS. Yet, only a few studies report PFAS occurrence in urban reservoirs and lakes, especially those located in the Global South due to resource limitations. This is the first study aimed to assess PFAS occurrence and ecological risks in Pampulha Lake, Brazil, a site which represents the reality of many other urban watersheds in LMIC as it is surrounded by densely populated areas and manufacturing plants. Surface water samples were collected monthly for 1 year from four sampling points at Pampulha Lake. Sample analysis was based on US Environmental Protection Agency Method 1633, which employs solid phase extraction followed by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS). Species sensitivity distribution (SSD) curves were built to identify potentially susceptible species based on detected water concentrations. Bioaccumulation was estimated for fish tissue. Short-chain (perfluorobutanesulfonic acid, PFBS and perfluorohexanoic acid, PFHxA) and long-chain PFAS (perfluorodecanoic acid, PFDA; perfluorooctanoic acid, PFOA; perfluorododecanoic acid, PFDoA; and perfluorooctanesulfonic acid, PFOS) were detected at the µg L-1 range. Total PFAS concentrations in the wet season were generally higher than in the dry season, likely due to limited capacity of the treatment plant processing water from tributaries which receive raw sewage. More than 5 % of aquatic species are potentially susceptible to chronic effects of PFOS at detected concentrations (0.2-2.2 µg L-1). Predicted bioaccumulation of PFOS in fish was above advisory diet intake levels for humans. Results emphasize the need for studies related to PFAS occurrence in watersheds located in LMIC.

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.

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.

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.

Characterization of per- and polyfluoroalkyl substances (PFAS) and other constituents in MSW landfill leachate from Puerto Rico.

Elevated per- and polyfluoroalkyl substance (PFAS) concentrations have been reported in municipal solid waste (MSW) landfill leachate with higher levels in wet and warmer subtropical climates. Information about landfill leachate characteristics is much more limited in tropical climates. In this study, 20 landfill leachate samples were collected from three MSW landfills on the tropical island of Puerto Rico and results were compared against landfills nationally and within Florida, USA. The samples collected in Puerto Rico underwent physical-chemical analysis, as well as a quantitative analysis of 92 PFAS. Samples described in this study include discrete leachate types, such as leachate, gas condensate, and leachate which has undergone on-site treatment (e.g., RO treatment, phytoremediation, lagoons). A total of 51 PFAS were detected above quantitation limits, including perfluorohexylphosphonic acid, a perfluoroalkyl acid (PFAA) which has not been reported previously in landfill leachate. ∑PFAS concentrations in this study (mean: 38,000 ng L-1), as well as concentrations of individual PFAS, are significantly higher than other reported MSW landfill leachate concentrations. The profiles of leachates collected from on-site treatment systems indicate possible transformation of precursor PFAS as a result of treatment processes - oxidizing conditions, for example, may facilitate aerobic transformation, increase the concentrations of PFAAs, and possibly increase the apparent ∑PFAS concentration. Extreme climate events, including rising temperatures and more frequent hurricanes, have placed additional strain on the solid waste management infrastructure on the island - adding complexity to an already challenging PFAS management issue. As concern grows over PFAS contamination in drinking water, these findings should inform solid waste and leachate management decisions in order to minimize PFAS emissions in island environments.

Global quantification of emerging and legacy per- and polyfluoroalkyl substances in indoor dust: Levels, profiles and human exposure.

This study investigated the occurrence and distribution of per- and polyfluoroalkyl substances (PFASs) in house dust samples from six regions across four continents. PFASs were detected in all indoor dust samples, with total median concentrations ranging from 17.3 to 197 ng/g. Among the thirty-one PFAS analytes, eight compounds, including emerging PFASs, exhibited high detection frequencies in house dust from all six locations. The levels of PFASs varied by region, with higher concentrations found in Adelaide (Australia), Tianjin (China), and Carbondale (United States, U.S.). Moreover, PFAS composition profiles also differed among regions. Dust from Australia and the U.S. contained high levels of 6:2 fluorotelomer phosphate ester (6:2 diPAP), while perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) were predominant in other regions. Furthermore, our results indicate that socioeconomic factors impact PFAS levels. The assessment of human exposure through dust ingestion and dermal contact indicates that toddlers may experience higher exposure levels than adults. However, the hazard quotients of PFASs for both toddlers and adults were below one, indicating significant health risks are unlikely. Our study highlights the widespread occurrence of PFASs in global indoor dust and the need for continued monitoring and regulation of these chemicals.

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.

Characterization of the inheritance of field-evolved resistance to diamides in the fall armyworm (Spodoptera frugiperda) (Lepidoptera: Noctuidae) population from Puerto Rico.

