Excess of sulfate and dissolved inorganic carbon in groundwaters fueled by pyrite oxidation and organic matter loads – A multi-isotope approach

The biogeochemistry of sulfur and carbon in groundwater of a Quaternary porous aquifer system and associated surface (lake) waters was investigated to identify processes of water mixing and the sources of dissolved sulfate and dissolved inorganic carbon (DIC). The study area is situated in North-Eastern Germany (Mecklenburg-Western Pomerania) close to the Baltic Sea coastline. The area is under impact by agricultural activity on a regional scale. A major goal was to identify the natural and anthropogenic key hydrobiogeochemical processes controlling the coupled element cycles upon groundwater development. Besides major and minor elements, redox-sensitive trace elements, nutrients, and stable mulit-isotope signatures (H, C, O, S) were considered.

While water isotopes of most groundwaters are positioned on the meteoric water line, surface waters are affected by an evaporation-induced enrichment of heavy isotopes. These shifts allow for a quantification of mixing proportions in influenced groundwater wells between direct precipitation-derived groundwater and  infiltrating lake water born fractions.

Major element hydrochemical and the carbon isotope composition of DIC indicate soil CO₂ and the subterrestrial dissolution of carbonate minerals within the aquifer matrix as primary sources for DIC. Furthermore, contributions from oxidized dissolved organic carbon (DOC) under water-saturated conditions are found.

The coupled sulfur and oxygen isotope composition of dissolved sulfate indicates an origin dominatly  from the subterrestrial oxidation of iron sulfides, mainly pyrite. These iron sulfides are found in the sediments making the modern porous aquifer, in the study area with a deduced sulfur isotope composition of about -12 per mil vs. VCDT. These findings coupled to enhanced loads in dissolved iron and manganese, but low nutrient concentrations indicate nitrate as an important driver for lithoautothrophic pyrite oxidation. At several sites, the enhanced sulfate loads led to dissimilatory sulfate reduction and, thereby, to in-situ transformation of DOC (and/or Methane) to DIC. The enhancements of sulfate and DIC seems to be a typical feature in North German younger groundwaters and strongly (in)directly impacted by anthropogenic forces.