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  1. Abstract

    Detrital zircons from the Jack Hills are the dominant source of Hadean (pre-4000 Ma) terrestrial material available for study today. Values of δ18O in many of these zircons (6.0 to 7.5‰ are above the mantle-equilibrated value. For two decades, these mildly elevated values have been the primary evidence that protoliths of the zircon-forming magmas interacted at low temperature with liquid water before burial and melting, implying that the surface of Earth cooled quickly after core and moon formation, and that habitable conditions for life existed within 250 Myr of the formation of Earth, over 800 Myr before the oldest generally accepted microfossils. These conclusions are based on oxygen isotope analyses of zircon domains with well-defined growth zoning and nearly concordant U-Pb ages within zircon grains with low magnetic susceptibility, which are further inferred to be unaltered by various tests. However, no studies of Jack Hills zircons have directly correlated oxygen isotope ratios and radiation damage, which facilitates alteration in zircon. Several previous studies have selected zircons that show radiation damaged, discordant and/or hydrous domains, and have shown that such altered material is not reliable as a record of igneous composition. In contrast, this study targeted zircons that are interpreted to pristine and not altered, and demonstrates the importance of testing zircons for radiation damage and alteration as part of any geochemical study, regardless of age. This study expands on existing data, and presents the first comprehensive evaluation of δ18O, OH/O, CL imaging, U-Pb concordance and radiation-damage state within Jack Hills zircons. A total of 115 Hadean zircon grains in this study have water contents similar to nominally anhydrous standard reference zircons and are interpreted as pristine. In situ Raman data for band broadening correlated with δ18O analyses document low levels of radiation damage, indicating significant annealing. The present-day effective doses (Deff) are uniformly less than the first percolation point (dose where damage domains, that are isolated at lower damage state, overlap to form a continuous pathway through the crystal, ~2×1015 α-decays/mg, Ewing et al., 2003) and most zircons have Deff<1×1015 α-decays/mg. Modeling of representative alpha-recoil damage and annealing histories indicates that most zircons in this study have remained below the Deff of the first percolation point throughout their history. The δ18O values for these primary zircons include many that are higher than would be equilibrated with the mantle at magmatic temperatures and average 6.32 ± 1.3‰ in the Hadean and 6.26 ± 1.6‰ in the Archean. There is no correlation in our suite of pristine Hadean zircons between δ18O and OH/O, Deff, age, or U-Pb age-concordance. These carefully documented Hadean-age zircons possess low amounts of radiation damage in domains sampled by δ18O analysis, are water-poor. The mildly elevated δ18O values are a primary-magmatic geochemical signature. These results strengthen the conclusion that mildly elevated-δ18O magmas existed during the Hadean, supporting the hypothesis that oceans and a habitable Earth existed before 4300 Ma.

     
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    Free, publicly-accessible full text available March 28, 2025
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  4. Abstract Rationale

    The use of secondary ion mass spectrometry (SIMS) to perform micrometer‐scalein situcarbon isotope (δ13C) analyses of shells of marine microfossils called planktic foraminifers holds promise to explore calcification and ecological processes. The potential of this technique, however, cannot be realized without comparison to traditional whole‐shell δ13C values measured by gas source mass spectrometry (GSMS).

    Methods

    Paired SIMS and GSMS δ13C values measured from final chamber fragments of the same shell of the planktic foraminiferOrbulina universaare compared. The SIMS–GSMS δ13C differences (Δ13CSIMS‐GSMS) were determined via paired analysis of hydrogen peroxide‐cleaned fragments of modern cultured specimens and of fossil specimens from deep‐sea sediments that were either untreated, sonicated, and cleaned with hydrogen peroxide or vacuum roasted. After treatment, fragments were analyzed by a CAMECA IMS 1280 SIMS instrument and either a ThermoScientific MAT‐253 or a Fisons Optima isotope ratio mass spectrometer (GSMS).

    Results

    Paired analyses of cleaned fragments of cultured specimens (n = 7) yield no SIMS–GSMS δ13C difference. However, paired analyses of untreated (n = 18) and cleaned (n = 12) fragments of fossil shells yield average Δ13CSIMS‐GSMSvalues of 0.8‰ and 0.6‰ (±0.2‰, 2 SE), respectively, while vacuum roasting of fossil shell fragments (n = 11) removes the SIMS–GSMS δ13C difference.

    Conclusions

    The noted Δ13CSIMS‐GSMSvalues are most likely due to matrix effects causing sample–standard mismatch for SIMS analyses but may also be a combination of other factors such as SIMS measurement of chemically bound water. The volume of material analyzed via SIMS is ~105times smaller than that analyzed by GSMS; hence, the extent to which these Δ13CSIMS‐GSMSvalues represent differences in analyte or instrument factors remains unclear.

     
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