In this study, the extraction and characterization of aquatic humic substances (AHS) from two blackwater rivers in the Amazon basin was carried out in order to assess the seasonal effects in the AHS structure. In addition, an investigation of the complexing capacities (CC) of the structures containing the metal ions CdII, NiII and PbII was also done. The characterization (of the AHS) was done using UV-Vis, molecular fluorescence, and infrared spectroscopy. AHS from the Negro River showed more aromatic characteristics in its structures and molecular weight, than the AHS from the Carú River. The AHS studied presented a seasonal pattern characterized by higher humification levels during the rainy season. For all the metals, the AHS complexing capacity was higher for the Negro River. The highest complexing capacities were observed for the NiII assays, which were 0.56 and 0.12 µmol NiII mg-1 dissolved organic carbon (DOC), for AHS RN and AHS RC-II, respectively. We concluded that the transport, bioavailability, and toxicity, of these metal species should be higher for Carú River.

As elevadas concentrações de mercúrio em diferentes matrizes ambientais na Amazônia têm sido atribuídas a atividades mineradoras. Entretanto, altas concentrações de mercúrio também estão presentes no solo e na água em locais como a Bacia do médio Rio Negro, distantes de fontes emissoras antropogênicas. A região Amazônica é caracterizada por dois diferentes regimes sazonais, bem definidos em períodos de cheias e vazantes. O objetivo deste trabalho foi investigar as influências sazonais na interação entre mercúrio e substâncias húmicas aquáticas (AHS), que são os principais complexantes orgânicos naturais. Os resultados obtidos por análise estatística multivariada dos dados mostraram que as substâncias húmicas possuem diferentes características estruturais, dependendo do período sazonal. A capacidade das substâncias húmicas em formar complexos com Hg(II) não está diretamente relacionada ao seu teor de carbono, mas sim natureza e disponibilidade dos grupos funcionais presentes em sua estrutura. Os grupos funcionais carboxílicos e aromáticos estão diretamente relacionados maior capacidade de complexação de AHS por íons mercúrio.

High mercury concentrations in different environmental matrices in the Amazon have been attributed to mining activities. However, high concentrations of mercury are also present in the soil and water in places like in the middle of the Negro River Basin, which is far away from any anthropogenic emission sources. The Amazon region is characterized by two different regional seasons, with well-defined flood and low water periods. The objective of this work was to investigate the seasonal influences of the interaction between mercury and aquatic humic substances (AHS), which are the main agents of the natural organic complexation capacity. The results of the multivariate statistical analysis of the data showed that the humic substances had different structural characteristics, depending on each season. The ability of humic substances to form complexes with Hg(II) is not directly related to their carbon content, but to the nature and availability of the functional groups present in its structure. The functional groups are carboxylic and aromatic directly related to the higher complexation capacity of AHS by mercury ions.

Neste trabalho, substâncias húmicas foram extraídas de amostras de água coletadas mensalmente na Bacia do Rio Negro-AM para estudar suas propriedades no ambiente amazônico e interações com íons mercúrio, considerando a influência da variação sazonal na sua formação. Os parâmetros razões atômicas C/H, C/N e C/O, grupos funcionais, radicais livres do tipo semiquinona, pH, índices pluviométricos e fluviométricos, concentrações de mercúrio foram interpretados por análise hierárquica de cluster (AHC) e análise de componentes principais (ACP). As análises estatísticas mostraram que, quanto maior o índice pluviométrico e menor o índice fluviométrico maior o grau de humificação das substâncias húmicas aquáticas. A seguinte ordem decrescente do grau de humificação das SHA coletadas mensalmente pode ser estabelecida: Nov/02 a Fev/03 > Mar/02 a Mai/02 > Jun/02 a Out/02. As maiores concentrações de mercúrio foram determinadas nas amostras mais humificadas, sugerindo que devido a rearranjos inter e/ou intramoleculares, quanto maior o grau de humificação maior a afinidade dos íons Hg(II) pelas substâncias húmicas aquáticas.

In this work, humic substances were extracted from water samples collected monthly from the Negro River basin in the Amazon state (Brazil) to study their properties in the Amazonian environment and interactions with the mercury ion considering the influence of seasonalness in this formation. The C/H, C/N and C/O atomic ratio parameters, functional groups, concentration of semiquinone-type free radicals, pH, pluviometric and fluviometric indices, and mercury concentrations were interpreted using hierarchical cluster analysis (HCA) and principal component analysis (PCA). The statistical analyses showed that when the pluviometric index was greater and the fluviometric index was smaller, the degree of humification of aquatic substances was greater. The following decreasing order of the degree of humification of the AHS collected monthly was established: Nov/02 to Feb/03 > Mar/02 to May/02 > Jun/02 to Oct/02. The greatest concentrations of mercury were detected in more humidified samples. These results suggest that due to inter and/or intra-molecular rearrangements, the degree of humification of aquatic humic substances is related to its affinity for Hg(II) ions.