Field: Earth Science/Environment Session Topic: Primitive Earth and Atmosphere Speaker: Yuichiro Ueno/Tokyo Institute of Technology Stable Isotope Geochemistry of 3.5-Billion-Years-Old Seafloor Hydrothermal Deposits How to detect biological activities from ancient geological record is a difficult issue for investigation of the earliest evolution of Earth’s life. The record of prokaryotic microfossils dates back to ~3.5 billion years old (Shopf, 1993), however, biological origins of these “fossils” have been still debated (Buick 1990; Brasier et al., 2002). Moreover, morphology-based study of prokaryotic fossil provides only limited information for physiology of the ancient life. On the other hand, the ratios of stable carbon (12C/13C) and sulfur (32S/33S/34S/36S) isotopes between reactant and product are useful tracers for specific metabolic activities in the past. In principle, significant depletions of heavier (thus rarer) isotopes in reaction products could be expected under low temperature condition, in which chemical reactions are usually prohibited due to kinetic barrier. Hence, the large isotopic fractionations could be a good indicator for “catalysis” accelerating the low temperature reactions. This is a reason why stable isotope ratio could be a tracer for biological activities, though we have to ask then whether the inferred reactions were catalyzed by inorganic catalysts or by biological enzymes. In order to detect the ancient metabolic activities, we have conducted stable carbon and sulfur isotope geochemistry of the ~3.5-billion-years-old hydrothermal deposit occurring in Western Australia together with detailed field geology. Recent geological studies revealed that this deposit consists of hydrothermal sediments deposited in caldera of submarine basaltic volcano (Isozaki et al., 1997; Ueno et al., 2004; Van Kranendonk, 2006). Unique character of this deposit is the occurrence of prominent swarm of hydrothermal dykes, which are rocks precipitated in the past conduits of the hydrothermal fluid beneath the seafloor. Significant isotope depletions have been observed for several reduced forms of carbon and sulfur in the deposits: 1) 13C-depleted organic matter in seafloor sediments and sub-seafloor dykes (Ueno et al., 2001; 2004), 2) 13C-depleted methane preserved in the dyke (Ueno et al., 2006), and 3) 34S-depleted sulfide minerals in the seafloor sediment (Shen et al., 2001; Ueno et al., 2003). The observed large isotopic fractionations relative to co-existing oxidizing compounds could be expected from enzymatically catalyzed biological reactions: 1) autotrophic carbon fixation, 2) methanogenesis, and 3) sulfate reduction, respectively. Alternatively, these isotopically depleted compounds may have possibly been produced by non-biological reactions, for example, Fischer-Tropsch-type (FTT) reactions to produce CH4 and hydrocarbons, and thermochemical sulfate reduction to produce sulfide minerals (McCollom & Seewald, 2006; Runnegar et al., 2001). However, the lack of native metal (i.e., effective catalyst of FTT reactions) in the deposit and isotopic relationships among CH4, CO2, organic matter, and carbonate are inconsistent with the FTT origin of the methane and the organic matter. On the other hand, it is still ambiguous whether the 34S-depletion of the sulfide mineral was resulted from thermochemical or biological reactions. These results indicate that microbial ecosystem would have existed in the 3.5-billion-years-old hydrothermal system including sub-seafloor environment. The ecosystem included methanogen (methane-producing microbe), which would have gained energy through the conversion of CO2 and H2 into CH4. 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