Polybrominated diphenyl ether flame retardants in the antarctic environment

Polybrominated diphenyl ethers (PBDEs) are anthropogenic chemicals whose environmental behavior is similar to the well-known polychlorinated biphenyls (PCBs). Few studies have quantified the amount and distribution of PBDEs in the southern hemisphere and Antarctica. The analyses reported in this dissertation document the levels of PBDEs in lichens, mosses and seabird eggs collected at King George Island, Antarctic Peninsula. The analyses were carried out using Gas Chromatography/Electron Impact-Mass Spectrometry (GC/EI-MS). Employing the ion stacking technique lowered detection limits and ensured instrument selectivity and sensitivity to the compounds of interest. Lichens and mosses absorb PBDEs directly from the atmosphere and their contamination indicates that long-range transport is the primary source of these chemicals to King George Island. The congener patterns of PBDEs in plants indicate that commercial mixtures of Penta-BDE and Octa-BDE have reached Antarctica. Differences in the levels of PBDEs observed in lichens and mosses are probably due to factors that govern the uptake of PBDEs from the atmosphere. Contamination in lichens showed a positive correlation with local precipitation. Conversely, absorption of PBDEs in mosses appears to be controlled by other plant-specific factors. Marine phytoplankton-derived aerosols are hypothesized to play an important role in the atmospheric transport of PBDEs to the Antarctic environment. PBDEs in south polar skua eggs revealed much higher concentration than in penguin eggs. This is likely associated with the northward migration of these seabirds during the non-breeding season. While penguins reside year-round in Antarctica, south polar skuas migrate northward and can be seen in boreal oceans during the austral winter. Distribution of PBDEs in penguin eggs matches the pattern found in local vegetation suggesting a common source for the chemicals. In contrast, the congener pattern of south polar skuas suggests that birds breeding at King George Island are wintering in the northwestern Pacific Ocean. A potential metabolism of PBDEs in penguin eggs during the incubation period seems to be limited. Most congeners were unaltered from source material in the eggs of chinstrap and gentoo penguins. Low levels of PBDEs, short incubation periods and energy constraints may explain these observations

The legacy of man-made organic compounds in surface sediments of Pina Sound and Suape Estuary, northeastern Brazil

Polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) are man-made organic chemicals that have adverse effects on aquatic organisms, sometimes altering ecosystem functioning with potential consequences for the coastal carbon cycle. This study assessed PCBs and OCPs in surface sediments of two estuaries with distinct historical land use on the coast of Pernambuco, northeastern Brazil. OCPs such as HCB, aldrin, dieldrin, isodrin, mirex, methoxychlor, endosulfans (α- and β-isomers), HCHs (α-, β-, γ- and δ-isomers) and chlordane-related compounds were below their respective limits of detection in all samples. Mean levels of PCBs in Pina Sound and Suape Estuary were 4.37 and 0.94 ng g-1 dry weight (dw), respectively. Average concentrations of DDTs in those same estuaries were 5.24 and 0.42 ng g-1 dw, respectively. No significant correlations were found between mud and contaminants (either PCBs or DDTs) at Pina Sound. In contrast, PCBs were significantly associated with mud at Suape Estuary. The greater contamination found at Pina Sound is consistent with land use of the urban, densely populated city of Recife. Residues of DDTs found in sediments of both estuaries reflect past local usage. Occasional adverse biological effects may be expected due to the levels of DDTs at several sites in Pina Sound. Lower levels of chemicals such as PCBs in the newly industrialized Suape Estuary suggest that a similarly low impact of legacy pollutants may be expected for future industrial enterprises around the world.Bifenilas policloradas (PCBs) e pesticidas organoclorados (OCPs) são compostos orgânicos sintéticos que causam efeitos negativos em organismos aquáticos, eventualmente alterando o funcionamento de ecossistemas com consequências locais para o ciclo do carbono. O presente estudo investigou PCBs e OCPs em sedimentos superficiais de dois estuários com distintos históricos de ocupação na costa de Pernambuco. Os pesticidas HCB, aldrin, dieldrin, isodrin, mirex, metoxicloro, endosulfans, HCHs e clordanos não foram encontrados acima de seus limites de detecção nas amostras. As concentrações médias de PCBs na Bacia do Pina e no Estuário de Suape foram 4,37 e 0,94 ng g-1 peso seco (ps), respectivamente. Para DDTs, as concentrações médias nesses estuários foram 5,24 e 0,42 ng g-1 ps, respectivamente. Não foram encontradas correlações significativas entre a fração lamosa do sedimento e os contaminantes (PCBs e DDTs) na Bacia do Pina. Em contrapartida, os PCBs foram encontrados associados à lama no Estuário de Suape. A maior contaminação na Bacia do Pina é condizente com a área historicamente urbanizada e densamente povoada da cidade do Recife. A composição de DDTs no sedimento de ambos os estuários indica uso antigo desse pesticida. Os níveis de DDTs em diversos pontos da Bacia do Pina podem ocasionalmente desencadear efeitos negativos na biota local. Por outro lado, os baixos níveis de PCBs encontrados no Estuário de Suape - uma área que passa por recente processo de industrialização - sugerem que novos complexos industriais tendem a causar baixo impacto em termos de poluentes orgânicos persistentes herdados de práticas antigas

