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.

Mobilization of persistent organic pollutants in humpback whales: Insights from feeding areas in the Antarctic peninsula and Strait of Magellan to migration, breeding, and calving grounds along the Brazilian coast.

Southern Hemisphere Megaptera novaeangliae undertake the longest migration, which reflect their exposure to lipophilic contaminants. To assess these changes, persistent organic pollutants were analyzed in blubber samples of humpback whales from three regions: the Antarctic Peninsula (n = 46), the Strait of Magellan, Chile (n = 22), and the Brazilian coast (n = 38). The similarity in PCB and HCB levels between individuals from feeding grounds and breeding grounds suggests contamination during feeding. The whales around the Antarctic Peninsula exhibited a predominance of tetrachlorobiphenyl PCBs. Whales feeding in the Strait of Magellan showed a slight prevalence of 5Cl biphenyls, likely due to their consumption of subantarctic krill species as well as small fishes potentially contaminated by industrial activities in Chile. The dominance of 5-6Cl congeners in whales in Brazil, may be attributed to the extreme physiological changes during fasting when whales utilize blubber reserves and metabolize lighter congeners, or transfer them to their calves.

Perfluoroalkyl Substances in the Western Tropical Atlantic Ocean.

The dispersion of perfluoroalkyl substances (PFAS) in surface and deep-water profiles (down to 5845 m deep) was evaluated through the Western Tropical Atlantic Ocean (TAO) between 15°N and 23°S. The sum concentrations for eight quantifiable PFAS (∑8PFAS) in surface waters ranged from 11 to 69 pg/L, which is lower than previously reported in the same area as well as in higher latitudes. Perfluoroalkyl carboxylic acids (PFCAs) were the predominant PFASs present in the Western TAO. The 16 surface samples showed variable PFAS distributions, with the predominance of perfluorooctanoic acid (PFOA) along the transect (67%; 11 ± 8 pg/L) and detection of perfluoroalkyl sulfonic acids (PFSAs) only in the Southern TAO. Perfluoroheptanoic acid (PFHpA) was often detected in the vertical profiles. PFAS distribution patterns (i.e., profiles and concentrations) varied with depth throughout the TAO latitudinal sectors (North, Equator, South Atlantic, and in the Brazilian coastal zone). Vertical profiles in coastal samples displayed decreasing PFAS concentrations with increasing depth, whereas offshore samples displayed higher PFAS detection frequencies in the intermediate water masses. Together with the surface currents and coastal upwelling, the origin of the water masses was an important factor in explaining PFAS concentrations and profiles in the TAO.

Bioaccumulation of Per- and polyfluoroalkyl substances (PFASs) in a tropical estuarine food web.

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.

Sulfluramid use in Brazilian agriculture: A source of per- and polyfluoroalkyl substances (PFASs) to the environment.

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.

Biodegradation and Uptake of the Pesticide Sulfluramid in a Soil-Carrot Mesocosm.

N-ethyl perfluorooctane sulfonamide (EtFOSA) is the active ingredient of Sulfluramid, a pesticide which is used extensively in South America for control of leaf-cutting ants. Despite being a known precursor to perfluorooctanesulfonate (PFOS), the importance of EtFOSA as a source of environmental PFOS remains unclear. In the present work, uptake, leaching, and biodegradation of EtFOSA and its transformation products were assessed over 81 days in soil-carrot ( Daucus carota ssp sativus) mesocosms for the first time. Experiments performed in the presence of carrot produced PFOS yields of up to 34% using a technical EtFOSA standard and up to 277% using Grão Forte, a commercial Sulfluramid bait formulation containing 0.0024% EtFOSA. Perfluorooctane sulfonamido acetate (FOSAA), perfluorooctane sulfonamide (FOSA), and perfluorooctanoic acid (PFOA) also formed over the course of the experiments, with the latter substance attributed to the presence of perfluorooctanamide impurities. The leachate contained low levels of transformation products and a high FOSA:PFOS ratio, consistent with recent observations in Brazilian surface water. In carrots, the more hydrophilic transformation products (e.g., PFOS) occurred primarily in the leaves, while the more hydrophobic products (e.g., FOSA, FOSAA, and EtFOSA) occurred in the peel and core. Remarkably, isomer-specific analysis revealed that the linear EtFOSA isomer biodegraded significantly faster than branched isomers. These data collectively show that the application of Sulfluramid baits can lead to the occurrence of PFOS in crops and in the surrounding environment, in considerably higher yields than previously thought.

Is Ongoing Sulfluramid Use in South America a Significant Source of Perfluorooctanesulfonate (PFOS)? Production Inventories, Environmental Fate, and Local Occurrence.

