Spatial and seasonal variation of arsenic speciation in Pantanal soda lakes.

The occurrence of high arsenic concentrations (up to 3000 µg L-1) in water of soda lakes of the Pantanal wetland is a remarkable case of natural arsenic contamination in South America. However, little is known about arsenic speciation in this environment, particularly regarding speciation changes related to lake trophic status and seasonal variations. To fill this gap, arsenic speciation analysis was carried out in surface (SW) and subsurface (SSW) waters sampled in five soda lakes with different eutrophication status, in two dry and one wet season. As(V) was the dominant species in these waters, while As(III), DMA, MMA and likely complex organic species were present in lower amounts. The results allow to conclude that the arsenic speciation in SW and SSW varies seasonally according to the regional wet or dry periods and lake water levels. In eutrophic turbid and in oligotrophic vegetated soda lakes, arsenic speciation was also characterized by spatial differences between edge and center or between the SW and SSW. Cyanobacteria or macrophytes/algae are involved in arsenic biotransformation in soda lakes through its metabolic and detoxification processes. Significant variation in surface water arsenic speciation occurs as a result of seasonal primary production fluctuation or water arsenic concentration changes in the soda lakes, increasing organoarsenics in dry periods, whereas in flood periods, As(V) prevails. Spatial distribution of arsenic species is significantly impacted by biogeochemical conditions at the water/sediment interface in soda lakes.

In situ arsenic speciation at the soil/water interface of saline-alkaline lakes of the Pantanal, Brazil: A DGT-based approach.

Arsenic (As) is a naturally occurring element in the Earth's crust, exhibiting toxicity towards a wide range of living organisms. Its properties and environmental dynamics are strongly regulated by its speciation, and the species As(III) and As(V) are the most commonly found in environmental systems. Recently, high concentrations of As were found in saline-alkaline lakes of the Pantanal (Brazil), which is the largest wetland area in the world. Therefore, we evaluated As contamination and its redox speciation (As(III) and As(V)) at the soil/water interface of biogeochemically distinct saline-alkaline lakes of Pantanal wetlands (Brazil). Both conventional sampling and in situ diffusive gradients in thin films (DGT) technique were employed. Zirconium oxide and 3-mercaptopropyl were used as ligand phases in DGT to selectively bind As species. High concentrations of total dissolved As in a shallow water table were found (<2337.5 µg L-1), whereas levels in soils were up to 2.4 µg g-1. Distinct scenarios were observed when comparing speciation analysis through spot sampling and DGT. Considering spot sampling, As(V) was the main species detected, whereas As(III) was only detected in only a few samples (<4.2 µg L-1). Conversely, results obtained by DGT showed that labile As(III) dominated arsenic speciation at the soil/water interface with levels up to 203.0 µg L-1. Coupling DGT data and DGT induced fluxes in sediments and soils model allowed obtaining kinetic data, showing that the soil barely participated in the arsenic dynamics on the shore of the lakes, and that this participation depends on the evapoconcentration process occurring in the region. Therefore, soil acts like a nonreactive matrix depending on the natural concentration process. In addition, our results reinforced the different geochemical characteristics of the studied saline-alkaline lakes and highlights the importance of robust passive sampling techniques in the context of metal/metalloid speciation in environmental analysis.

Biogeochemical diversity, O2-supersaturation and hot moments of GHG emissions from shallow alkaline lakes in the Pantanal of Nhecolândia, Brazil.

Nhecolândia is a vast sub-region of the Pantanal wetland in Brazil with great diversity in surface water chemistry evolving in a sodic alkaline pathway under the influence of evaporation. In this region, >15,000 shallow lakes are likely to contribute an enormous quantity of greenhouse gas to the atmosphere, but the diversity of the biogeochemical scenarios and their variability in time and space is a major challenge to estimate the regional contribution. From 4 selected alkaline lakes, we compiled measurements of the physico-chemical characteristics of water and sediments, gas fluxes in floating chambers, and sedimentation rates to illustrate this diversity. Although these lakes have a similar chemical composition, the results confirm a difference between the black-water and green-water alkaline lakes, corresponding to distinct biogeochemical functioning. This difference does not appear to affect lake sedimentation rates, but is reflected in gas emissions. Black-water lakes are CO2 and CH4 sources, with fairly constant emissions throughout the seasons. Annual carbon dioxide and methane emissions approach 0.86molm-2y-1 and 0.07molm-2y-1, respectively, and no clear trend towards N2O capture or emission was observed. By contrast, green-water lakes are CO2 and N2O sinks but important CH4 sources with fluxes varying significantly throughout the seasons, depending on the magnitude of the phytoplankton bloom. The results highlight important daily and seasonal variations in gas fluxes, and in particular a hot moments for methane emissions, when the O2-supersaturation is reached during the afternoon under extreme bloom and sunny weather conditions, provoking an abrupt O2 purging of the lakes. Taking into account the seasonal variability, annual methane emissions are around 10.2molm-2y-1, i.e., much higher than reported in previous studies for alkaline lakes in Nhecolândia. Carbon dioxide and nitrous oxide consumption is estimated about 1.9molm-2y-1 and 0.73mmolm-2y-1, respectively. However, these balances must be better constrained with systematic and targeted measurements throughout the seasons.

Nonheterocytous cyanobacteria from Brazilian saline-alkaline lakes.

Saline-alkaline lakes are extreme environments that limit the establishment and development of life. The Nhecolândia, a subregion of the Pantanal wetland in Brazil, is characterized by the existence of ~500 saline-alkaline lakes, which support an underexplored and rich diversity of microorganisms. In this study, unicellular and homocytous cyanobacteria from five saline-alkaline lakes were accessed by culture-dependent approaches. Morphological evaluation and analyses of near complete sequences (~1400 nt) of the 16S rRNA genes were applied for phylogenetic and taxonomic placement. This polyphasic approach allowed for the determination of the taxonomic position of the isolated strains into the following genera: Cyanobacterium, Geminocystis, Phormidium, Leptolyngbya, Limnothrix, and Nodosilinea. In addition, fourteen Pseudanabaenales and Oscillatoriales representatives of putative novel taxa were found. These sequences fell into five new clades that could correspond to new generic units of the Pseudanabaenaceae and Phormidiaceae families.