Abstract This study evaluated the bioavailability of polycyclic aromatic hydrocarbons (PAHs) in Santos Bay (SB) and the adjacent Santos Continental Shelf (SCS) in Brazil. Biliary metabolites were measured in several fish species to establish a baseline for future monitoring programs. Bile samples from different species of fish were collected monthly from July to December 2005 in SB, and in August 2005 and February 2006 on SCS. Metabolite concentrations were determined using high-performance liquid chromatography with fluorescence detectors. Naphthalene, phenanthrene, and benzo[a]pyrene metabolite concentrations ranged from 24 to 810 µg g -1 of bile, 1.8 to 68 µg g -1 of bile, and below the limit of quantitation to 1.3 µg g -1 of bile, respectively. Despite its high concentrations, the levels of naphthalene metabolites were in regions of low-contamination, while benzo[a]pyrene metabolite were in the same range as those reported in moderately contaminated areas, which may indicate pyrolytic contamination by PAHs. No significant differences in the metabolite concentrations were found between the SB and the SCS samples or during the periods of collection. Future studies with a single biomonitoring species should be conducted, considering age, sex, and feeding condition of the individuals. The metabolite data presented in this study is an important baseline information for this urbanized region, which hosts several sources of contaminants. PAHs (PAHs (SB (SCS Brazil programs 200 highperformance performance detectors Naphthalene phenanthrene benzoapyrene benzo pyrene 2 81 1 - bile 18 8 1. 6 13 3 respectively lowcontamination, lowcontamination low contamination, low-contamination areas collection conducted age sex individuals region contaminants 20

Resumo A contaminação dos sedimentos superficiais foi avaliada neste estudo em amostras de áreas marinhas protegidas (AMP) da costa central de São Paulo. Quatro campanhas de amostragem foram feitas entre 2013 e 2015 em 10 sítios localizados nos Parques Estaduais Marinho da Laje de Santos e Xixová-Japuí (PEMLS e PEXJ, respectivamente), e Área de Proteção Ambiental Litoral Centro (APAMLC). As amostras foram analisadas quanto granulometria, carbono orgânico total, CaCO3, metais (Al, Fe, Hg, Cd, Co, Cr, Cu, Ni, Pb e Zn) e hidrocarbonetos alifáticos(AHs) e policíclicos aromáticos (PAHs). Em geral os sedimentos foram arenosos (exceto aqueles de APAMLC, que foram lamosos) e com quantidades variáveis de COT, MO e CaCO3. A maioria das amostras apresentaram baixas concentrações de metais de acordo com índices geoquímicos (Igeo e fatores de enriquecimento - FE). Baixa contaminação por hidrocarbonetos foi encontrada e em APAMLC os sedimentos apresentaram as maiores concentrações de AHs de origem biogênica e PAHs de pirogênicos. Nos sedimentos de APAMLC e PEMLS, os níveis de metais podem ser considerados como valores de referência. Já em PEXJ, os dados indicaram baixa qualidade de sedimentos, possivelmente devido às fontes antrópicas.

Abstract The presence of legacy contaminants in sediments from three Marine Protected Areas (MPAs) of the coast of São Paulo State was evaluated. Four sampling surveys were conducted between 2013 and 2015 in 10 sites, distributed along the Laje de Santos Marine and Xixova-Japui State Parks (PEMLS and XJSP, respectively) and Central Coast Marine Protection Area (APAMLC). Samples were analyzed for sediment texture, total organic carbon, CaCO3, metals (Al, Fe, Hg, Cd, Co, Cr, Cu, Ni, Pb and Zn), aliphatic and polycyclic aromatic hydrocarbons (AH and PAH). Sediments were generally sandy (excepting muddy samples from APAMLC), with variable amounts of TOC, OM and CaCO3. Most of the sediments exhibited low to moderate concentrations of metals, except APAMLC. Low contamination of sediments by hydrocarbons was found but samples from XLSP and APAMLC exhibited the highest concentrations of biogenic AH and PAH from pyrogenic sources. In APAMLC and PEMLS, the levels of metals can be considered as background levels according to geochemical indices (Igeo and EF). In XJSP and especially in APAMLC data indicated poor sediment quality, probably due to the effect of anthropic activities.