Despite international phase-out initiatives, production and use of perfluorooctanesulfonate (PFOS) and related substances continues in some countries. In Brazil, the PFOS-precursor N-ethyl perfluorooctane sulfonamide (EtFOSA) is used in Sulfluramid, a pesticide for controlling leaf-cutting ants. New data on production, environmental fate, and occurrence of Brazilian Sulfluramid are reported herein. From 2003 to 2013, Brazilian Sulfluramid manufacturing increased from 30 to 60 tonnes yr(-1) EtFOSA. During this time <1.3 tonnes yr(-1) were imported, while exports increased from ∼0.3 to 2 tonnes yr(-1). From 2004 to 2015, most EtFOSA was exported to Argentina (7.2 tonnes), Colombia (2.07 tonnes), Costa Rica (1.13 tonnes), Equador (2.16 tonnes), and Venezuela (2.4 tonnes). Within Brazil, sales occurred primarily in the states of Minas Gerais, São Paulo, Mato Grosso do Sul, Espírito Santo, and Bahia. Model simulations predict EtFOSA will partition to soils, while transformation products perfluorooctane sulfonamide (FOSA) and PFOS are sufficiently mobile to leach into surface waters. In support of these predictions, up to 3400 pg L(-1) of FOSA and up to 1100 pg L(-1) of PFOS were measured in Brazilian surface water, while EtFOSA was not detected. The high FOSA/PFOS ratio observed here (up to 14:1) is unprecedented in the scientific literature to our knowledge. Depending on the extent of conversion of EtFOSA, cumulative Brazilian Sulfluramid production and import from 2004 to 2015 may contribute between 167 and 487 tonnes of PFOS/FOSA to the environment. These levels are clearly nontrivial and of concern since production is continuing unabated.

Estudo brasileiro de validação para localização e lista de qualidade formal do Rorschach-SC: não-pacientes psiquiátricos / Brazilian validation study to locate and list of formal quality of the Rorschach-CS: non-psychiatric patients / Estudio brasileño de validación para localización y lista de calidad formal del Rorschach-SC: no-pacientes psiquiátricos

Este estudo se refere à validação do Atlas de Localização de respostas e da Lista de Qualidade Formal de respostas e conteúdos, FQ, do Rorschach-SC de uma amostra brasileira. Foram selecionados, 46 adultos não-pacientes psiquiátricos, de ambos os sexos, níveis sociais e escolaridade diversos. Os instrumentos utilizados foram o SRQ-20 e o Método de Rorschach. As respostas ao Rorschach foram codificadas segundo as áreas e a lista de qualidade formal norte-americanas e brasileiras. As análises comparativas realizadas por meio da ANOVA não encontraram diferenças entre os dois grupos, no que diz respeito às áreas de localização, W, D, Dd nas áreas brasileiras e norte-americanas, comprovando-se a validade das áreas brasileiras. Não foram também encontradas diferenças quanto à qualidade formal FQo e X+%, nas listas brasileiras e norte-americanas, comprovando-se a validade da lista brasileira para essas duas variáveis. Os resultados indicam validade para o atlas brasileiro.

This study aimed at validating the Atlas Rorschach-CS Location Areas and Formal Quality List from a Brazilian sample. 46 adults, non-patients psychiatric cases, both genders and different educational levels and social status were selected. The instruments used were the SRQ-20 and the Rorschach method. The Rorschach responses were scoredaccording to the areas and the North-American and Brazilian Lists of formal quality . The comparative analyzes performed by ANOVA did not established differences between the two groups regarding the Location Areas W, D, Dd in both North-American and Brazilian areas, proving the validity of the Brazilian areas. Differences were not found as regarding the Formal Quality FQo and X+% both using the North-American and Brazilian lists, proving the validity of the Brazilian list for these two variables.. The results indicate validity to the Brazilian Atlas.

Este estudio se refiere a la validación del Atlas de Localización de respuestas y de la Lista de Calidad Formal de respuestas y contenidos, FQ, del Rorschach-SC de una muestra brasileña. Fueron seleccionados, 46 adultos no-pacientes psiquiátricos, de ambos sexos, niveles sociales y de escolaridad diversos. Los instrumentos utilizados fueron el SRQ-20 y el Método de Rorschach. Las respuestas al Rorschach fueron codificadas según las áreas y la lista de calidad formal norteamericanas y brasileñas. Los análisis comparativos realizados, por medio de la ANOVA, no encontraron diferencias entre los dos grupos en lo que respecta a las áreas de localización, W, D, Dd en las áreas brasileñas y norteamericanas, comprobando la validez de las áreas brasileñas. No fueron también encontradas diferencias cuanto a la calidad formal FQo y X+%, en las listas brasileñas y norteamericanas, comprobando la validez de la lista brasileña para esas dos variables. Los resultados indicaron validez para el atlas brasileño.

