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  • 1
    Publication Date: 2021-04-23
    Description: Dissolved iron (DFe) concentrations in oxygen minimum zones (OMZs) of Eastern Boundary Upwelling Systems are enhanced as a result of high supply rates from anoxic sediments. However, pronounced variations in DFe concentrations in anoxic coastal waters of the Peruvian OMZ indicate that there are factors in addition to dissolved oxygen concentrations (O2) that control Fe cycling. Our study demonstrates that sediment-derived reduced Fe (Fe(II)) forms the main DFe fraction in the anoxic/euxinic water column off Peru, which is responsible for DFe accumulations of up to 200 nmol L-1. Lowest DFe values were observed in anoxic shelf waters in the presence of nitrate and nitrite. This reflects oxidation of sediment-sourced Fe(II) associated with nitrate/nitrite reduction and subsequent removal as particulate Fe(III) oxyhydroxides. Unexpectedly, the highest DFe levels were observed in waters with elevated concentrations of hydrogen sulfide (up to 4 µmol L-1) and correspondingly depleted nitrate/nitrite concentrations (〈0.18 µmol L-1). Under these conditions, Fe removal was reduced through stabilization of Fe(II) as aqueous iron sulfide (FeSaqu) which comprises complexes (e.g., FeSH+) and clusters (e.g., Fe2S2|4H2O). Sulfidic events on the Peruvian shelf consequently enhance Fe availability, and may increase in frequency in future due to projected expansion and intensification of OMZs.
    Type: Article , PeerReviewed
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  • 2
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    American Chemical Society
    In:  Abstracts of Papers of the American Chemical Society, 245 . 173-GEOC.
    Publication Date: 2016-04-21
    Type: Article , NonPeerReviewed
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  • 3
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    American Chemical Society
    In:  Analytical Chemistry, 83 (16). pp. 6395-6400.
    Publication Date: 2016-04-25
    Description: Titanium (Ti) is present as a trace element in seawater at extremely low concentrations (5-350 pM, where 1 pM = 10(-12) mol L(-1)) throughout the water column. Presently, little is known about the marine biogeochemistry of Ti and there is a distinct lack of oceanic measurements of Ti, because of the combined difficulties of trace-metal clean sampling for an element at such low levels and the lack of a suitable shipboard method of analysis. Here, a new cathodic stripping voltammetry procedure is presented for the rapid determination of Ti at pM concentrations in seawater that is capable of being used directly at sea. This method utilizes the catalytic enhancement of the reduction of the complex formed between Cupferron (N-nitrosophenylhydroxylamine) and Ti(IV). While Cupferron itself acts as both a complexing agent and an oxidizing agent, it was found that the optimal sensitivity was with bromate as an auxiliary oxidant. An advantage of this method is that it is useable over the pH range of 5.5-8. Under the conditions employed in this work, detection limits ranged from 5 pM to 12 pM. This new catalytic method is significantly more sensitive than existing methods and has been extensively tested at sea in the Atlantic and Southern Oceans.
    Type: Article , PeerReviewed
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  • 4
    Publication Date: 2022-01-31
    Description: The marine iodine cycle has significant impacts on air quality and atmospheric chemistry. Specifically, the reaction of iodide with ozone in the top few micrometres of the surface ocean is an important sink for tropospheric ozone (a pollutant gas) and the dominant source of reactive iodine to the atmosphere. Sea surface iodide parameterisations are now being implemented in air quality models, but these are currently a major source of uncertainty. Relatively little observational data is available to estimate the global surface iodide concentrations, and this data has not hitherto been openly available in a collated, digital form. Here we present all available sea surface (〈20 m depth) iodide observations. The dataset includes values digitised from published manuscripts, published and unpublished data supplied directly by the originators, and data obtained from repositories. It contains 1342 data points, and spans latitudes from 70°S to 68°N, representing all major basins. The data may be used to model sea surface iodide concentrations or as a reference for future observations.
    Type: Article , PeerReviewed
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