Wanilson Luiz-Silva

Variabilidade espacial e sazonal da concentração de elementos-traço em sedimentos do sistema estuarino de Santos-Cubatão (SP)

Multi-element analyses of sediment samples from the Santos-Cubatao 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 Cubatao river than in other sites, while the other elements showed greater concentrations in the Morrao 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.

Elevated rates of organic carbon, nitrogen, and phosphorus accumulation in a highly impacted mangrove wetland

The effect of nutrient enrichment on mangrove sediment accretion and carbon accumulation rates is poorly understood. Here we quantify sediment accretion through radionuclide tracers to determine organic carbon (OC), total nitrogen (TN), and total phosphorus (TP) accumulation rates during the previous 60 years in both a nutrient-enriched and a pristine mangrove forest within the same geomorphological region of southeastern Brazil. The forest receiving high nutrient loads has accumulated OC, TN, and TP at rates that are fourfold, twofold, and eightfold respectively, higher than those from the undisturbed mangrove. Organic carbon and TN stable isotopes (δ13C and δ15N) reflect an increased presence of organic matter (OM) originating with either phytoplankton, benthic algae, or another allochthonous source within the more rapidly accumulated sediments of the impacted mangrove. This suggests that the accumulation rate of OM in eutrophic mangrove systems may be enhanced through the addition of autochthonous and allochthonous nonmangrove material.

Multi-elemental contamination and historic record in sediments from the Santos-Cubatão Estuarine System, Brazil

Este trabalho registra pela primeira vez o historico da contaminacao e as fontes de 38 elementos em sedimentos do sistema estuarino de Santos-Cubatao (SE do Brasil), em uma das areas mais industrializadas da America Latina. A composicao de um testemunho de 260 cm de profundidade do estuario do rio Morrao foi determinada por ICP-MS e avaliada por meio de fatores de enriquecimento, analise de componentes principais, matrizes de correlacao e assinaturas geoquimicas. Elementos contaminantes como Cr, Mn, Ni, Zn, Ga, Ag, Cd, Sn, Sb, Pb e Bi foram associados ao Fe, derivados de atividades siderurgicas, 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 sobreposicao da distribuicao do Fe sedimentar e producao local de aco indicaram que o Fe e um marcador confiavel do historico da contaminacao, permitindo a estimativa de taxas de sedimentacao 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-Cubatao 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 Morrao 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.

Processos físico-químicos em drenagem ácida de mina em mineração de carvão no sul do Brasil

Acid mine drainage generated from coal mine showed a pH of 3.2, high concentrations of SO42-, 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.

Coupled anthropogenic anomalies of radionuclides and major elements in estuarine sediments.

Concentrations of fertilizer industry-derived P (up to 3.4%), Ca (up to 6.1%), (226)Ra (up to 744 Bq kg(-1)) and (210)Pb (up to 1317 Bq kg(-1)) at least one order of magnitude above natural levels were recorded in a sediment core from Morrão River estuary (SE Brazil). Unsupported (210)Pb (= total (210)Pb-(226)Ra) activities unexplained by atmospheric fallout and deviations from the radionuclides secular equilibrium also indicated strong anomalies. Anomalous constituents were positively correlated with each other and negatively correlated with clay mineral-bearing elements. These negative correlations were explained by a depletion of natural sediment constituents due to a dilution caused by elevated inputs of steel industry-derived elements (mainly by Fe levels up to 24%). Absolute data and normalizations by a proxy for clays (Al) and anthropogenic Fe evidenced variabilities in the quality of coastal and land-derived sediment inputs, mainly due to changes in the relative contributions from industrial sources.

Geochemistry of acid mine drainage from a coal mining area and processes controlling metal attenuation in stream waters, southern Brazil

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.

Mercury dilution by autochthonous organic matter in a fertilized mangrove wetland.

A dated sediment core from a highly-fertilized mangrove wetland located in Cubatão (SE Brazil) presented a negative correlation between mercury (Hg) and organic carbon contents. This is an unusual result for a metal with well-known affinity to organic matter. A dilution of Hg concentrations by autochthonous organic matter explained this observation, as revealed by carbon stable isotopes signatures (δ(13)C). Mercury dilution by the predominant mangrove-derived organic matter counterbalanced the positive influences of algal-derived organic matter and clay contents on Hg levels, suggesting that deleterious effects of Hg may be attenuated. Considering the current paradigm on the positive effect of organic matter on Hg concentrations in coastal sediments and the expected increase in mangrove organic matter burial due to natural and anthropogenic stimulations of primary production, predictions on the influences of organic matter on Hg accumulation in mangrove wetlands deserve caution.

Geochemistry of intertidal sediment pore waters from the industrialized Santos-Cubatão Estuarine System, SE Brazil

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 SO(4)(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.

O papel dos sulfetos volatilizados por acidificação no controle do potencial de biodisponibilidade de metais em sedimentos contaminados de um estuário tropical, no sudeste do Brasil

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-Cubatao Estuarine System (SE Brazil), which is located in one of the most industrialized areas in the Latin America. Intertidal sediments from the Morrao 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.

Fractionation of rare earth and other trace elements in crabs, Ucides cordatus, from a subtropical mangrove affected by fertilizer industry

Fractionation of rare earth elements (REE) and other trace metal concentrations (Th, U, Cd, Cr, Cu, Ni, Pb, and Zn) between mangrove sediments and claw muscles and shells of male crabs (Ucides cordatus) from a subtropical estuary highly impacted by fertilizer industry activities was investigated. This is the first record of REE distribution in these organisms, and the results showed higher accumulations of these metals, U and Th in shells, probably related to the replacement of Ca during molting. Contents of Cd, Cr and Ni were similar in both tissues, but Cu, Zn and Pb were mostly accumulated in the claw muscle with concentrations above those considered safe for human consumption according to the Brazilian legislation. REE fractionation was different in the analyzed tissues being softer in the shells. The results provided evidences that the water absorbed during molting controls the chemistry of REE in shells. In contrast, the chemistry of REE in the claw muscle, in which was observed preferential absorption of light REE, is controlled by diet. REE fractionation obtained for the claw muscles was closely correlated to the observed in the contaminated substrate and in materials related to the production of phosphate fertilizers (contamination source), which supports their transference to this Ucides cordatus tissue without fractionation by the ingestion of sediments. Our results showed the potential use of crab tissues for monitoring REE and trace element sources in mangrove areas, with claw muscle exhibiting the contaminant source fingerprint.