Estudo brasileiro de validação para localização e lista de qualidade formal do Rorschach-SC: não-pacientes psiquiátricos / Brazilian validation study to locate and list of formal quality of the Rorschach-CS: non-psychiatric patients / Estudio brasileño de validación para localización y lista de calidad formal del Rorschach-SC: no-pacientes psiquiátricos

Este estudo se refere à validação do Atlas de Localização de respostas e da Lista de Qualidade Formal de respostas e conteúdos, FQ, do Rorschach-SC de uma amostra brasileira. Foram selecionados, 46 adultos não-pacientes psiquiátricos, de ambos os sexos, níveis sociais e escolaridade diversos. Os instrumentos utilizados foram o SRQ-20 e o Método de Rorschach. As respostas ao Rorschach foram codificadas segundo as áreas e a lista de qualidade formal norte-americanas e brasileiras. As análises comparativas realizadas por meio da ANOVA não encontraram diferenças entre os dois grupos, no que diz respeito às áreas de localização, W, D, Dd nas áreas brasileiras e norte-americanas, comprovando-se a validade das áreas brasileiras. Não foram também encontradas diferenças quanto à qualidade formal FQo e X+%, nas listas brasileiras e norte-americanas, comprovando-se a validade da lista brasileira para essas duas variáveis. Os resultados indicam validade para o atlas brasileiro.(AU)

This study aimed at validating the Atlas Rorschach-CS Location Areas and Formal Quality List from a Brazilian sample. 46 adults, non-patients psychiatric cases, both genders and different educational levels and social status were selected. The instruments used were the SRQ-20 and the Rorschach method. The Rorschach responses were scoredaccording to the areas and the North-American and Brazilian Lists of formal quality . The comparative analyzes performed by ANOVA did not established differences between the two groups regarding the Location Areas W, D, Dd in both North-American and Brazilian areas, proving the validity of the Brazilian areas. Differences were not found as regarding the Formal Quality FQo and X+% both using the North-American and Brazilian lists, proving the validity of the Brazilian list for these two variables.. The results indicate validity to the Brazilian Atlas.(AU)

Este estudio se refiere a la validación del Atlas de Localización de respuestas y de la Lista de Calidad Formal de respuestas y contenidos, FQ, del Rorschach-SC de una muestra brasileña. Fueron seleccionados, 46 adultos no-pacientes psiquiátricos, de ambos sexos, niveles sociales y de escolaridad diversos. Los instrumentos utilizados fueron el SRQ-20 y el Método de Rorschach. Las respuestas al Rorschach fueron codificadas según las áreas y la lista de calidad formal norteamericanas y brasileñas. Los análisis comparativos realizados, por medio de la ANOVA, no encontraron diferencias entre los dos grupos en lo que respecta a las áreas de localización, W, D, Dd en las áreas brasileñas y norteamericanas, comprobando la validez de las áreas brasileñas. No fueron también encontradas diferencias cuanto a la calidad formal FQo y X+%, en las listas brasileñas y norteamericanas, comprobando la validez de la lista brasileña para esas dos variables. Los resultados indicaron validez para el atlas brasileño.(AU)

Contamination by chlorinated pesticides, PCBs and PBDEs in Atlantic spotted dolphin (Stenella frontalis) in western South Atlantic.

Chlorinated pesticides, PCBs and PBDEs were analysed in nine blubber samples of Atlantic spotted dolphins, Stenella frontalis, incidentally captured during fishing operations in southern and southeastern Brazil between 2005 and 2007. The majority of compounds analysed were detected, suggesting widespread contamination over the region. Although the samples came from a location far from main coastal industrial areas, the results revealed an influence from such sources. Therefore, levels of PCBs (774-23659 ng g(-1) lipid wt.) and PBDEs (23-1326 ng g(-1) lipid wt.) detected seem to be related to the movement of individuals throughout near-shore and offshore waters. The sample from a lactating female exhibited a lower level of contamination and a distinct pattern, indicating selective transfer favouring less lipophilic compounds.

Long-term trends of polychlorinated biphenyls and chlorinated pesticides in franciscana dolphin (Pontoporia blainvillei) from Southern Brazil.

Selected POPs were analyzed in blubber samples of Pontoporia blainvillei from Southern Brazil to appraise temporal trend over a 10 year period (1994-2004). Overall, levels of POPs were relatively low, especially when compared to Northern Hemisphere concentrations. Apart from Mirex and PCBs, which showed stable concentrations, DDTs, HCB, CHLs, Dieldrin levels presented a slight decrease over the studied period. In addition, the increase in the PCBs/DDTs ratio supports the idea that inputs of DDTs are decaying faster than PCBs.