Geochemical and stable isotopic evolution of the Guarani Aquifer System in the state of São Paulo, Brazil

The purpose of this report is to explain geochemical and stable isotopes trends in the Brazilian unit of the Guarani Aquifer System (Botucatu and Piramboia aquifers) in S?o Paulo State, Brazil. Trends of dissolved species concentrations and geochemical modeling indicated a significant role of cation exchange and dissolution of carbonates in downgradient evolution of groundwater chemistry. Loss of calcium by the exchange for sodium drives dissolution of carbonates and results in Na–HCO₃ type of groundwater. The cation-exchange front moves downgradient at probably much slower rate compared to the velocity of groundwater flow and at present is located near to the cities of Sert?ozinho and águas de Santa Barbara (wells PZ-34 and PZ-148, respectively) in a shallow confined area, 50–70 km from the recharge zone. Part of the sodium probably enters the Guarani Aquifer System. together with chloride and sulfate from the underlying Piramboia Formation by diffusion related to the dissolution of evaporates like halite and gypsum. High concentrations of fluorine (up to 13.3 mg/L) can be explained by dissolution of mineral fluoride also driven by cation exchange. However, it is unclear if the dissolution takes place directly in the Guarani Aquifer System or in the overlying basaltic Serra Geral Formation. There is depletion in δ ²H and δ ¹⁸O values in groundwater downgradient. Values of δ ¹³C(DIC) are enriched downgradient, indicating dissolution of calcite under closed system conditions. Values of δ ¹³C(DIC) in deep geothermal wells are very high (>–6.0‰) and probably indicate isotopic exchange with carbonates with δ ¹³C about –3.0‰. Future work should be based on evaluation of vertical fluxes and potential for penetration of contamination to the Guarani Aquifer System. Electronic Publication