Influência de drenagem ácida sobre a qualidade de água e sedimento foi investigada em uma área de mineração de carvão (sul do Brasil). A drenagem ácida mostrou pH entre 3,2 e 4,6 e elevadas concentrações de sulfato, As e metais, dos quais, Fe, Mn e Zn excederam os limites para emissão de efluentes da legislação brasileira. Arsênio também excedeu levemente o limite. Poços de monitoramento de água subterrânea situados em áreas de mina ativa e pilhas de rejeitos revelaram intervalo de pH e concentrações químicas semelhantes aqueles da drenagem ácida. Entretanto, amostras de águas subterrânea e de rio utilizadas para o abastecimento público municipal revelaram pH entre 7,2 e 7,5 e baixas concentrações químicas, embora a concentração de Cd tenha superado um pouco o limite adotado pela legislação brasileira para águas subterrâneas. Em geral, as águas de superfície mostraram grande intervalo de pH (6 a 10,8), e a influência da drenagem ácida em sua composição química não foi muito significativa. Localmente, drenagem ácida parece ter dissolvido rochas carbonáticas presentes na sequência estratigráfica local, atenuando a dispersão de metais e As. Anomalias destes elementos foram encontradas em sedimentos de corrente, e elas foram fortemente dependentes da proximidade de depósitos de rejeitos e minas abandonadas. Neste trabalho, processos de precipitação em sedimentos e diluição de fases dissolvidas foram considerados como os principais mecanismos responsáveis pela atenuação das concentrações de metais e As nas zonas de mistura entre drenagem ácida e água fluvial. Em geral, observou-se uma maior influência das atividades de mineração sobre a composição química de águas superficiais e sedimentos quando fatores de enriquecimento em relação aos níveis de background regionais foram utilizados.

Acid drainage influence on the water and sediment quality was investigated in a coal mining area (southern Brazil). Mine drainage showed pH between 3.2 and 4.6 and elevated concentrations of sulfate, As and metals, of which, Fe, Mn and Zn exceeded the limits for the emission of effluents stated in the Brazilian legislation. Arsenic also exceeded the limit, but only slightly. Groundwater monitoring wells from active mines and tailings piles showed pH interval and chemical concentrations similar to those of mine drainage. However, the river and ground water samples of municipal public water supplies revealed a pH range from 7.2 to 7.5 and low chemical concentrations, although Cd concentration slightly exceeded the limit adopted by Brazilian legislation for groundwater. In general, surface waters showed large pH range (6 to 10.8), and changes caused by acid drainage in the chemical composition of these waters were not very significant. Locally, acid drainage seemed to have dissolved carbonate rocks present in the local stratigraphic sequence, attenuating the dispersion of metals and As. Stream sediments presented anomalies of these elements, which were strongly dependent on the proximity of tailings piles and abandoned mines. We found that precipitation processes in sediments and the dilution of dissolved phases were responsible for the attenuation of the concentrations of the metals and As in the acid drainage and river water mixing zone. In general, a larger influence of mining activities on the chemical composition of the surface waters and sediments was observed when enrichment factors in relation to regional background levels were used.

A composição geoquímica das águas intersticiais de sedimentos foi estudada em comparação com a composição das partículas sedimentares e de águas superficiais em um estuário de uma das áreas mais industrializadas da América Latina (sistema estuarino de Santos-Cubatão, sudeste do Brasil). Águas intersticiais e superficiais apresentaram altos níveis de F-, NH4+, Fe, Mn e P, devido a duas fontes industriais pontuais. No verão, quando as razões SO4(2-)/Cl- sugeriram aumento na redução do sulfato, os níveis mais elevados de alguns metais dissolvidos nas águas intersticiais (como Cu e Ni) foram atribuídos à dissolução redutiva de fases oxidadas. Os resultados sugerem que os riscos de aumento nas concentrações das águas superficiais por difusão ou advecção das águas intersticiais provavelmente dependem de influências conjuntas do aporte de águas de maré e águas subterrâneas.

The geochemical composition of sediment pore water was investigated in comparison with the composition of sediment particles and surface water in an estuary within one of the most industrialized areas in Latin America (Santos-Cubatão estuarine system, SE Brazil). Pore and surface waters presented anomalously high levels of F-, NH4+, Fe, Mn and P due to two industrial point sources. In the summer, when SO4(2-)/Cl- ratios suggested an enhanced sulfate reduction, the higher dissolved levels observed in pore waters for some metals (e.g., Cu and Ni) were attributed to reductive dissolution of oxidized phases. Results evidenced that the risks of surface water concentration increase due to diffusion or advection from pore water are probably dependent on coupled influences of tidal pumping and groundwater inputs.

Acid mine drainage generated from coal mine showed a pH of 3.2, high concentrations of SO4(2-), Al, Fe, Mn, Zn and minor As, Cd, Co, Cr, Cu, Ni and Pb. The major reduction in the concentration occurred for Al, As, Cr, Fe and Pb after the treatment with CaO. The evolution of these acid waters within the tributary stream showed decreasing concentration for all soluble constituents, except Al. This natural attenuation was controlled by pH (6.4 to 10.8) as a result of concurrent mixing with tributary stream and reaction with local bedrock that contains limestone. Aluminum increasing concentration during this evolution seems to be related to an input of Al-enriched waters due to the leaching of silicate minerals in alkaline conditions.

Measurements of acid volatile sulfide (AVS) and simultaneously extracted metals (SEM) were combined in order to verify the ecological hazard of contaminated sediments from the Santos-Cubatão Estuarine System (SE Brazil), which is located in one of the most industrialized areas in the Latin America. Intertidal sediments from the Morrão River estuary were collected seasonally in short cores. The redox conditions, organic matter contents and grain-size were the main controlling factors on SEM distribution. However, clear relationships among these variables and AVS were not observed. The molar SEM/AVS ratios were frequently > 1 especially in the summer, suggesting major metal bioavailability hazard in this humid hot season.

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.

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.

The concentrations of mercury in surface sediments (<63mum fraction) from Santos-Cubatão Estuary, located in State of São Paulo, southeast Brazil, were determined to obtain the level of contamination in this highly polluted area. Fifteen stations distributed though seven rivers were sampled (156 samples collected) from September 1997 to August 1998 (12 stations sampled monthly) and during March, June, September and December 1998 (three stations sampled quarterly). The levels of mercury varied from 0.10 to 6.77 ppm, with the index of geoaccumulation of the rivers varying between grades 1 and 3 (annual average). The Cubatão is the most polluted river and the main agent of Hg dispersion in the study area. Geochemical data revealed that Hg levels in surface from Santos-Cubatão Estuary at present are as elevated as in past (for instance, by comparison 1980's), when Cubatão city was known as one of the most polluted cities in the world.