Constraining oxygen levels in the early Precambrian surface ocean has been a longstanding goal, but efforts have been challenged by the availability of suitable proxies. Here we present a novel approach, iodine geochemistry, which broadens our perspective by providing constraints on shallow, carbonate-dominated marine settings. Iodate (IO3 -) persists exclusively in oxic waters and is the sole iodine species incorporated into carbonate minerals, allowing iodine-to-calcium ratios (I/Ca) in shallow carbonates to be used as a paleoredox indicator. Our data from a series of Mesoarchean through Paleoproterozoic carbonates deposited under shallow-marine conditions reveal a progressive surface ocean oxygenation in the early Paleoproterozoic. These data seem to indicate that a largely anoxic surface ocean extended throughout the Archean until the Great Oxidation Event (GOE) at ca. 2.4 Ga, implying that previous inferences of pre-GOE oxygen production may refl ect oxygen oases, transient oxidation events, or oxygen levels below those required for IO3- accumulation. The data suggest formation and persistence of IO3- and, consequently, surface ocean oxygen concentrations of at least 1 μM during the GOE. Following the initial rise of oxygen, carbonate-associated iodine in globally extensive carbonate units deposited during the Lomagundi positive carbon isotope excursion at ca. 2.22-2.1 Ga suggests a widespread aerobic iodine cycle beyond that operating prior to the event, synchronous with high relative rates of organic carbon burial and apparent expansion of oxidative conditions.
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