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Serpentinization plays an important role in fluid and mass transfer between the ocean, the crust, and the mantle, in biogeochemical processes, and CO2 sequestration within oceanic and continental settings. The physical-chemical conditions of serpentinization, such as temperature and fluid source, are often investigated using oxygen isotopes. However, the ability to precisely constrain such parameters is limited by the accuracy of calibrations for oxygen isotope fractionation between serpentine and water – i.e. 1000 lnα(Srp-w) – which disagree by up to 20‰ when extrapolated to T < 200 °C [1-5]. In this study, we present a new empirical calibration of 1000 lnα(Srp-w) aiming to improve applications of oxygen isotope thermometry to very low-T serpentinization (T < 100 °C). We used the high-spatial resolution capabilities of Secondary Ion Mass Spectrometry (SIMS) to analyze oxygen isotope ratios in mineral pairs of calcite+serpentine, quartz+serpentine and talc+serpentine co-crystallized at scales ≤ 50 μm in six serpentinite samples from the Samail ophiolite (Oman). SIMS analysis shows that the mineral pairs are relatively homogeneous in oxygen isotope ratios with variability in δ18O values ≤ 2‰ (2s). Clumped isotope thermometry and petrological constraints indicate crystallization temperatures from ~20 to 90 °C for the investigated samples [6,7]. These independent constraints on temperature allowed us to derive 1000 lnα(Srp-w) by combining mineral-serpentine oxygen isotope fractionations measured by SIMS with published mineral-water oxygen isotope fractionations. Our empirical calibration of 1000 lnα(Srp-w) = 1.12±0.42 × 106/T2 (T in K), from T = 20 to 90 °C, is within uncertainty of former high-temperature empirical calibrations [1,4] extrapolated to T < 100 °C. The new 1000 lnα(Srp-w) calibration enables more accurate reconstructions of fluid-rock interactions occurring during low-temperature serpentinization processes in various tectonic settings.

Oxygen isotope ratios were measured in zircon by laser fluorination and by SIMS from in over 50 silicic (dacite–rhyolite) volcanic rocks of Triassic to Cretaceous (230-98 Ma) age from the Sierra Nevada batholith, White-Inyo Mountains, and Mojave Desert. These data give broad geographic and temporal context of volcanism in the Mesozoic California arcs system that was previously unobtainable because of secondary hydrothermal exchange that routinely alters original magmatic δ18O values in these rocks (c.f., Sorensen et al. GSAB 1998). SIMS analysis of δ18O using 10 µm spot size, augmented by U-Pb dating by LA-ICP-MS, further allows appraisal of variability within zircon grains and grain populations as potential evidence of assimilation or magma mixing within caldera systems, including mixing during eruptions. Values of δ18O(zircon) in most rocks studied are 5.0–7.5‰, and overlap with values of δ18O in plutonic rocks (6.80±1.85‰, S.D., Lackey et al. 2005,2006,2008,2012). A subset of Late Jurassic (152-148 Ma) tuffs distributed from the Mojave Desert to Mt. Goddard pendant that contain zircons whose δ18O values commonly are

第4回極域科学シンポジウム個別セッション：[OA] 南極隕石11月14日（木） 国立国語研究所 ２階 講堂

Spatiotemporal variability in the carbon isotope composition of sedimentary organic matter (OM) preserves information about the evolution of the biosphere and of the exogenic carbon cycle as a whole. Primary compositions, and imprints of the post-depositional processes that obscure them, exist at the scale of individual sedimentary grains (mm to μm). Secondary ion mass spectrometry (SIMS) (1) enables analysis at these scales and in petrographic context, (2) permits morphological and compositional characterization of the analyte and associated minerals prior to isotopic analysis, and (3) reveals patterns of variability homogenized by bulk techniques. Here we present new methods for in situ organic carbon isotope analysis with sub-permil precision and spatial resolution to 1 μm using SIMS, as well as new data acquired from a suite of Archean rocks. Three analytical protocols were developed for the CAMECA ims1280 at WiscSIMS to analyze domains of varying size and carbon concentration. Average reproducibility (at 2SD) using a 6 μm spot size with two Faraday cup detectors was 0.4‰, and 0.8‰ for analyses using 1 μm and 3 μm spot sizes with a Faraday cup (for 12C) and an electron multiplier (for 13C). Eight coals, two ambers, a shungite, and a graphite were evaluated for μm-scale isotopic heterogeneity, and LCNN anthracite (δ13C = -23.56 ± 0.1‰, 2SD) was chosen as the working standard. Correlation between instrumental bias and H/C was observed and calibrated for each analytical session using organic materials with H/C between 0.1 and 1.5 (atomic), allowing a correction based upon a 13CH/13C measurement included in every analysis and a 12CH measurement made immediately after every analysis. The total range of the H/C effect observed for the Archean samples analyzed was < 3‰. Analyses of Archean OM domains for which 12C count rate varies with the proportions of organic carbon, carbonate carbon, and quartz suggest that instrumental bias is consistent for 12C count rates as low as 10% relative to anthracite. Samples from the ABDP-9 (n=3; Mount McRae Shale, ~2.5 Ga), RHDH2a (n=2; Carrawine Dolomite and Jeerinah Fm, ~2.6 Ga), WRL1 (n=3; Wittenoom Fm, Marra Mamba Iron Formation, and Jeerinah Fm, ~2.6 Ga), and SV1 (n=1; Tumbiana Fm, ~2.7 Ga) drill cores, each previously analyzed for bulk organic carbon isotope composition, yielded 100 new, in situ data from Neoarchean sedimentary OM. In these samples, δ13C varies between -53.1 and -28.3‰ and offsets between in situ and bulk compositions range from -8.3 to 18.8‰. In some cases, isotopic composition and mode of occurrence (e.g. morphology and mineral associations) are statistically correlated, enabling the identification of distinct reservoirs of OM. Our results support previous evidence for aerobiosis and depth gradients of oxidation in Neoarchean environments driven by photosynthesis and methane metabolism. The relevance of these findings to questions of bio- and syngenicity as well as the alteration history of this OM and similar, previously reported Archean OM will be discussed.

