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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
  2. Introduction

    Astarte borealisholds great potential as an archive of seasonal paleoclimate, especially due to its long lifespan (several decades to more than a century) and ubiquitous distribution across high northern latitudes. Furthermore, recent work demonstrates that the isotope geochemistry of the aragonite shell is a faithful proxy of environmental conditions. However, the exceedingly slow growth rates ofA. borealisin some locations (<0.2mm/year) make it difficult to achieve seasonal resolution using standard micromilling techniques for conventional stable isotope analysis. Moreover, oxygen isotope (δ18O) records from species inhabiting brackish environments are notoriously difficult to use as paleoclimate archives because of the simultaneous variation in temperature and δ18Owatervalues.

    Methods

    Here we use secondary ion mass spectrometry (SIMS) to microsample anA. borealisspecimen from the southern Baltic Sea, yielding 451 SIMS δ18Oshellvalues at sub-monthly resolution.

    Results

    SIMS δ18Oshellvalues exhibit a quasi-sinusoidal pattern with 24 local maxima and minima coinciding with 24 annual growth increments between March 1977 and the month before specimen collection in May 2001.

    Discussion

    Age-modeled SIMS δ18Oshellvalues correlate significantly with bothin situtemperature measured from shipborne CTD casts (r2 = 0.52, p<0.001) and sea surface temperature from the ORAS5-SST global reanalysis product for the Baltic Sea region (r2 = 0.42, p<0.001). We observe the strongest correlation between SIMS δ18Oshellvalues and salinity when both datasets are run through a 36-month LOWESS function (r2 = 0.71, p < 0.001). Similarly, we find that LOWESS-smoothed SIMS δ18Oshellvalues exhibit a moderate correlation with the LOWESS-smoothed North Atlantic Oscillation (NAO) Index (r2 = 0.46, p<0.001). Change point analysis supports that SIMS δ18Oshellvalues capture a well-documented regime shift in the NAO circa 1989. We hypothesize that the correlation between the SIMS δ18Oshelltime series and the NAO is enhanced by the latter’s influence on the regional covariance of water temperature and δ18Owatervalues on interannual and longer timescales in the Baltic Sea. These results showcase the potential for SIMS δ18Oshellvalues inA. borealisshells to provide robust paleoclimate information regarding hydroclimate variability from seasonal to decadal timescales.

     
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    Free, publicly-accessible full text available December 6, 2024
  3. Free, publicly-accessible full text available January 1, 2025
  4. Free, publicly-accessible full text available August 1, 2024
  5. Abstract Subannual climate reconstructions of the Holocene are rare despite the ability of such records to provide a better understanding of the underlying factors that drive subannual climate variability. We used specialized confocal laser fluorescent microscope imaging and automated secondary ion mass spectrometry microanalysis to resolve a seasonal oxygen isotope (δ18O) record of a late Holocene–aged (2.7–2.1 ka) speleothem from mid-continental North America. We did this by measuring intra-band δ18O variability (Δ18O) within 117 annual bands over a 600 yr span of the late Holocene. We interpret a change in Δ18O values after 2.4 ± 0.1 ka to reflect an increase in the amount of winter precipitation. Our study produced direct measurements of past seasonality, offers new insights into shifting seasonal precipitation patterns that occurred during the late Holocene in central North America, and adds a new tool for understanding the complex precipitation and temperature histories of this region. 
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