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.

Abstract Pockmarks are circular or elliptical structures formed at the seabed by the expulsion of gas from the subsurface. They are widely distributed along the continental margin off southeastern Brazil and can be over a kilometer wide and 100 meters deep. However, studies concerning the organic characteristics of these pockmark areas are scarce. This study sought to evaluate the organic composition of the sedimentary matter in pockmark areas located in the continental slope region of the southern Brazilian coast. Hydrocarbons, sterols, long-chain alcohols, stable isotopes of C and N, total organic carbon, and total nitrogen were assessed to provide an organic molecular characterization of the pockmarks located in the Southwestern Atlantic Ocean. These compounds did not reflect the organic characteristics of the scape of fluids that generate pockmark structures.

For the evaluation of PAH extraction techniques in adipose and liver tissues of marine tetrapod, samples of some species (Pontoporia blainvillei, Chelonia mydas, Thalassarche melanophris, and Balaenoptera brydei) were spiked with PAH standards and extracted using soxhlet system and microwave oven. The results of both extraction techniques for the two different tissues of the four species of tetrapod were within the quality assurance and quality control criteria, that means both extraction techniques produced acceptable recoveries for surrogate and spiked compounds added to the sample tissues. Although both techniques of extraction met quality criteria and were considered suitable for extraction of marine tetrapod tissues, the soxhlet system produced a higher recovery of the spiked compounds and a lower standard deviation between the replicates than the microwave extraction; therefore the soxhlet system was considered the more efficient extraction method for PAH. The evaluation of liver and adipose tissue PAH accumulation, as well as the influence of tissue heterogeneity, was impaired as the concentrations of PAHs in almost all samples were lower than the detection limits of the analytical method.

Resumo 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.

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.

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.

Resumo Este estudo analisou a qualidade dos sedimentos de três Áreas Marinhas Protegidas (AMP) situadas na porção central do litoral paulista (Parque Estadual Marinho da Laje de Santos - PEMLS; Parque Estadual Xixová-Japuí- PEXJ; Área de Proteção Ambiental Marinha do Litoral Centro - APAMLC). Quatro campanhas de coleta foram organizadas (Setembro/Outobro-2013; Janeiro-2014; Julho-2014; Janeiro-2015). Amostras de sedimento foram coletadas em 10 pontos ao longo das 3 AMP. As amostras foram analisadas para granulometria, carbono orgânico total, CaCO3, metais, hidrocarbonetos alifáticos e policíclico aromáticos, e toxicidade de sedimento integral e interface sedimento-água. Análise de Componentes Principais foi utilizada na integração dos dados. A maioria das amostras exibiu baixa contaminação, exceto a amostra de P2 (APAMLC) onde níveis moderados de contaminantes foram detectados. Sedimentos de P7 e P9 (PEMLS) eventualmente apresentaram sinais de hidrocarbonetos de petróleo. As demais amostras não apresentaram contaminação relevante, mas tiveram toxicidades variáveis, especialmente os sedimentos predominantemente bioclásticos. A PCA indicou forte contribuição das propriedades do sedimento, principalmente CaCO3 e amônia, na geração da toxicidade, indicando que fatores naturais e/ou antrópicos podem estar induzindo a toxicidade nas AMP estudadas.

Abstract In this study, the quality of sediments from three Marine Protected Areas (MPAs) located on the coast of São Paulo (Laje de Santos Marine State Park - PEMLS; Xixova-Japui State Park - XJSP; and Central Coast Marine Protection Area - APAMLC) was assessed. Four sampling surveys were conducted (September/October 2013; January 2014; July 2014; January 2015). Sediment samples were collected at10 sites, distributed along the 3 MPAs. Samples were analyzed for sediment texture, total organic carbon, CaCO3, metals, aliphatic and polycyclic aromatic hydrocarbons, and for whole-sediment and sediment-water interface toxicities. Principal component analysis (PCA) was used to integrate data. Most of the sediments exhibited low concentrations of chemicals, with the exception of those from P2 (APAMLC) where moderate levels of contaminants were detected. Sediments from P7 and P9 (PEMLS) occasionally showed signs of petroleum hydrocarbons. The other sediments showed no relevant contamination but presented variable toxicity, especially those of bioclastic composition. The PCA indicated a contribution of the sediment properties to the toxicities, especially the CaCO3. In bioclastic sediments, toxicity might be due to physical causes by or any indirect factor such as the presence of ammonia. It was concluded that both natural and anthropic factors are causing toxicity in sediments from the MPAs studied.

Resumo Os sistemas aquáticos amazônicos são geralmente associados a águas intactas, no entanto, a ocupação urbana de forma irregular das bacias hidrográficas e a deficiência no saneamento básico podem levar a contaminação pontual e difusa. A contaminação por esgoto em sedimentos superficiais de entremarés do Estuário Guajará, costa amazônica brasileira, foi investigada usando um conjunto de esteróides como biomarcadores. Os sedimentos coletados ao longo da margem urbanizada também foram submetidos a análises de clorofila-a, carbono orgânico total e granulometria. Coprostanol, o principal esterol de origem fecal, foi encontrado em concentrações entre 0,06 a 7,93 µg g-1 de sedimento seco, na sequência Tucunduba > Ver-o-Peso > Porto da Palha > Tamandaré > Icoaraci > Miramar. As baixas correlações entre os parâmetros investigados provavelmente foram resultantes de fontes mistas de matéria orgânica e processos costeiros. Os esteróis derivados de plantas, incluindo álcoois n-C30 e β-amirinil alcanoatos, mostraram-se abundantes nas amostras, porém não impediram o uso dos outros esteróides na avaliação da contaminação por esgoto. Índices específicos envolvendo estanóis e estanonas 5α and 5β evidenciaram a contaminação por esgoto nas amostras com as menores concentrações absolutas de coprostanol. A predominância de estanóis 5β indicou contaminação crônica por esgoto na área.