The fall armyworm (Spodoptera frugiperda) is one of the most destructive pests of corn. New infestations have been reported in the East Hemisphere, reaching India, China, Malaysia, and Australia, causing severe destruction to corn and other crops. In Puerto Rico, practical resistance to different mode of action compounds has been reported in cornfields. In this study, we characterized the inheritance of resistance to chlorantraniliprole and flubendiamide and identified the possible cross-resistance to cyantraniliprole and cyclaniliprole. The Puerto Rican (PR) strain showed high levels of resistance to flubendiamide (RR50 = 2,762-fold) and chlorantraniliprole (RR50 = 96-fold). The inheritance of resistance showed an autosomal inheritance for chlorantraniliprole and an X-linked inheritance for flubendiamide. The trend of the dominance of resistance demonstrated an incompletely recessive trait for H1 (♂ SUS × â™€ PR) × and an incompletely dominant trait for H2 (♀ SUS × â™‚ PR) × for flubendiamide and chlorantraniliprole. The PR strain showed no significant presence of detoxification enzymes (using synergists: PBO, DEF, DEM, and VER) to chlorantraniliprole; however, for flubendiamide the SR = 2.7 (DEM), SR = 3.2 (DEF) and SR = 7.6 (VER) indicated the role of esterases, glutathione S- transferases and ABC transporters in the metabolism of flubendiamide. The PR strain showed high and low cross-resistance to cyantraniliprole (74-fold) and cyclaniliprole (11-fold), respectively. Incomplete recessiveness might lead to the survival of heterozygous individuals when the decay of diamide residue occurs in plant tissues. These results highlight the importance of adopting diverse pest management strategies, including insecticide rotating to manage FAW populations in Puerto Rico and other continents.

Occurrence of antibiotics, hormones and PFAs in surface water from a Nile tilapia aquaculture facility in a Brazilian hydroelectric reservoir.

This study assessed the occurrence of five antibiotics, three hormones, caffeine, and long and short-chain perfluoroalkyl and polyfluoroalkyl substances (PFASs) in surface water and feedstuff samples obtained from aquaculture cages in Três Marias reservoir in Brazil. This is the first work to evaluate the presence of PFAS in surface water used for aquaculture in Brazil. Solid-phase extraction and low temperature partitioning extraction followed by liquid chromatography coupled to mass spectrometry (LC-MS) were performed to process and analyze surface water samples and feedstuff, respectively. The ecotoxicological risk quotient was calculated for target compounds detected in water. Ciprofloxacin and caffeine were detected in all surface water samples. Pharmaceutical drugs ranged from 0.7 ng L-1 (trimethoprim) to 389.2 ng L -1 (ß-estradiol). Estrone (10.24 ng g-1) and ß-estradiol (66.20 ng g-1) were also found in feedstuff. Four PFASs (PFOA, PFDoA, PFTeDA, and PFBS) were detected (9.40-15.2 µg L-1) at levels higher than reported in studies conducted worldwide. Ecotoxicological risk assessment indicated high risks for caffeine and PFOA, PFDoA, and PFTeDA with RQ values from 10 to 103. These findings reveal risks to biodiversity, ecosystem integrity and human health considering possible intake of these contaminants by fish consumption due to potential bioaccumulation of these substances. Hence, it is critical to conduct more studies in this direction in Brazil and other low and middle-low-income countries.

Perfluorooctanoate (PFOA) cell-autonomously promotes thermogenic and adipogenic differentiation of brown and white adipocytes.

Perfluorooctanoic acid (PFOA) is a synthetic organofluoride surfactant associated with several toxic effects in humans and animals. Particularly, it has been observed that PFOA treatment of mice results in weight loss associated with recruited brown adipose tissue (BAT), including an increased amount of uncoupling protein 1 (UCP1). The molecular mechanism behind this BAT recruitment is presently unknown. To investigate the existence of possible cell-autonomous effects of PFOA, we treated primary cultures of brown and white (inguinal) adipocytes with PFOA, or with the non-fluorinated equivalent octanoate, or with vehicle, for 48 h (from day 5 to day 7 of differentiation). PFOA in itself increased the gene expression (mRNA levels) of UCP1 and carnitine palmitoyltransferase 1A (CPT1α) (thermogenesis-related genes) in both brown and white adipocytes. In addition, PFOA increased the expression of fatty acid binding protein 4 (FABP4) and peroxisome proliferator-activated receptor α (PPARα) (adipogenesis-related genes). Also the protein levels of UCP1 were increased in brown adipocytes exposed to PFOA. This increase was more due to an increase in the fraction of cells that expressed UCP1 than to an increase in UCP1 levels per cell. The PFOA-induced changes were even more pronounced under simultaneous adrenergic stimulation. Octanoate induced less pronounced effects on adipocytes than did PFOA. Thus, PFOA in itself increased the levels of thermogenic markers in brown and white adipocytes. This could enhance the energy metabolism of animals (and humans) exposed to the compound, resulting in a negative energy balance, leading to diminished fitness.

