Especiação de metais e sua interação com a matéria orgânica dissolvida em um reservatório artificial
Tonietto, Alessandra Emanuele
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Environmental degradation of aquatic ecosystems stimulates investigations about the interactions between dissolved organic matter, trace metals and the biota. This study aimed to investigate the speciation of cadmium, copper, lead and zinc in a reservoir subjected to antropic activities. To develop this study, we have chosen Barra Bonita Reservoir (SP), an eutrophic and contaminated ecosystem that receives urban, industrial and agricultural efluents. Water samples were obtained in three locations within the reservoir considering local seasonality (dry winter and rainny summer) during 24 months. The samples were analysed for total, total dissolved, labile and ionic concentrations of the metals, as well as complexation parameters (CL e logK ML) and competition between copper and zinc for the ligands, fluorimetric characterization, and physico-chemical parameters of the water. The results showed a high degree of deterioration of the ecosystem. Independent of sampling location, the concentration order for the metals was Zn>Cu>Pb>Cd (total and total dissolved). In general copper and zinc remained as complexes in the dissolved fraction, while lead was mostly associated with particulate materials. MineqL+ calculations showed that Zn2+ and Cd2+ dominated the labile form, whereas copper and lead remained associated with carbonates. The increased concentration of total dissolved metal showed an increase of copper and zinc complexes, and labile form of zinc and lead. Through principal component analysis (PCA), seasonal influences related to the main sources of metals supply into the reservoir were identified. Metal competition analysis showed that previously added copper affected zinc speciation. However, prior addition of zinc indicated that this metal was complexed by the ligands that were previously available to copper. Nevertheless, no differences were observed in copper speciation. Because the resevoir is subject to intense and frequent cyanobacteria blooms, Cylindrospermopsis raciborskii was isolated from that environment and cultured in the laboratory to obtain its excreted materials. This excreted material was then separated into three molecular weight fractions (> 30 kDa; 30-10 kDa; 10-3 kDa) that were analyzed for complexation capacity (CL e logK ML) with cadmium, copper, lead and zinc, elemental (C, H, N and S) and biochemical composition, fluorescence characteristics and competition for ligands between copper and zinc, and cadmium xvii and lead. The results showed that the fraction >30 kDa and 30-10 kDa had high carbohydrates contents, but low proteins and lipids, whereas for the 10-3 kDa fraction no variation on the biochemical composition was obtained. Fluorescence analysis showed peaks that define proteinaceous materials with 2 5 aromatic rings ususally assigned to be of phytoplankton origin. The CL and logK'ML for the different molecular weight fractions indicated a broad chemical diversity of the ligands that had different affinities for the metals. Metal competition titrations on the excreted material showed that it was only for the >30 kDa fraction that either previously added copper or zinc were complexed by ligands previously available to zinc and copper, respectively. In the 30-10 kDa fraction previously added lead, was complexed by ligands that were available to cadmium. In all fractions no lead complexation capacity was detected when cadmium had been previously added.