Photosynthesis and microbial sulfate reduction are the two key biogeochemical processes which control the global carbon cycle in Earth history. While geochemical signatures of these metabolisms are ambiguous in carbonate rocks, the emergence of carbonate dual clumped isotope (Δ47 and Δ48) can shed on whether biogeochemical processes are sensitive to the kinetic isotope effects induced by microbial metabolism and hence identify these in the geological record. Here we applied dual clumped isotopes to decipher, photosynthesis and microbial sulfate reduction during the formation of the lacustrine carbonates in the western part of Qaidam Basin. This bioherm skeleton is comprised of low-Mg calcites and coated by isopachous dolomite cement. After a chemical separation leached by buffered-acetic acid, the skeletal low-Mg calcites have the positive disequilibrium of Δ48 values than the expected, but the Δ48 values of dolomite cements show the negative disequilibrium. The positive Δ48-disequilibrium of the skeletal low-Mg calcites is probably attributed to the photosynthesis which can remove CO2 from the surrounding water and, resultantly, enhance pH and saturation state. In contrast, the isopachous dolomite cement may be a product microbial sulfate reduction which was suggested to induce the disequilibrium as a result of CO2 hydration/hydroxylation (Lu et al., 2025; Lu and Swart, 2024). This study highlights the importance of kinetic isotope effects in deciphering geochemical signals of modern and ancient carbonate rocks.
Reference:
Lu, C., Moore, M. E., and Swart, P. K., 2025, Dual clumped isotopes reveal an out-of-equilibrium state in shallow-water carbonate sediments on Great Bahama Bank: Earth and Planetary Science Letters, v. 658, p. 119322.
Lu, C., and Swart, P. K., 2024, The application of dual clumped isotope thermometer (Δ
47 and Δ
48) to the understanding of dolomite formation: Geology, v. 52, no. 1, p. 56-60.