Stable isotopic compositions of biologically important elements (e.g., C and S) in sedimentary rocks are valuable biosignatures to the extent that they indicate the presence and variable expression of microbial metabolisms in space and time. Strong interactions between the carbon and sulfur cycles (e.g., via organic matter remineralization during microbial sulfate reduction) make coordinated, in situ C and S isotope analysis by secondary ion mass spectrometry (SIMS) a particularly powerful tool. In rocks ranging in age from 2.7-2.5 Ga, expansions in the ranges of delta C-13 of organic matter and delta S-34 of pyrite likely reflect the increasing influence of oxygenic photosynthesis in the surface ocean (as well as methane and sulfur metabolisms in deeper waters), whereas the large range of mass independent sulfur isotope fractionation (Delta S-33) suggests that the atmosphere remained anoxic until approx 2.4 Gyr ago. We report in situ delta C-13 measurements of organic matter in the approx 2.7-2.6 Ga Carawine Dolomite, Marra Mamba Iron Formation, and Jeerinah, Wittenoom, and Tumbiana Formations, as well as the approx 2.5 Ga Mount McRae Shale. We also report in situ delta S-24 and Delta S-33 measurements of pyrite associated with organic matter in a subset of these samples. In a single square cm sample of the Tumbiana Formation with bulk delta C-13(sub org) of -49.7% (VPDB), two distinct kerogen types have delta C-13 values, measured in situ, consistent with oxygenic photosynthesis (-33%) and methane metabolism (-52%). In a sample from the ABDP-9 core, radiobitumen associated with a uraniferous mineral grain is C-13-enriched by 8% (-26.8%0) relative to average in situ kerogen (-34.9%0) and similar in delta C-13 to solvent extractable hydrocarbons from the Mount McRae Shale (avg delta C-13 = -27.1 %). Average reproducibility for delta C-13 was 0.4% (2 SD) using a 6 micron spot and 0.8% using a 3 micron spot. In situ sulfur isotope analyses of 33 authigenic pyrite grains in 3 samples of the ABDP-9 core using a 10 micron spot (2 SD reproducibility = 0.4% for delta S-34 and -0.1% for Delta S-33) show a range of 28.1 % in delta S-34 (-10.3 to 17.8%) and 13.3%0 in Delta S-33 (-3.8 to 9.5%), whereas the range from 132 bulk analyses across 84 m of core is 19.4% for delta S-34 and 11.5% for Delta S-33. Coordinated, in situ carbon and sulfur isotope analyses in one ABDP-9 sample are shown. In situ values from this kerogen-pyrite association are within 0.1% of the bulk value in the case of delta C-13 and higher by several permil in the case of delta S-34 and Delta S-33. Coordinated in situ carbon and sulfur isotope analyses in rocks deposited during key intervals of environmental change (e.g., the Great Oxidation Event) can refine our understanding of the mode and tempo of change. In Earth's oldest sedimentary rocks, and in extraterrestrial samples, these coordinated in situ analyses may reveal biosignatures in the form of isotopic correlations at the scale of individual microorganisms and their microhabitats.

Exchange of oxygen isotopes encrypts a sensitive record of the thermal evolution and fluid-exchange history of igneous and metamorphic rocks. Deciphering this record requires measurement of isotope ratios at an appropriate scale together with understanding of the processes involved: diffusion, recrystallization, new mineral growth, and fluid flow.