Item talk:Q251714

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   "abstract": "Superoxide radical (O2\u2212) has been proposed to be an important participant in oxidation\u2212reduction reactions of metal ions in natural waters. Here, we studied the reaction of nanomolar Mn(II) with O2\u2212\u00a0in seawater and simulated freshwater, using chemiluminescence detection of O2\u2212\u00a0to quantify the effect of Mn(II) on the decay kinetics of O2\u2212. With 3\u221224 nM added [Mn(II)] and <0.7 nM [O2\u2212], we observed effective second-order rate constants for the reaction of Mn(II) with O2\u2212\u00a0of 6 \u00d7 106\u00a0to 1 \u00d7 107\u00a0M\u22121\u00b7s\u22121\u00a0in various seawater samples. In simulated freshwater (pH 8.6), the effective rate constant of Mn(II) reaction with O2\u2212\u00a0was somewhat lower, 1.6 \u00d7 106\u00a0M\u22121\u00b7s\u22121. With higher initial [O2\u2212], in excess of added [Mn(II)], catalytic decay of O2\u2212\u00a0by Mn was observed, implying that a Mn(II/III) redox cycle occurred. Our results show that reactions with nanomolar Mn(II) could be an important sink of O2\u2212\u00a0in natural waters. In addition, reaction of Mn(II) with superoxide could maintain a significant fraction of dissolved Mn in the +III oxidation state.",
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