Bioaccumulation and speciation of arsenic in plankton from tropical soda lakes along a salinity gradient.

Uptake and transformation of arsenic (As) by living organisms can alter its distribution and biogeochemical cycles in the environment. Although well known for its toxicity, several aspects of As accumulation and biological transformation by field species are still little explored. In this study, the bioaccumulation and speciation of As in phytoplankton and zooplankton from five soda lakes in the Brazilian Pantanal wetland were studied. Such lakes exhibited contrasting biogeochemical characteristics along an environmental gradient. Additionally, the influence of contrasting climatic events was assessed by collecting samples during an exceptional drought in 2017 and a flood in 2018. Total As (AsTot) content and speciation were determined using spectrometric techniques, while a suspect screening of organoarsenicals in plankton samples was carried out by high-resolution mass spectrometry. Results showed that AsTot content ranged from 16.9 to 62.0 mg kg-1 during the dry period and from 2.4 to 12.3 mg kg-1 during the wet period. The bioconcentration and bioaccumulation factors (BCF and BAF) in phytoplankton and zooplankton were found to be highly dependent on the lake typology, which is influenced by an ongoing evapoconcentration process in the region. Eutrophic and As-enriched lakes exhibited the lowest BCF and BAF values, possibly due to the formation of non-labile As complexes with organic matter or limited uptake of As by plankton caused by high salinity stress. The season played a decisive role in the results, as significantly higher BCF and BAF values were observed during the flooding event when the concentration of dissolved As in water was low. The diversity of As species was found to be dependent on the lake typology and on the resident biological community, cyanobacteria being responsible for a significant portion of As metabolism. Arsenosugars and their degradation products were detected in both phytoplankton and zooplankton, providing evidence for previously reported detoxification pathways. Although no biomagnification pattern was observed, the diet seemed to be an important exposure pathway for zooplankton.

In situ fractionation and redox speciation of arsenic in soda lakes of Nhecolândia (Pantanal, Brazil) using the diffusive gradients in thin films (DGT) technique.

In situ fractionation and redox speciation of As in three different saline-alkaline lakes (green, black and crystalline lakes) in the Pantanal of Nhecolândia (Brazil) were performed by using Diffusive Gradients in Thin films (DGT). The results indicated that As is present mainly in dissolved form. Total As concentration was similar when using different filter membranes, demonstrating that the species adsorbed by DGT devices were <10 kDa. Higher concentrations of labile total As were observed in the center of the lakes, indicating that the nature of the organic matter influences the formation of As complexes. Total As concentrations determined by using ZrO2 DGT were consistent with As concentration in ultrafiltered water samples collected in the black lake. However, part of the data about As(III) obtained in grab samples contrasted with DGT results. The differences observed may indicate that alterations in the species occur during the storage period before analysis by ultrafiltration. As(III) concentrations measured by DGT in the black and crystalline lakes were 1-3 µg L-1 and 4-7 µg L-1, respectively, accounting for only 4%-8% of the total DGT inorganic As. In the green lake, As(III) concentrations were significantly higher at the center (217 µg L-1). Both the phytoplankton community and the dissolved organic carbon influence the As speciation and bioavailability in the lakes of Nhecolândia. The DGT approach used in the present work was able to perform As speciation and demonstrates that in situ sampling analytical techniques are essential in understanding As speciation and its behavior in complex natural aquatic systems.

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.

Dissolved arsenic in the upper Paraguay River basin and Pantanal wetlands.

Although high levels of dissolved arsenic were detected in surface and ground waters of Nhecolândia, a sub-region of the vast Pantanal wetlands in Brazil, the possible sources have not been clearly identified and the potential release from the wetland to the draining rivers has not been investigated. In this study we measured the dissolved As content in all the rivers and small streams that supply the southern Pantanal region, as well as in the two main rivers draining the wetland, i.e., the Cuiaba and Paraguay rivers and tributaries. In addition, Arsenic in surface waters, perched water-table, soils and sediments from 3 experimental sites located in the heart of Nhecolândia were compared. On the one hand, the results show the absence of As contamination in rivers that supply the Pantanal floodplain, as well as a lack of significant release from the floodplain to the main drains. The As contents in the rivers are <2 µg L-1, with variations that depend on the lithology and on the geomorphology at the collection point (uplands or floodplain). On the other hand, they confirm the regional extension of As contamination in Nhecolândia's alkaline waters with some values above 3 mg L-1. Arsenic is mainly in the arsenate form, and increases with the evaporation process estimated from sodium ion concentrations. The pH of soil solution and surface water increases rapidly during evapo-concentration up to values above 9 or 10, preventing adsorption processes on oxides and clay minerals and promoting the retention of dissolved arsenic in solution. Solutions from organic soil horizons show higher As contents in relation to Na, attributed to the formation of ternary complex As-(Fe/Al)-OM. In this alkaline pH range, despite high levels of dissolved As, soil horizons and lake sediments in contact with these waters show As values that correspond to uncontaminated environments.