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Abstract Understanding the interaction between molybdenum (Mo) and organic matter during microbial sulfate reduction is critical for the use of Mo to reconstruct marine redox conditions throughout Earth's history. However, little is known about Mo isotope fractionation and how it relates to organic matter remineralization during microbial sulfate reduction. Here, we report Mo abundances and isotopic (δ98Mo) compositions for bulk‐rock, non‐lithogenic and sequentially extracted fractions, including carbonate (carb), pyrite, and organic matter (OM), of seep carbonate rocks. Our data indicate that the difference between δ98Mocarb and δ98MoOM (Δ98Mocarb‐OM) displays significant variability in the studied samples, ranging between 0.72 and 1.01‰. Remarkably, the obtained Δ98Mocarb‐OM values indicate correlative trends with stable carbon isotope ratios and bulk abundances of (a) total organic carbon, (b) Mo, and (c) pyrite in seep carbonates, which we interpret as reflecting sustained adsorption of isotopically light Mo onto organic matter during enhanced sulfate reduction. On this basis, we put forward the concept that Δ98Mocarb‐OM of authigenic carbonate rocks can be used as a measure of the intensity of sulfate reduction and for reconstructing past interactions between Mo and organic matter in marine sediments.

Abstract Authigenic molybdenum (Moauth) in marine sediments holds great potential to archive the Mo isotopic composition of seawater and biogeochemical processes. However, the factors that control authigenic Mo isotope (δ98Moauth) distribution patterns remain poorly constrained. Here, we report Mo abundances and δ98Mo compositions for bulk‐rock (bulk) and sequentially extracted fractions—including total authigenic (auth; i.e., non‐lithogenic fraction), carbonate (carb), iron and manganese oxyhydroxides, pyrite (py), and organic fractions (OM)—of authigenic carbonates recovered from various hydrocarbon seep sites in the Gulf of Mexico and the South China Sea. Extracted pyrite fractions exhibit Mo contents varying from 0.1 to 23.4 μg/g and generally dominate the Mo budget of seep carbonate rocks. Our data indicate large ranges of δ98Mobulk and δ98Moauth values relative to NIST 3134 (0.25‰), varying from 1.02 to 1.98‰ (n = 4) and from 0.15 to 3.07‰ (n = 34), respectively. The difference in δ98Mo values between carbonate and pyrite fractions of seep carbonate rocks formed under sulfidic conditions increases with higher Moauth contents, suggesting a control of dissolved hydrogen sulfide concentrations on Mo isotope fractionation during carbonate precipitation. Compared with δ98Moauth and δ98Mopy, δ98Mocarb of seep carbonate rocks formed under sulfidic conditions shows a relatively narrow range with an average of 1.98 ± 0.31‰ (1 SD; n = 10), providing constraints on the δ98Mo composition of seawater in the course of Earth history. Overall, our findings show that the δ98Mo composition of sequentially extracted phases of carbonate‐rich sedimentary rocks can provide insights into seawater‐sediment interactions and biogeochemical pathways of Mo during early diagenesis.

Authigenic carbonates that form at hydrocarbon seeps, known as seep carbonates, are direct records of past fluid flow close to the seafloor. Stable carbon isotopes of seep carbonates (δ13Ccarb) have been widely used as a proxy for determining fluid sources and seepage mode. Although the spatial heterogeneity of δ13C in seep carbonates is increasingly understood, the temporal heterogeneity of δ13C in seep carbonates is not well studied. In this study, we report δ13C values of different components (clasts, matrix, and pore-filling cements) for 124 subsamples drilled across an authigenic carbonate block from Green Canyon block 140 (GC140) of the northern Gulf of Mexico continental slope. High-Mg calcite is the dominant mineral regardless the types of components. The δ13Ccarb values range from −39.6‰ to 3.6‰, indicating multiple dissolved inorganic carbon (DIC) sources that include methane carbon (13C-depleted), seawater DIC, and residual CO2 from methanogenesis (13C-enriched). Specifically, the clasts show large variability in δ13C values (−39.6‰ to 2.3‰; mean: −27.6‰, n = 71), demonstrating the dominance of methane-derived fluids during formation at the initial seepage stage. The δ13C values of the matrix vary between −29.4‰ and 3.4‰ (mean: −11.6‰, n = 21). The carbon isotopes of pore-filling cements that formed most recently vary narrowly, with δ13C values of −3.2‰ to 3.6‰ (mean: 1.7‰, n = 28). Isotopic variations within individual samples were observed in seep carbonate. However, common trends occur across components of carbonates that formed during different seepage stages. This suggests that the temporal evolution of local fluid sources may play an important role in determining carbonate isotope geochemistry. Studies regarding seeps must take into account the highly variable fluids that leave their geochemical imprints on the seep carbonate.