Carbon diagenesis in dolomite- and calcite-bearing limnic sediments: A multi-phase stable isotope geochemical perspective on Lake Constance

Placed in a carbonate-rich catchment at the northern foot of the Alps, Lake Constance is one of the largest lakes in Central Europe, and the hard water lake chemistry makes it a natural laboratory to investigate in detail the carbonate formation, preservation, and the interactions with the detrital carbonate fraction, the latter with a major dolomite component. The highly reactive lacustrine carbonates are great paleoenvironment archives - due to the climate sensitivity in their formation either as erosional sources of suspended matter or through lake internal processes; still, they are prone to diagenetic overprints that shall be considered in a major context. For that, the (post-)glacial sediment deposits were investigated up to 24 m long cores recovered from the northernmost deep portions of Lake Constance, at approximately 200 mwd. The benthic carbon cycle and mineral sources and (trans)formations, were investigated through porewaters and sedimentary solid phases analyses for stable isotope signatures (CHOS), and major- and trace element compositions. The water isotope signatures display a trend towards lighter data with depth, indicating the development in the lake water composition with time, superimposed by diffusion processes in the sediments. The dissolved inorganic carbon (DIC) concentrations increase below the sediment-water interface and are generally higher in the postglacial sediments, indicating that mineralization rates followed the enhancement of lake productivity under milder climate conditions. The δ13C-DIC shows the lightest values in the glacial sediments and displays an enrichment in Holocene sediments, together with pore water hydrochemistry, indicative of organic matter (OM) oxidation, carbonate dissolution, and potential involvement of methane. The sulfur isotope record indicates that minor dissimilatory sulfate reduction is involved in OM degradation. Bulk carbonate C and O isotope signatures show strong variations partly induced by non-authigenic dolomite. Vertical variations in the composition of porewaters, bulk, and acid-soluble phases, in combination with SEM investigations, allow insights about the (trans)formation of authigenic mineral phases and the destruction of allochthonous carbonates, as possible modifiers of the sedimentary record.