Tracing sulfate recycling in the hypersaline Pétrola Lake (SE Spain): A combined isotopic and microbiological approach

Sulfur (S) plays a significant role in saline environments, and sulfate (SO42 -) is an important component of the biogeochemical S-cycle since it acts as the main electron acceptor in anoxic sediments. The purpose of this paper is to evaluate the fate of S, its origin, and processes affecting sulfate outcome in the hypersaline Pétrola Lake in the Castilla-La Mancha region (High Segura Basin, SE Spain). The lake is the terminal discharge zone of an endorheic basin with considerable anthropogenic pressures. Anthropogenic activities (mainly agricultural inputs and wastewater discharge), together with bedrock leaching of sulfate and sulfide-rich sediments, increase dissolved SO42 - in surface and groundwater up to 123,000 mg/L. The source and fate of sulfate in this environment was investigated coupling hydrochemistry, including hydrogen sulfide (H2S) microprofiles, isotopic analyses (d34S, d18OSO4, d2HH2O, d18OH2O, and tritium), mineralogical determinations, and molecular biology tools (16S rDNA amplification and sequencing). The origin of dissolved SO42 - in water is related to pyrite oxidation from Lower Cretaceous sediments, and secondary gypsum dissolution. Under the lake, dissolved SO42 - decreases with depth, controlled by three main processes: (1) seasonal evaporation cycles, (2) hydrodynamic instability caused by the different density-driven groundwater flow, and (3) sulfate-reduction processes, i.e. dissimilatory bacterial sulfate reduction (BSR). These processes control the continuous recycling of sulfur in the system. Lake water and groundwater are in hydraulic connection, and a density-driven flow (DDF) is able to transport reactive organic matter and dissolved SO42 - towards the underlying aquifer. Hydrochemical evolution in depth, H2S production (up to 0.024 nmol/cm3·s) and the presence of sulfate-reducing bacteria suggest the existence of BSR processes. However, isotope techniques are insufficient to elucidate BSR processes since their isotopic effect is masked by low isotope fractionation and high SO42 - concentrations. The pattern here described may be found in other saline basins worldwide.