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  • Elsevier  (3)
  • 2015-2019  (3)
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  • 1
    Publication Date: 2021-04-23
    Description: Constraints on the variability of chromium (Cr) isotopic compositions in the modern ocean are required to validate the use of Cr isotopic signatures in ancient authigenic marine sediments for reconstructing past levels of atmospheric and ocean oxygenation. This study presents dissolved Cr concentrations (Cr-T, where Cr-T = Cr(VI) + Cr(III)) and Cr isotope data (delta Cr-53) for shelf, slope and open ocean waters within the oxygen minimum zone (OMZ) of the eastern sub-tropical Atlantic Ocean. Although dissolved oxygen concentrations were as low as 44-90 mu mol kg(-1) in the core of the OMZ, there was no evidence for removal of Cr(VI). Nonetheless, there was significant variability in seawater delta Cr-53, with values ranging from 1.08 to 1.72 parts per thousand. Shelf Cr-T concentrations were slightly lower (2.21 +/- 0.07 nmol kg(-1)) than in open ocean waters at the same water depth (between 0 and 160 m, 2.48 +/- 0.07 nmol kg(-1)). The shelf waters also had higher delta Cr-53 values (1.41 +/- 0.14 parts per thousand compared to 1.18 +/- 0.05 parts per thousand for open ocean waters shallower than 160 m). This is consistent with partial reduction of Cr(VI) to Cr(III), with subsequent removal of isotopically light Cr(III) onto biogenic particles. We also provide evidence for input of relatively isotopically heavy Cr from sediments on the shelf. Intermediate and deep water masses (AAIW and NADW) show a rather limited range of delta Cr-53 values (1.19 +/- 0.09 parts per thousand) and inputs of Cr from remineralisation of organic material or re-oxidation of Cr (III) appear to be minimal. Authigenic marine precipitates deposited in deep water in the open ocean therefore have the potential to faithfully record seawater delta Cr-53, whereas archives of seawater delta Cr-53 derived from shelf sediments must be interpreted with caution.
    Type: Article , PeerReviewed
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  • 2
    Publication Date: 2020-02-06
    Description: Offshore western Svalbard plumes of gas bubbles rise from the seafloor at the landward limit of the gas hydrate stability zone (LLGHSZ; ∼400 m water depth). It is hypothesized that this methane may, in part, come from dissociation of gas hydrate in the underlying sediments in response to recent warming of ocean bottom waters. To evaluate the potential role of gas hydrate in the supply of methane to the shallow subsurface sediments, and the role of anaerobic oxidation in regulating methane fluxes across the sediment–seawater interface, we have characterised the chemical and isotopic compositions of the gases and sediment pore waters. The molecular and isotopic signatures of gas in the bubble plumes (C1/C2+ = 1 × 104; δ13C-CH4 = −55 to −51‰; δD-CH4 = −187 to −184‰) are similar to gas hydrate recovered from within sediments ∼30 km away from the LLGHSZ. Modelling of pore water sulphate profiles indicates that subsurface methane fluxes are largely at steady state in the vicinity of the LLGHSZ, providing no evidence for any recent change in methane supply due to gas hydrate dissociation. However, at greater water depths, within the GHSZ, there is some evidence that the supply of methane to the shallow sediments has recently increased, which is consistent with downslope retreat of the GHSZ due to bottom water warming although other explanations are possible. We estimate that the upward diffusive methane flux into shallow subsurface sediments close to the LLGHSZ is 30,550 mmol m−2 yr−1, but it is 〈20 mmol m−2 yr−1 in sediments further away from the seafloor bubble plumes. While anaerobic oxidation within the sediments prevents significant transport of dissolved methane into ocean bottom waters this amounts to less than 10% of the total methane flux (dissolved + gas) into the shallow subsurface sediments, most of which escapes AOM as it is transported in the gas phase.
    Type: Article , PeerReviewed
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  • 3
    Publication Date: 2021-04-23
    Description: Highlights • Evaluation of currently available marine pCO2 sensors with respect to in situ deployment potential. • In depth review of novel optode technology for pCO2. • A pCO2 optode was calibrated using modified time-domain dual lifetime referencing, over the range 280–480 μatm, with a precision of 0.8 μatm. Abstract The oceanic uptake of anthropogenic CO2 causes pronounced changes to the marine carbonate system. High quality pCO2 measurements with good temporal and spatial coverage are required to monitor the oceanic uptake, identify regions with pronounced carbonate system changes, and observe the effectiveness of CO2 emission mitigation strategies. There are currently several instruments available, but many are unsuitable for autonomous deployments on in situ platforms such as gliders, moorings and Argo floats. We assess currently available technology on its suitability for in situ deployment, with a focus on optode technology developments. Optodes for pCO2 measurements provide a promising new technological approach, and were successfully calibrated over the range of 280–480 μatm applying modified time-domain dual lifetime referencing. A laboratory precision of 0.8 μatm (n = 10) and a response time (τ90) of 165 s were achieved, and with further development pCO2 optodes may become as widely used as their oxygen counterparts.
    Type: Article , PeerReviewed
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