A ruptura de um oleoduto em maio de 1994 introduziu 2.700 tons de óleo cru no Canal de São Sebastião, contaminando algumas áreas. Na ocasião um monitoramento de hidrocarbonetos em sedimentos estava sendo realizado na região, utilizando o método de cromatografia em fase gasosa/ detecção por ionização de chama. Os dados obtidos nesse monitoramento foram comparados aos resultados das amostras coletadas logo após o acidente, com o objetivo de verificar a extensão da contaminação por óleo e os lugares mais atingidos. Os dados prévios mostraram duas fontes de introdução de hidrocarbonetos: biogênica, com predomínio de plantas superiores, e antrópica, causada por atividades náuticas e esgotos. Os dados posteriores mostraram que a estação de coleta mais próxima ao oleoduto foi a mais atingida. Na sequencia, as duas estações localizadas na entrada norte do canal apresentaram as maiores concentrações de n-alcanos, sugerindo que as correntes NE, impulsionadas pelo vento, transportaram o óleo no sentido norte do canal. Sete meses depois uma destas estações, aquela situada em local de alta energia, mostrou sinais de recuperação, o que, contudo, não foi observado na outra, considerada de ambiente deposicional. Em conclusão, pode-se afirmar que análises de hidrocarbonetos são ferramentas poderosas para avaliar o destino de um óleo e que a parte norte do Canal de São Sebastião tem maior probabilidade de ser afetada na ocasião de um derrame de óleo.

An oil pipeline ruptured in May 1994 and 2 700 tons of crude oil leaked into the São Sebastião Channel, affecting several neighboring areas. A program for the monitoring of hydrocarbons in sediments, using the gas chromatography / flame ionization detector methodology, was being undertaken in the area at the time. The data obtained were compared to those of samples collected after the accident to determine the fate of the oil spilled and ascertain its contribution to the environment. The earlier results showed that hydrocarbons were introduced from two different sources: biogenic, mainly from terrestrial plants, and anthropogenic, as oil, in sewage and from shipping. The later data indicated that the site closest to the pipeline rupture had been the most affected. Following that, two stations located at the north entrance of the channel presented the highest n-alkane concentrations, suggesting that the northeasterly wind-driven currents had carried the oil northward. Seven months later, one of these stations, a high-energy site, showed some signs of recovery, but this process was not observed at the other, which seemed to be a low-energy site. In conclusion, the data showed that the aliphatic hydrocarbon analyses were powerful tools for the assessment of the fate of the oil spill and that the northern part of the São Sebastião Channel is more subject to the effects of oil spills.

Foi realizado um levantamento dos níveis de hidrocarbonetos do petróleo em águas superficiais do Canal de São Sebastião, São Paulo, Brasil. Esse levantamento foi feito para avaliar a influência de hidrocarbonetos do petróleo do maior terminal de óleo do país. Foram coletadas 44 amostras a 1 m de profundidade, extraídas em n-hexano e analisadas por espectrofluorescência. O ponto de maior concentração, 45,29 µg.1-1, foi coletado ao lado de um navio petroleiro ancorado na região, e o menor valor detectado foi de 0.19 µg.1-1 proveniente da parte sul do Canal.

A survey of the petroleum aromatic hydrocarbons levels on the surface waters of the São Sebastião Channel, São Paulo, Brazil is presented. The survey was done in order to assess the influence of the biggest maritime oil terminal of Brazil on the petroleum hydrocarbons levels of the area. Fourty four samples taken from 1 m depth were analysed by fluorescence spectroscopy. The highest level, 45.29 µg.1-1, was found on the side of an anchored tanker and the lowest detectable level was 0.19 µg.1-1.