Hermoso Michael

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Hermoso
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Michael
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  • Preprint
    Constraints on the vital effect in coccolithophore and dinoflagellate calcite by oxygen isotopic modification of seawater
    ( 2014-05) Hermoso, Michael ; Horner, Tristan J. ; Minoletti, Fabrice ; Rickaby, Rosalind E. M.
    In this study, we show that there are independent controls of 18O/16O and 13C/12C fractionation in coccolithophore and dinoflagellate calcite due to the contrasting kinetics of each isotope system. We demonstrate that the direction and magnitude of the oxygen isotope fractionation with respect to equilibrium is related to the balance between calcification rate and the replenishment of the internal pool of dissolved inorganic carbon (DIC). As such, in fast growing cells, such as those of Emiliania huxleyi and Gephyrocapsa oceanica (forming the so-called “heavy group”), calcification of the internal carbon pool occurs faster than complete isotopic re-adjustment of the internal DIC pool with H2O molecules. Hence, coccoliths reflect the heavy oxygen isotope signature of the CO2 overprinting the whole DIC pool. Conversely, in large and slow growing cells, such as Coccolithus pelagicus ssp. braarudii, complete re-equilibration is achieved due to limited influx of CO2 leading to coccoliths that are precipitated in conditions close to isotopic equilibrium (“equilibrium group”). Species exhibiting the most negative oxygen isotope composition, such as Calcidiscus leptoporus (“light group”), precipitate coccolith under increased pH in the coccolith vesicle, as previously documented by the “carbonate ion effect”. We suggest that, for the carbon isotope system, any observed deviation from isotopic equilibrium is only “apparent”, as the carbon isotopic composition in coccolith calcite is controlled by a Rayleigh fractionation originating from preferential incorporation of 12C into organic matter. Therefore, species with low PIC/POC ratios as E. huxleyi and G. oceanica are shifted towards positive carbon isotope values as a result of predominant carbon fixation into the organic matter. By contrast, cells with higher PIC/POC as C. braarudii and C. leptoporus maintain, to some extent, the original negative isotopic composition of the CO2. The calcareous dinoflagellate Thoracosphaera heimii exhibits different behaviour for both isotopic systems, in particular with respect to its very negative carbon isotope composition, owing to coeval intra and extracellular biomineralisation in this group. In this study, we also investigate the sensitivity of 18O/16O fractionation to varying ambient oxygen isotope composition of the medium for inorganic, coccolithophore, and dinoflagellate calcite precipitated under controlled laboratory conditions. The varying responses of different taxa to increased oxygen isotope composition of the growth medium may point to a potential bias in sea surface temperature reconstructions that are based on the oxygen isotopic compositions of sedimentary calcite, especially during times of changing seawater oxygen isotopic composition. Overall, this study represent an important step towards establishing a mechanistic understanding of the “vital effect” in coccolith and dinoflagellate calcite, and provides valuable information for interpreting the geochemistry of the calcareous nannofossils in the sedimentary record, at both monospecific and interspecies levels.
  • Article
    Diatom silicon isotopes as a proxy for silicic acid utilisation : a Southern Ocean core top calibration
    (Elsevier, 2012-08-11) Egan, Katherine E. ; Rickaby, Rosalind E. M. ; Leng, Melanie J. ; Hendry, Katharine R. ; Hermoso, Michael ; Sloane, Hilary J. ; Bostock, Helen ; Halliday, Alex N.
    Despite a growing body of work that uses diatom δ30Si to reconstruct past changes in silicic acid utilisation, few studies have focused on calibrating core top data with modern oceanographic conditions. In this study, a microfiltration technique is used to divide Southern Ocean core top silica into narrow size ranges, separating components such as radiolaria, sponge spicules and clay minerals from diatoms. Silicon isotope analysis of these components demonstrates that inclusion of small amounts of non-diatom material can significantly offset the measured from the true diatom δ30Si. Once the correct size fraction is selected (generally 2–20 μm), diatom δ30Si shows a strong negative correlation with surface water silicic acid concentration (R2 = 0.92), highly supportive of the qualitative use of diatom δ30Si as a proxy for silicic acid utilisation. The core top diatom δ30Si matches well with mixed layer filtered diatom δ30Si from published in situ studies, suggesting little to no effect of either dissolution on export through the water column, or early diagenesis, on diatom δ30Si in sediments from the Southern Ocean. However, the core top diatom δ30Si shows a poor fit to simple Rayleigh or steady state models of the Southern Ocean when a single source term is used. The data can instead be described by these models only when variations in the initial conditions of upwelled silicic acid concentration and δ30Si are taken into account, a caveat which may introduce some error into quantitative reconstructions of past silicic acid utilisation from diatom δ30Si.