Recebido em 22/3/05; aceito em 28/6/05; publicado na web em 20/1/06 SPATIAL AND SEASONAL VARIABILITY OF TRACE-ELEMENT CONCENTRATIONS IN SEDIMENTS FROM THE SANTOS-CUBATÃO ESTUARINE SYSTEM, SÃO PAULO, BRAZIL. Multi-element analyses of sediment samples from the Santos-Cubatão Estuarine System were carried out to investigate the spatial and seasonal variability of trace-element concentrations. The study area contains a rich mangrove ecosystem that is a habitat for tens of thousands of resident and migratory birds, some of them endangered globally. Enrichments of metals in fine-grained surface sediments are, in decreasing order, Hg, Mn, La, Ca, Sr, Cd, Zn, Pb, Ba, Cu, Cr, Fe, Nb, Y, Ni and Ga, relative to pre-industrial background levels. The maximum enrichment ranged from 49 (Hg) to 3.1 (Ga). Mercury concentrations were greater in the Cubatão river than in other sites, while the other elements showed greater concentrations in the Morrão river. Concentrations of Mn were significantly greater in winter and autumn than in summer and spring. However, other elements (e.g. Cd and Pb) showed the opposite, with greater concentrations in summer and spring. This study suggests that seasonal changes in physical and chemical conditions may affect the degree of sediment enrichment and therefore make the assessment of contamination difficult. Consequently, these processes need to be considered when assessing water quality and the potential contamination of biota.

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Este trabalho registra pela primeira vez o histórico da contaminação e as fontes de 38 elementos em sedimentos do sistema estuarino de Santos-Cubatão (SE do Brasil), em uma das áreas mais industrializadas da América Latina. A composição de um testemunho de 260 cm de profundidade do estuário do rio Morrão foi determinada por ICP-MS e avaliada por meio de fatores de enriquecimento, análise de componentes principais, matrizes de correlação e assinaturas geoquímicas. Elementos contaminantes como Cr, Mn, Ni, Zn, Ga, Ag, Cd, Sn, Sb, Pb e Bi foram associados ao Fe, derivados de atividades siderúrgicas, enquanto Be, Ca, Sc, Co, Cu, Sr, Y, Zr, Nb, Hf, Ta, Th e U estiveram associados ao P, relacionados ao processo produtivo de fertilizantes. Uma sobreposição da distribuição do Fe sedimentar e produção local de aço indicaram que o Fe é um marcador confiável do histórico da contaminação, permitindo a estimativa de taxas de sedimentação para 45 anos de atividades industriais. This paper records for the first time the contamination history and identifies the sources of 38 elements in sediments from the Santos-Cubatão Estuarine System (SE Brazil), at one of the most industrialized areas in Latin America. The compositions of samples from a 260 cm long sediment core collected in the Morrão River estuary were determined by ICP-MS. Enrichment factors, principal component analysis, correlation matrixes, and the characterization of geochemical signatures permitted a consistent data evaluation. Contaminant elements such as Cr, Mn, Ni, Zn, Ga, Ag, Cd, Sn, Sb, Pb, and Bi were associated with steel plant-derived Fe concentrations, while Be, Ca, Sc, Co, Cu, Sr, Y, Zr, Nb, Hf, Ta, Th, and U were associated with fertilizer industry-derived P concentrations. An overlap of sedimentary Fe distribution and local steel plant production indicated that Fe is a reliable marker of the contamination history, allowing the estimation of sedimentation rates over a period of 45 years of industrial activities. Keywords: intertidal sediments, pollution, trace-elements, contamination source, industrial contamination IntroductionHuman activities in coastal areas have accelerated the input of chemical contaminants to coastal ecosystems, implying in environmental concerns at local, regional and global scales. Despite the implementation of contamination control policies, anomalously high levels of multiple contaminants have still been recorded in many coastal sediments, as observed in the Santos-Cubatão Estuarine System in São Paulo State, Southeastern Brazil. 1 This setting is historically, economically and environmentally important at a regional scale. Human activities in the estuary started in the beginning of the 16 th century, just after the arrival of the first Portuguese explorers in Brazil. The process of colonization began in São Vicente City, the oldest Brazilian colonization settlement, and soon afterwards in Santos City, the home of the largest harbor in Latin America today.The riverine and estuarine systems in this area have been seriously contami...