Occurrence of organochlorine compounds (pesticides and PCBs) in marine mammals from São Paulo coast (Brazil) and King George Island (Antarctica).

Os compostos organoclorados causam grande impacto na natureza devido a três características básicas: persistência ambiental, bioacumulação e alta toxicidade. Os mamíferos marinhos estão entre os organismos mais vulneráveis à toxicidade crônica desses contaminantes porque, além de concentrá-los em grande quantidade, a fêmea transfere parte de sua carga ao filhote durante a gestação e a lactação. Assim, o presente trabalho teve como objetivos otimizar uma metodologia para determinação de organoclorados (pesticidas e PCBs) em matrizes gordurosas e verificar a ocorrência dos mesmos na gordura subcutânea de mamíferos marinhos amostrados na costa de São Paulo (Brasil) e na Ilha Rei George (Antártica). No protocolo metodológico otimizado, a extração foi realizada em extrator Soxhlet (8 h) com uma mistura de n-hexano e diclorometano. A etapa de purificação foi feita através de tratamento ácido e o extrato final analisado em cromatógrafo a gás equipado com detector de captura de elétrons (GC-ECD). A performance do método foi avaliada com material de referência certificado, enquadrando-se dentro de padrões internacionais de controle de qualidade. O limite de detecção do método foi em média 2 ng g-1. As análises apontaram DDTs e PCBs como os grupos que mais causam impacto nos cetáceos da costa de São Paulo. Isso refletiu o histórico de ambos no Brasil, tanto em indústria como em agricultura e saúde pública. Em contrapartida, HCHs e HCB não apresentaram concentrações elevadas, fato que pode ser atribuído à volatilidade dos mesmos em regiões de clima tropical. Da mesma maneira, a-clordano, g-clordano e mirex não foram detectados em níveis significativos. A foca de Weddell (Leptonychotes weddelli), habitante do continente antártico, evidenciou as menores cargas de contaminante entre os animais estudados. As toninhas (Pontoporia blainvillei) e o golfinho-nariz-de-garrafa (Tursiops truncatus) também apresentaram baixos níveis de organoclorados. Os botos-cinza (Sotalia fluviatilis) revelaram concentrações de DDT iguais ou superiores a cetáceos da Índia, país onde esse pesticida ainda não está proibido. Já o golfinho-de-dentes-rugosos (Steno bredanensis) mostrou a maior contaminação entre os animais analisados, comparável a espécies estudadas em águas costeiras de países desenvolvidos (onde os organoclorados foram muito utilizados).Organochlorine compounds cause strong impact on the nature, as a consequence of three basic characteristics: environmental persistence, bioaccumulation, and high toxicity. The marine mammals are one of the most vulnerable organisms to the chronic toxicity of these contaminants. Besides the high concentration in the body, the female transfers part of her load to the offspring during gestation and lactation. The aim of this study was (1) the optimization of a methodology for determining chlorinated hydrocarbons (pesticides and PCBs) in fatty biological matrices and (2) the analysis of organochlorines in marine mammals blubber sampled along São Paulo coast (Brazil) and King George Island (Antarctica). According to the optimized methodology, the extraction was carried out in Soxhlet apparatus (8 h) with a mixture of n-hexane and dichloromethane. The clean-up was carried out with acid treatment and the resulting extract injected into gas chromatography coupled to electron capture detector (GC-ECD). The method performance was evaluated with certified reference material and fitted for international standards of control quality. The mean method detection limit was 2 ng g-1. DDTs and PCBs were the most concentrated organochlorines in the cetaceans from São Paulo coast. These findings reflected their past usage in Brazil by industry, agriculture, and public health. On the other hand, both HCHs and HCB were not found in high concentration likely due to their volatility in tropical climate areas. Mirex, a-chlordane and g-chlordane were not detected in elevated levels. The Weddell seal (Leptonychotes weddelli), from Antarctic continent, presented the smallest load among the studied animals. As the same way, the franciscanas (Pontoporia blainvillei) and the bottlenose dolphin (Tursiops truncatus) presented low organochlorine levels. The marine tucuxi (Sotalia fluviatilis) showed equal or higher DDT concentration than Indian cetaceans where that pesticide is still in use. The rough-toothed dolphin (Steno bredanensis) revealed the greatest contamination among the analyzed animals, comparable to species studied in the coastal waters of developed countries (where organochlorines were extensively used)

