RESUMEN
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.
Asunto(s)
Ácidos Alcanesulfónicos , Monitoreo del Ambiente , Fluorocarburos , Contaminantes Químicos del Agua , Fluorocarburos/análisis , Contaminantes Químicos del Agua/análisis , Ácidos Alcanesulfónicos/análisis , Brasil , Sedimentos Geológicos/química , Caproatos/análisisRESUMEN
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.
Asunto(s)
Ácidos Alcanesulfónicos , Fluorocarburos , Contaminantes Químicos del Agua , Ácidos Alcanesulfónicos/análisis , Océano Atlántico , Ácidos Carboxílicos , Monitoreo del Ambiente , Fluorocarburos/análisis , Ácidos Sulfónicos/análisis , Contaminantes Químicos del Agua/análisisRESUMEN
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.
Asunto(s)
Ácidos Alcanesulfónicos , Fluorocarburos , Contaminantes Químicos del Agua , Ácidos Alcanesulfónicos/análisis , Animales , Bioacumulación , Brasil , Monitoreo del Ambiente , Fluorocarburos/análisis , Cadena Alimentaria , Contaminantes Químicos del Agua/análisisRESUMEN
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 5400â¯pgâ¯g-1, 979â¯pgâ¯g-1, and 1020â¯pgâ¯L-1, respectively, with PFAS profiles generally dominated by PFOS and perfluorooctane sulfonamide (FOSA). Coastal sediment contained ∑PFAS concentrations of up to 198 pgâ¯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 8930â¯pgâ¯L-1 were observed. PFOS and PFOA were detected in all river water samples. Groundwater also exhibited PFAS contamination (5730â¯pgâ¯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.
Asunto(s)
Ácidos Alcanesulfónicos/análisis , Ácidos Carboxílicos/análisis , Fluorocarburos/análisis , Insecticidas/análisis , Contaminantes del Suelo/análisis , Sulfonamidas/análisis , Contaminantes Químicos del Agua/análisis , Agricultura , Brasil , Monitoreo del Ambiente , Eucalyptus , Agua Dulce/análisis , Sedimentos Geológicos/análisis , Hojas de la Planta/química , Suelo/químicaRESUMEN
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.
Asunto(s)
Ácidos Alcanesulfónicos , Daucus carota , Fluorocarburos , Plaguicidas , Contaminantes del Suelo , Brasil , Suelo , SulfonamidasRESUMEN
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 â¼0.3 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.
Asunto(s)
Ácidos Alcanesulfónicos/análisis , Fluorocarburos/análisis , Sulfonamidas/análisis , Contaminantes Químicos del Agua/análisis , Brasil , Monitoreo del Ambiente , Fluorocarburos/economía , Modelos Teóricos , Sulfonamidas/economía , Contaminantes Químicos del Agua/economíaRESUMEN
We report here on the spatial distribution of C(4), C(6), and C(8) perfluoroalkyl sulfonates, C(6)-C(14) perfluoroalkyl carboxylates, and perfluorooctanesulfonamide in the Atlantic and Arctic Oceans, including previously unstudied coastal waters of North and South America, and the Canadian Arctic Archipelago. Perfluorooctanoate (PFOA) and perfluorooctanesulfonate (PFOS) were typically the dominant perfluoroalkyl acids (PFAAs) in Atlantic water. In the midnorthwest Atlantic/Gulf Stream, sum PFAA concentrations (∑PFAAs) were low (77-190 pg/L) but increased rapidly upon crossing into U.S. coastal water (up to 5800 pg/L near Rhode Island). ∑PFAAs in the northeast Atlantic were highest north of the Canary Islands (280-980 pg/L) and decreased with latitude. In the South Atlantic, concentrations increased near Rio de la Plata (Argentina/Uruguay; 350-540 pg/L ∑PFAAs), possibly attributable to insecticides containing N-ethyl perfluorooctanesulfonamide, or proximity to Montevideo and Buenos Aires. In all other southern hemisphere locations, ∑PFAAs were <210 pg/L. PFOA/PFOS ratios were typically ≥1 in the northern hemisphere, â¼1 near the equator, and ≤1 in the southern hemisphere. In the Canadian Arctic, ∑PFAAs ranged from 40 to 250 pg/L, with perfluoroheptanoate, PFOA, and PFOS among the PFAAs detected at the highest concentrations. PFOA/PFOS ratios (typically â«1) decreased from Baffin Bay to the Amundsen Gulf, possibly attributable to increased atmospheric inputs. These data help validate global emissions models and contribute to understanding of long-range transport pathways and sources of PFAAs to remote regions.