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.

Removing polyfluoroalkyl substances (PFAS) from wastewater with mixed matrix membranes.

Polyfluoroalkyl and perfluoroalkyl (PFAS) chemicals are fluorinated and exhibit complicated behavior. They are determined and highly resistant to ecological modifications that render plants ecologically robust. Thermal stability and water and oil resistance are examples of material qualities. Their adverse consequences are causing increasing worry due to their bioaccumulative nature in humans and other creatures. Direct data indicates that PFAS exposure in humans causes endocrine system disruption, immune system suppression, obesity, increased cholesterol, and cancer. Several PFASs are present in drinking water at low doses and may harm people. These cancer-causing PFAS have caused concern for water bodies all around the globe. Analytical techniques are used to identify and measure PFAS in an aqueous medium (membrane). Furthermore, a deeper explanation is provided for PFAS removal methods, including mixed matrix membrane (MMM) technology. By removing over 99 % of the PFAS from wastewater, MMMs may effectively remove PFAS from sewage when the support matrix contains adsorbing components. Furthermore, we consider several factors affecting the removal of PFAS and practical sorption methods for PFAS onto various adsorbents.

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.

Perfluorohexane sulfonate (PFHxS) disturbs the estrous cycle, ovulation rate, oocyte cell communication and calcium homeostasis in mice.

Perfluoroalkyl substances are man-made chemicals with ample consumer and industrial applications. They are widely used and are resistant to environmental and metabolic degradation. Several studies have evaluated the effects of Perfluorohexane sulfonate on reproduction. However, there are few reports exploring the cell and molecular mechanisms of its toxicity in the ovary. The aim of this study was to investigate the effects of PFHxS exposure on the estrous cycle, ovulation rate, and the underlying mechanisms of action in female mice in vivo. The animals received a single sub-lethal dose of PFHxS (25.1 mg/kg, 62.5 mg/kg) or vehicle and were stimulated to obtain immature cumulus cell-oocyte complexes (COCs) from the ovaries, or superovulated to develop mature COCs. To evaluate oocyte physiology, Gap-junction intercellular communication (GJIC) was analyzed in immature COCs and calcium homeostasis was evaluated in mature oocytes. PFHxS exposure prolonged the estrous cycle and decreased ovulation rate in female mice. Connexins, Cx43 and Cx37, were downregulated and GJIC was impaired in immature COCs, providing a possible mechanism for the alterations in the estrous cycle and ovulation. No morphological abnormalities were observed in the mature PFHxS-exposed oocytes, but calcium homeostasis was affected. This effect is probably due, at least partially, to deregulation of the endoplasmic reticulum calcium modulator, Stim1. These mechanisms of ovarian injury could explain the reported correlation among PFHxS levels and subfertility in women undergoing fertility treatments.

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.

Confirming sulfluramid (EtFOSA) application as a precursor of perfluorooctanesulfonic acid (PFOS) in Brazilian agricultural soils.

Perfluorooctanesulfonic acid (PFOS) is a manmade chemical with several industrial applications and also a potential byproduct of many other per- and polyfluorinated substances (PFAS) in the environment. Due to the gathered evidence on its environmental persistence, long-range transport, toxicity, and bioaccumulative and biomagnifying properties, PFOS, its salts and perfluorooctane sulfonyl fluoride (PFOSF), were listed for global restriction under the Stockholm Convention on Persistent Organic Pollutants in 2009. Nevertheless, Brazil has granted an acceptable purpose exemption for using PFOSF to produce sulfluramid (EtFOSA) and to apply it as insecticide to control leaf-cutting ants of the genus Atta and Acromyrmex. Previous studies have pointed out EtFOSA as a precursor of PFOS in the environment, including in soils. Therefore, we aimed to confirm the role of EtFOSA in PFOS formation in soils representing areas where sulfluramid-based ant baits are used. A biodegradation assay was carried out by applying technical EtFOSA in triplicate samples of ultisol (PV) and oxisol (LVd) and measuring the contents of EtFOSA, perfluorooctane sulfonamide acetic acid (FOSAA), perfluorooctane sulfonamide (FOSA), and PFOS at seven moments (0, 3, 7, 15, 30, 60, and 120 days). The monitored byproducts started being noticed on the 15th day. After 120 days, PFOS yields were 30% for both soils, whereas FOSA yields were 46% (PV soil) and 42% (LVd soil) and FOSAA yields were 6% (PV soil) and 3% (LVd soil). It can be expected that FOSAA and FOSA contents will eventually be converted into PFOS in the environment and that the presence of plants could boost PFOS formation. Therefore, the ongoing extensive and intensive use of sulfluramid-based ant baits pose a considerable source of PFOS to the environment.

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.

