Carbonate precipitation is a major process in the global carbon cycle. It was recently proposed that authigenic carbonate (carbonate precipitated in situ at the sediment–water interface and/or within the sediment) played a major role in the carbon cycle throughout Earth’s history. The carbon isotopic composition of authigenic carbonates in ancient oceans have been assumed to be significantly lower than that of dissolved inorganic carbon (DIC) in seawater, as is observed in the modern oceans. However, the δ13Ccarb values of authigenic carbonates in the past has not been analyzed in detail. Here, we report authigenic carbonates in the uppermost Guadalupian (Middle Permian) rocks at Chaotian, Sichuan, South China. Monocrystalline calcite crystals <20 mm long are common in the black mudstone/chert sequence that was deposited on a relatively deep anoxic slope/basin along the continental margin. Textures of the crystals indicate in situ precipitation on the seafloor and/or within the sediments. The calcite precipitation corresponds stratigraphically with denitrification and sulfate reduction in the anoxic deep-water mass, as indicated by previously reported nitrogen and sulfur isotope records, respectively. Relatively high δ13Ccarb values of the authigenic carbonates (largely −1 ‰) compared with those of organic matter in the rocks (ca. −26 ‰) suggest that the main carbon source of the carbonates was DIC in the water column. The calcite crystals precipitated in an open system with respect to carbonate, possibly near the sediment–water interface rather than deep within the sediments. The δ13Ccarb values of the carbonates were close to the δ13CDIC value of seawater due to mixing of 13C-depleted remineralized organic carbon (that was released into the water column by the water-mass anaerobic respiration) with the large DIC pool in the oceans. Our results imply that δ13Ccarb values of authigenic carbonates in the anoxic oceans might have been systematically different from the values in the oxic oceans in Earth’s history, controlled by the depth of the redoxcline in the water column and sediments. If our model is correct, authigenic carbonates with relatively high δ13Ccarb values in the ancient anoxic oceans may have had a less substantial influence on the bulk δ13Ccarb values in geologic records than has been previously suggested.
To understand the chemical nature of hydrothermal fluids in the komatiite-hosted seafloor hydrothermal system in the Hadean, we conducted two hydrothermal serpentinization experiments involving synthetic komatiite and a CO2-rich acidic NaCl fluid at 250 and 350 °C, 500 bars. During the experiments, the komatiites were strongly carbonated to yield iron-rich dolomite (3–9 wt.% FeO) at 250 °C and calcite (<0.8 wt.% FeO) at 350 °C, respectively. The carbonation of komatiites suppressed H2 generation in the fluids. The steady-state H2 concentrations in the fluid were approximately 0.024 and 2.9 mmol/kg at 250 and 350 °C, respectively. This correlation between the Fe content in carbonate mineral and the H2 concentration in the fluid suggests that the incorporation of ferrous iron into the carbonate mineral probably limited magnetite formation and consequent generation of hydrogen during the serpentinization of komatiites. The H2 concentration of the fluid at 350 °C corresponds to that of modern H2-rich seafloor hydrothermal systems, such as the Kairei hydrothermal field, where hydrogenotrophic methanogens dominate in the prosperous microbial ecosystem. Accordingly, the high-temperature serpentinization of komatiite would provide the H2-rich hydrothermal environments that were necessary for the emergence and early evolution of life in the Hadean ocean. In contrast, H2-rich fluids may not have been generated by serpentinization at temperatures below 250 °C because carbonate minerals become more stable with decreasing temperature in the komatiite-H2O-CO2 system.
Abstract In order to establish kinetic expressions for Raman spectroscopic parameters of organic matter in chondritic meteorites with heating, a series of heating experiments (at 600–900 °C for 3–48 h) of the Murchison (CM2) meteorite was conducted. For comparison, several carbonaceous chondrites with various metamorphic degrees—Allende (CV3.2), Moss (CO3.6), Yamato (Y‐) 793321 (heated CM2), and Tagish Lake (ungrouped C2)—were also analyzed by the Raman spectrometer. Changes in the full width at half maximum of the D1 band (Γ D ) of heated Murchison correlated well with temperature and time, and showed similar trends of chondrites with various metamorphic degrees. We obtained the kinetic expressions for the changes in Γ D by heating to estimate the time–temperature history of thermally metamorphosed type 3 chondrites and heated CM chondrites. Our results may also be useful for asteroids which are the targets of Hayabusa2 and OSIRIS‐REx missions.