Organic pollutants and their correlation with stable isotopes in vegetation from King George Island, Antarctica

International audienceVegetation samples from King George Island, Antarctica (62º05'S, 058º23'W) were collected in the austral summer of 2004-05. Lichens (Usnea aurantiaco-atra and Usnea antarctica), mosses (Sanionia uncinata, Syntrichia princeps and Brachytecium sp.), and one angiosperm (Colobanthus quitensis) species were analyzed for persistent organic pollutants as well as δ13C and δ15N stable isotopes. The following contaminants were found above the method detection limit (MDL): HCB (0.141 to 1.06 ng g-1 dry weight), HCHs (< MDL to 1.20 ng g-1 dw), DDTs (< MDL to 1.73 ng g-1 dw), PCBs (7.76 to 18.6 ng g-1 dw) and PBDEs (0.146 to 0.811 ng g -1 dw). In all cases, levels in mosses were higher than in lichens (one order of magnitude higher for OCs), suggesting that specific biogeochemical processes were involved in the transport, exposure and absorption for each group. Carbon stable isotope ratios showed clearly different ranges for lichens (δ13C from -21.13 up to -18.43‰) and mosses (-25.99 to -21.64‰). The only angiosperm species investigated exhibited 13C signature within the moss range. A large range of δ15N was found (-7.67 to 20.75‰) and seemed to be related to nitrogen uptake from different animal-derived sources. Pearson's correlation showed significant results for some contaminants (e.g. HCHs/HCB and PCBs/DDTs) and suggested the influence of the origin of both nitrogen and pollutants, notably taking secondary sources (animal excrements/remains, for instance) into consideration

The legacy of man-made organic compounds in surface sediments of Pina Sound and Suape Estuary, northeastern Brazil