Perfluoropropionic Acid-Driven Nucleation of Atmospheric Molecules under Ambient Conditions.

A molecular-level understanding of the compositions and formation mechanism of secondary organic aerosols is important in the context of growing evidence regarding the adverse impacts of aerosols on the atmosphere and human health. The ever-growing emissions of pollutants and particulate matter in the atmosphere are a global concern. A particular class of pollutants, which are being important in this sense, are persistent organic pollutants (POPs) since they represent synthetic organic compounds with a long lifetime in the environment. Among the POPs, the perfluorinated compounds, such as perfluoroalkyl carboxylic acids (CnF2n+1COOH) or PFCAs, draw a lot of attention due to their adverse effect on human health. In the present work, we employ high-level density functional theory to investigate the electrostatic interaction of perfluoropropionic acid (C2F5COOH) or PFPA, a PFCA with n = 2, with well-known atmospheric molecules, namely, HCHO, HCOOH, CH3OH, H2SO4, and CH3SO3H [methanesulfonic acid (MSA)]. A detailed and systematic quantum chemical calculation has been performed to analyze the structural, energetic, electrical, and spectroscopic properties of several binary clusters in the context of atmospheric nucleation process. Our analysis shows that PFPA forms very stable hydrogen-bonded binary clusters with molecules like H2SO4 and MSA, which widely recognized atmospheric nucleation precursors. Scattering intensities of radiation (Rayleigh activities) are found to increase many fold when PFPA forms clusters. Analyses of the cluster-binding electronic energies and the free-energy changes associated with their formation at different temperatures indicate that PFPA could participate in the initial nucleation processes and contribute effectively to the new particle formation in the atmosphere.

Exposure to endocrine disruptors and alterations in mineralized tissues: a narrative review / Exposición a disruptores endocrinos y alteraciones en tejidos mineralizados: revisión narrativa

Background: Endocrine Disrupting Chemicals (EDCs) would cause alterations in organs/systems of exposed individuals or their progeny. Objetive: To identify and analyze the main published findings on the effects of exposure to EDCs on teeth, cartilage, and bone. Material and Methods: Two databases were analyzed: Medline and Web of Science. Only observational studies analyzing the effect of EDCs on mineralized tissues published since 2006 were included in the study. Results: 25 articles were selected, most of them involving EDCs pesticides, plasticizers, or personal care products, highlighting organochlorine compounds, bisphenols, phthalates, dioxins, parabens, and perfluoroalkyls. Thirty-six per cent of the studies reported an accumulation of EDCs in teeth or bones, while 64% reported alterations in their development or morphology, mainly at the bone level, primarily affecting their mineral density and size, as well as that of the bones of exposed individuals or their progeny. The type of effect observed was related to the EDCs analyzed, and it seemed to depend on variables such as age, sex, ethnicity/race, and even the metabolic status of the individuals in the different species analyzed. No evidence associated with effects on cartilage was found. Conclusion: EDCs in the environment, at work, or at home, under different exposure routes, are capable of accumulating in teeth and bone, particularly affecting the latter. It is necessary to study the effect of EDCs on mineralized tissues in agro-industrial areas, especially on teeth.

Antecedentes: Los Químicos Disruptores Endocrinos (EDCs) causarían alteraciones en órganos/sistemas de individuos expuestos, o su progenie. Objetivo: Identificar y analizar los principales hallazgos publicados sobre el efecto de la exposición a EDCs en dientes, cartílago y hueso. Material y Métodos: Se analizaron dos bases de datos: Medline y Web of Science, incluyendo solo estudios observacionales publicados desde el 2006, analizando el efecto de los EDCs sobre tejidos mineralizados. Resultados:25 artículos fueron seleccionados, siendo la mayoría de los EDCs pesticidas, plastificantes o productos de cuidado personal, destacando los compuestos Organo-clorados, Bisfenoles, Ftalatos, Dioxinas, Parabenos y los Perfluoroalquilos. Un 36% de los estudios reportaron un acúmulo de EDCs en dientes o huesos, mientras que un 64% informaron de alteraciones en su desarrollo o morfología, particularmente a nivel de huesos, afectando principalmente su densidad mineral y su tamaño, así como el de los individuos expuestos o su progenie. El tipo de efecto observado tuvo relación con el EDCs analizado, pareciendo depender de variables tales como edad, sexo, etnia/raza e incluso el estado metabólico de los individuos, en las diferentes especies analizadas. No se encontraron evidencias asociadas a efectos en el cartílago. Conclusión: Los EDCs en el medio ambiente, ámbito laboral o doméstico, bajo distintas rutas de exposición, son capaces de acumularse en diente y hueso, afectando particularmente a este último. Es necesario estudiar el efecto de los EDCs en los tejidos mineralizados en zonas agroindustriales, particularmente a nivel de dientes.