Post-depositional evolution over a time scale of 1 million years of eastern Mediterranean organic-rich and organic-poor sediments: new insights on the debromination and layer-silicate markers

Organic matter degradation is the engine behind the biogeochemical evolution of sediments during burial. Previous research has shown that eogenesis is the seat of a complex interplay between organic matter, microbes and the most reactive part of inorganic compounds, such as clay minerals. To explore the variability and stability of bromine and clay minerals as geochemical and mineral tracers, we selected an eastern Mediterranean core that has a high degree of stability in the quality and quantity of organic matter through time at a one-million-year scale and great variability in organic matter content at a 10 ky scale. According to the very low maximal burial depth reached by these sediments (the core length is only 36.5 m), physical parameters, such as temperature and pressure, did not significantly influence the evolution of the studied parameters during the burial history. The bulk clay mineralogy of organic-rich and organic-poor sediments is similar all along the investigated core material; smectite predominates over kaolinite. The only identified authigenic minerals are biogenetic framboidal pyrite and manganese oxides. The X-ray data and the chemical compositions of the smectite are characteristic of a montmorillonite which is representative of a detrital Nile source. At a one-million-year scale, the organic matter content has no significant influence on clay eogenesis, and detrital smectite and kaolinite remain unchanged. Bromine is present in marine organic matter as organobromine compounds. During eogenesis, bromine is released from organic matter as bromide ion, resulting in an increase in the bromide concentration in the pore water with depth. Dissolved bromide can be used as a conservative tracer of the debromination of sedimentary organic matter. For the first time, we established that solid-phase BrOrg is a reliable tracer of debromination rates in marine sediments. The rate of debromination depends on the organic matter content. The rate increases from less than 2.3 × 10−4 μmolBrOrg mol.C−1.y−1 to 6.3 × 10−4 μmolBrOrg mol.C−1.y−1 when TOC varies from 0.17 to 3%. This increase is related to the development of the bacterial population and provides the basis for further investigation of other oceanic basins. For TOC values  >4%, the rate of debromination decreases. We propose that the bioavailability of organic matter is another factor of variability in the debromination rate.