Abstract Polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) are man-made organic chemicals that have adverse effects on aquatic organisms, sometimes altering ecosystem functioning with potential consequences for the coastal carbon cycle. This study assessed PCBs and OCPs in surface sediments of two estuaries with distinct historical land use on the coast of Pernambuco, northeastern Brazil. OCPs such as HCB, aldrin, dieldrin, isodrin, mirex, methoxychlor, endosulfans (α- and β-isomers), HCHs (α-, β-, γ- and δ-isomers) and chlordane-related compounds were below their respective limits of detection in all samples. Mean levels of PCBs in Pina Sound and Suape Estuary were 4.37 and 0.94 ng g-1 dry weight (dw), respectively. Average concentrations of DDTs in those same estuaries were 5.24 and 0.42 ng g-1 dw, respectively. No significant correlations were found between mud and contaminants (either PCBs or DDTs) at Pina Sound. In contrast, PCBs were significantly associated with mud at Suape Estuary. The greater contamination found at Pina Sound is consistent with land use of the urban, densely populated city of Recife. Residues of DDTs found in sediments of both estuaries reflect past local usage. Occasional adverse biological effects may be expected due to the levels of DDTs at several sites in Pina Sound. Lower levels of chemicals such as PCBs in the newly industrialized Suape Estuary suggest that a similarly low impact of legacy pollutants may be expected for future industrial enterprises around the world

The legacy of man-made organic compounds in surface sediments of Pina Sound and Suape Estuary, northeastern Brazil

<div><p>Abstract Polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) are man-made organic chemicals that have adverse effects on aquatic organisms, sometimes altering ecosystem functioning with potential consequences for the coastal carbon cycle. This study assessed PCBs and OCPs in surface sediments of two estuaries with distinct historical land use on the coast of Pernambuco, northeastern Brazil. OCPs such as HCB, aldrin, dieldrin, isodrin, mirex, methoxychlor, endosulfans (α- and β-isomers), HCHs (α-, β-, γ- and δ-isomers) and chlordane-related compounds were below their respective limits of detection in all samples. Mean levels of PCBs in Pina Sound and Suape Estuary were 4.37 and 0.94 ng g-1 dry weight (dw), respectively. Average concentrations of DDTs in those same estuaries were 5.24 and 0.42 ng g-1 dw, respectively. No significant correlations were found between mud and contaminants (either PCBs or DDTs) at Pina Sound. In contrast, PCBs were significantly associated with mud at Suape Estuary. The greater contamination found at Pina Sound is consistent with land use of the urban, densely populated city of Recife. Residues of DDTs found in sediments of both estuaries reflect past local usage. Occasional adverse biological effects may be expected due to the levels of DDTs at several sites in Pina Sound. Lower levels of chemicals such as PCBs in the newly industrialized Suape Estuary suggest that a similarly low impact of legacy pollutants may be expected for future industrial enterprises around the world.</p></div

Shell alterations in limpets as putative biomarkers for multi-impacted coastal areas

During the last years, shell alterations in gastropods have been proposed as tools to be used in monitoring programs. However, no studies were so far performed investigating the relationships among shell parameters and classical biomarkers of damage. The relationship between shell alterations (biometrics, shape and elemental composition) and biomarkers (LPO and DNA strand break) was evaluated in the limpet L subrugosa sampled along a contamination gradient in a multi-impacted coastal zone from southeastern Brazil. Statistically significant differences were detected among sites under different pollution levels. The occurrence of shell malformations was consistent with environmental levels of several hazardous substances reported for the studied area and related to lipid peroxidation and DNA damage. In addition, considering the low mobility, wide geographic distribution, ease of collection and abundance of limpets in coastal zones, this putative tool may be a cost-effective alternative to traditional biomarkers. Thus, shell alterations in limpets seem to be good proxies for assessing biological adverse effects in multi-impacted coastal zones. (C) 2017 Elsevier Ltd. All rights reserved.Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)PIBIC/Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Univ Fed Sao Paulo UNIFESP, Dept Ciencias Mar, Santos, SP, BrazilUniv Fed Pernambuco UFPE, Dept Oceanog, Recife, PE, BrazilUniv Sao Paulo, Museu Zool, Sao Paulo, SP, BrazilUniv Catolica Pernambuco, Dept Biol, Recife, PE, BrazilUniv Estadual Paulista, UNESP, Inst Biociencias, Sao Vicente, SP, BrazilUniv Fed Sao Paulo UNIFESP, Dept Ciencias Mar, Santos, SP, BrazilFAPESP: 2015/25063-0PIBIC/CNPqCNPq: 166122/2015-7CNPq: PQ 306486/2015-6CNPq: PQ 307074/2013-7Web of Scienc