Abstract Amazonian aquatic systems are usually associated with pristine waters, however, irregular urban occupation of the hydrographic basins and sewerage deficiencies may lead to point and diffuse contamination. Sewage contamination in intertidal surface sediments from the Guajará Estuary, Brazilian Amazon coast, was evaluated using a set of steroids as biomarkers. Sediments collected along the urbanized margin were also analyzed for chlorophyll a, total organic carbon and grain sizes. Coprostanol, the main fecal sterol, was found at concentrations varying from 0.06 to 7.93 µg g-1 dry sediment, following the sequence Tucunduba > Ver-o-Peso > Porto da Palha > Tamandaré > Icoaraci > Miramar. Mixed sources of organic matter and coastal process probably concurred to produce weak correlations among the parameters. Plant derived sterols, including n-C30 alcohol and β-amyrinyl alkanoates, were clearly abundant, but they did not preclude the use of other steroid signals to the assessment of sewage contamination. High values of the steroid indexes involving 5α and 5β stanols and stanones highlighted sewage contamination at the sites with the lowest absolute coprostanol concentrations. The predominance of 5β stanols indicated a chronically sewage contamination of the area.

<p>Polycyclic aromatic hydrocarbons (PAHs) were identified and quantified in samples of superficial sediments of the Negro River, in the Amazon region of Brazil, through analyses performed by GC/MS. Total PAH concentration that includes parent and alkylated PAHs ranged from 6.5 to 5348 ng g^-1 of dry weight. The ∑16 PAHs prioritized in environmental studies by the U.S. Environmental Protection Agency (USEPA) ranged from 5.6 to 1187 ng g^-1. The most contaminated places were those where muddy sediments were found, with the highest concentrations of organic matter, carbon and total nitrogen. The priority PAHs with high molecular weight represented 70% of the total abundance and showed that the main source of contamination of the sediments was pyrogenic. However, petrogenic PAHs coming from oil and derivatives input is also an important contamination source to be considered.</p>

Avaliação técnica do resultado analítico é de extrema relevância, pois o mesmo será utilizado para comparação com legislações e tomadas de decisão, tais como, disposição adequada de sedimento dragado e avaliação da qualidade de água superficial salobra e salina frente à classificação da Resolução CONAMA 357/05. É fundamental que o gestor ambiental discuta com o laboratório contratado as recomendações e exigências técnicas da legislação em questão e do órgão ambiental, acompanhe o andamento das análises e solicite re-análise, quando há suspeita de resultados anômalos. As principais recomendações técnicas são: (1) limites de quantificação do método (LQs) inferiores aos padrões ambientais; (2) análises realizadas em laboratórios cujo escopo analítico esteja acreditado pelo Instituto Nacional de Metrologia (INMETRO) ou qualificado ou aceito pelo órgão ambiental licenciador; (3) cadeia-de-custódia para rastreabilidade das amostras; (4) cartas-controle para evidência de desempenho do método analítico empregado pelo laboratório; (5) análise com material de referência certificado ou, em sua ausência, ensaios realizados por adição padrão ou adição de reforço e (6) apresentação de cromatogramas para as análises realizadas por cromatografia. Dentro deste contexto, visando auxiliar o gestor ambiental na avaliação dos relatórios de ensaio, este trabalho tem como objetivo discutir as aplicações dos métodos SW 846 da US EPA usados para as matrizes marinhas, as implicações de basear os estudos em limites de detecção (LDM) e não nos de quantificação da amostra (LQA) e discutir modificações de metodologia propostas para atendimento aos padrões de qualidade.

Technical evaluation of analytical data is of extreme relevance considering it can be used for comparisons with environmental quality standards and decision-making as related to the management of disposal of dredged sediments and the evaluation of salt and brackish water quality in accordance with CONAMA 357/05 Resolution. It is, therefore, essential that the project manager discusses the environmental agency's technical requirements with the laboratory contracted for the follow-up of the analysis underway and even with a view to possible re-analysis when anomalous data are identified. The main technical requirements are: (1) method quantitation limits (QLs) should fall below environmental standards; (2) analyses should be carried out in laboratories whose analytical scope is accredited by the National Institute of Metrology (INMETRO) or qualified or accepted by a licensing agency; (3) chain of custody should be provided in order to ensure sample traceability; (4) control charts should be provided to prove method performance; (5) certified reference material analysis or, if that is not available, matrix spike analysis, should be undertaken and (6) chromatograms should be included in the analytical report. Within this context and with a view to helping environmental managers in analytical report evaluation, this work has as objectives the discussion of the limitations of the application of SW 846 US EPA methods to marine samples, the consequences of having data based on method detection limits (MDL) and not sample quantitation limits (SQL), and present possible modifications of the principal method applied by laboratories in order to comply with environmental quality standards.