S. Furian

Natural arsenic in groundwater and alkaline lakes at the upper Paraguay basin, Pantanal, Brazil

A distinctive feature of Nhecolândia, a sub-region of the Pantanal wetland in Brazil, is the presence of both saline (alkaline) and freshwater lakes. Saline lakes were attributed to a past arid phase during the Pleistocene, but recent studies have shown that the geochemistry of the saline lakes arises from the current concentration process of fresh waters that is supplied to the Pantanal every year. The region is mainly used for cattle farming, and more recently eco-tourism is becoming widespread and water conservation agencies have begun to worry about As contents in surface and shallow groundwater. The study was carried out along a 600-m-long transect that linked a freshwater lake to a saline lake. The spatial distribution of As is studied, based on soil morphology, according to pH, redox conditions (Eh) and dissolved organic carbon, and also compared to distribution of major elements. Three main processes, responsible for the chemical variability, were identified: (1) the concentration of the solution under the influence of evaporation and the associated precipitations (Mg-calcite, illite, sodium carbonate); (2) oxidation of sulphides included in clay layers and subsequent development of acid conditions and (3) buffering of acid conditions by clay dissolution. Arsenic contents are not affected by the last two processes (2 and 3), but evolve in proportion to the concentration. Arsenic concentrations in water ranged from 0.11 μg/l to 3.68 mg/l, i.e., 368 times higher than the World Health Organization guidelines for drinking water. The As speciation, as calculated from field conditions, indicated that the As(V) redox state dominated in the groundwater and in the lakes, whereas some proportion of As(III) could occur on the shore and in the sediments of the saline lake. Arsenic(III) from the sediment can be remobilized and dispersed into the water following the disturbance of the sediments by cattle that come to drink water. Arsenic contents increased with most of the other dissolved species; hence, competitive adsorption prevents dissolved As regulation by solid phase reaction. Moreover, the pH values increased above 8 with increasing As, favouring As(V) desorption. As a consequence, the good correlation established between As contents and electrical conductivity (r2 = 0.97) should help to indirectly evaluate the As contents in shallow groundwater and lakes of the region.

Organic Control of Dioctahedral and Trioctahedral Clay Formation in an Alkaline Soil System in the Pantanal Wetland of Nhecolândia, Brazil.

Recent studies have focused on the formation of authigenic clays in an alkaline soil system surrounding lakes of the Nhecolândia region, Pantanal wetland. The presence of trioctahedral Mg-smectites (stevensite and saponite types), which requires low Al and Fe contents in the soil solution for its formation, contrasts with the neoformation of dioctahedral Fe-mica (glauconite, and Fe-illite), which instead requires solutions relatively enriched in Al and Fe. This study aims to understand the conditions of co-existence of both, Mg-smectite and Fe-mica a common clay association in former or modern alkaline soil systems and sediments. The study was carried out along an alkaline soil catena representative of the region. The soil organization revealed that Mg-smectite occur in top soil close to the lake, whereas Fe-mica dominate in the clay fraction of deeper greenish horizons a few meters apart. We propose here that this spatial distribution is controlled by the lateral transfer of Fe and Al with organic ligands. Alkaline organic rich solutions (DOC up to 738 mg L-1) collected in the watertable were centrifuged and filtered through membranes of decreasing pore size (0.45 μm, 0.2 μm, 30 KDa, 10 KDa, 3 KDa) to separate colloidal and dissolved fractions. Fe, Al, Si, Mg and K were analysed for each fraction. Although the filtration had no influence on Si and K contents, almost 90% of Fe (up to 2.3 mg L-1) and Al (up to 7 mg L-1) are retained at the first cutoff threshold of 0.45μm. The treatment of the same solutions by oxygen peroxide before filtration shows that a large proportion of Fe and Al were bonded to organic colloids in alkaline soil solution at the immediate lake border, allowing Mg-smectite precipitation. The fast mineralization of the organic matter a few meters apart from the lake favors the release of Fe and Al necessary for Fe-mica neoformation. In comparison with chemical and mineralogical characteristics of alkaline environments described in the literature, the study suggests that the co-existence of trioctahedral Mg-smectite and dioctahedral Fe-mica should be regarded as a standard occurrence in alkaline soil systems with organic rich waters.

Impacts of Lithological and Anthropogenic Factors Affecting Water Chemistry in the Upper Paraguay River Basin

Located in the Upper Paraguay River Basin (UPRB), the Pantanal is considered the worlds largest wetland, being rather pristine although increasingly threatened by development programs. The main objective of this paper is to provide a baseline of water chemistry for this region, which is largely unknown as a result of poor accessibility. We used two datasets (70 and 122 water samples) collected in the Pantanal floodplain and surrounding uplands during the wet season occurring from November to March. From the major-ion mineral chemistry, dissolved silica, pH, electrical conductivity (EC), and the ionic forms of N, principal components analysis (PCA) treatments were used to identify and rank the main factors of variability and decipher the associated processes affecting the water chemistry. The results revealed that the water mineral concentration was a major factor of variability and it must be attributed first to lithology and second to agricultural inputs from extensive crop cultivation areas that mainly affects sulfate (SO) concentration on the eastern edge of the Pantanal. These processes influence the floodplain, where (i) the mixing of waters remains the main process, (ii) the weight of the biological and redox processes increased, and (iii) the chemical signature of the extensive cropping is transferred along the São Lourenço Basin down to its confluence with the Cuiaba River. Optimized parameters based on projections in the main factorial score plots were used for the mapping of lithological and agricultural impacts on water chemistry.