S- and O-isotopic character of dissolved sulphate in the cover rock aquifers of a Zechstein salt dome

Sulfur and O isotope analyses of dissolved SO4 were used to constrain a hydrogeological model for the area overlying the Gorleben-Rambow Salt Structure, Northern Germany. Samples were collected from 80 wells screened at different depth-intervals. The study area consists of a set of two vertically stacked aquifer systems. Generally, the isotope data show a good spatial correlation, outlining well-defined groundwater zones containing SO4 of characteristic isotopic composition. Highly saline waters from deeper parts of the lower aquifer system are characterized by rather constant SO4 isotopic compositions, which are typical of Permian Zechstein evaporites (δ34S=9.6-11.9 per mille; δ18O=9.5-12.1 per mille). Above this is a transition zone containing ground waters of intermediate salinity and slightly higher isotopic values (average δ34S=16.6 per mille; δ18O=15.3 per mille). The confined groundwater horizon on the top of the lower aquifer system below the low permeable Hamburg Clays is low in total dissolved solids and is characterized by an extreme 34S enrichment (average δ34S=39.1 per mille; δ18O=18.4 per mille), suggesting that bacterially mediated SO4 reduction is a dominant geochemical process in this zone. Two areas of distinct isotopic composition can be identified in the shallow ground water horizons of the upper hydrogeological system. Sulfate in groundwaters adjacent to the river Elbe and Loecknitz has a typical meteoric isotopic signature (δ34S=5.2 per mille; δ18O=8.2 per mille), whereas the central part of the area is characterized by more elevated isotopic ratios (δ34S=12.7 per mille; δ18O=15.6 per mille). The two major SO4 pools in the area are represented by Permian seawater SO4 and a SO4 of meteoric origin that has been mixed with SO4 resulting from the oxidation of pyrite. It is suggested that the S-isotope compositions observed reflect the nature of the SO4 source that have been modified to various extent by bacterial SO4 reduction. Groundwaters with transitional salinity have resulted from mixing between brines and low-mineralized waters affected by bacterial SO4 reduction