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  • 1
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    American Chemistry Society
    In:  Environmental Science & Technology, 47 (18). pp. 10249-10256.
    Publication Date: 2019-09-23
    Description: Superoxide (O2-: IUPAC name dioxide (•1−)) is an important transient reactive oxygen species (ROS) in the ocean formed as an intermediate in the redox transformation of oxygen (O2) into hydrogen peroxide (H2O2) and vice versa. This highly reactive and very short-lived radical anion can be produced both via photochemical and biological processes in the ocean. In this paper we examine the decomposition rate of O2- throughout the water column, using new data collected in the Eastern Tropical North Atlantic (ETNA) Ocean. For this approach we applied a semi factorial experimental design, to identify and quantify the pathways of the major identified sinks in the ocean. In this work we occupied 6 stations, 2 on the West African continental shelf and 4 open ocean stations, including the CVOO time series site adjacent to Cape Verde. Our results indicate that in the surface ocean, impacted by Saharan aerosols and sediment resuspension, the main decay pathways for superoxide is via reactions with Mn(II) and organic matter.
    Type: Article , PeerReviewed
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  • 2
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    American Chemistry Society
    In:  Environmental Science & Technology, 47 (18). pp. 10257-10265.
    Publication Date: 2019-09-23
    Description: Manganese (Mn) is a required element for oceanic phytoplankton as it plays a critical role in photosynthesis, through its unique redox chemistry, as the active site in photosystem II and in enzymes that act as defences against reactive oxygen species (ROS), most notably for protection against superoxide (O2-), through the action of superoxide dismutase (SOD), and against hydrogen peroxide (H2O2) via peroxidases and catalases. The distribution and redox speciation of Mn in the ocean is also apparently controlled by reactions with ROS. Here we examine the connections between ROS and dissolved Mn species in the upper ocean using field and laboratory experimental data. Our results suggest it is unlikely that significant concentrations of Mn(III) are produced in the euphotic zone, as in the absence of evidence for the existence of strong Mn(III) ligands, Mn(II) reacts with O2- to form the short lived transient manganous superoxide, MnO2+, which may react rapidly with other redox species in a similar manner to O2-. Experiments with the strong Mn(III) chelator, desferrioxamine B (DFB), in seawater indicated that the Mn(III) species is unlikely to form, as the pre-cursor Mn(II) complex under natural ambient conditions due to the high side reaction of DFB with Ca.
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