Hydrogeochemical models locating sulfate-methane transition zone in marine sediments overlying black shales: A new tool to locate biogenic methane?

• Organic matter conversion and sedimentation rate important in barite cycling.
• Barite peaks in sediments serve as indicators for underlying organic-rich layers.
• Geochemical modeling is important to decipher diagenetic reactions.

Precise hydrogeochemical modeling of early diagenesis is a key in the reconstruction of sedimentary basin models. This determines the mineralogical evolution of the sediment and consequently the porosity of the rock. During early diagenesis also part of the initial organic matter is converted into biogenic gas: CH4 CO2, and H2S. These processes are part of complex reaction chains during sedimentation, and biogeochemical reactions leave different signals that can be observed today. In this work, we reproduce the early diagenetic processes as integrated signals over geological times in sediments of the Demerara Rise by applying chemical thermodynamics using the PHREEQC (version 2) computer code. The investigated sediments are characterized by the presence of black shales in 410–490 mbsf and by a diagenetic barite layer above in 300–350 mbsf at depth of sulfate-methane transition (SMT). We determine the parameters that influence the location of diagenetic barite peaks in sediments overlying black shales by means of a novel modeling approach. Crucial parameters are the amount of bacterial organic matter mineralization, sedimentation rates and bottom water sulfate concentrations. All parameters are intertwining and influence the sulfate-methane cycle. They affect the location of the SMT visualized by diagenetic barite peaks. However, our model approach opens a wide field in exploring early diagenetic reactions, processes and products (such as biogenic methane) over geological times mirrored by diagenetic minerals and pore water concentration profiles that can be detected in present-day sediments.