4.8 Article

Neoproterozoic to early Phanerozoic rise in island arc redox state due to deep ocean oxygenation and increased marine sulfate levels

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NATL ACAD SCIENCES
DOI: 10.1073/pnas.1821847116

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Earth history; island arcs; ocean oxygenation; oxygen fugacity; subduction

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A rise in atmospheric O-2 levels between 800 and 400 Ma is thought to have oxygenated the deep oceans, ushered in modern biogeochemical cycles, and led to the diversification of animals. Over the same time interval, marine sulfate concentrations are also thought to have increased to near-modern levels. We present compiled data that indicate Phanerozoic island arc igneous rocks are more oxidized (Fe3+/Sigma Fe ratios are elevated by 0.12) vs. Precambrian equivalents. We propose this elevation is due to increases in deep-ocean O-2 and marine sulfate concentrations between 800 and 400 Ma, which oxidized oceanic crust on the seafloor. Once sub-ducted, this material oxidized the subarc mantle, increasing the redox state of island arc parental melts, and thus igneous island arc rocks. We test this using independently compiled V/Sc ratios, which are also an igneous oxybarometer. Average V/Sc ratios of Phanerozoic island arc rocks are elevated (by + 1.1) compared with Precambrian equivalents, consistent with our proposal for an increase in the redox state of the subarc mantle between 800 and 400 Ma based on Fe3+/Sigma Fe ratios. This work provides evidence that the more oxidized nature of island arc vs. midocean-ridge basalts is related to the subduction of material oxidized at the Earth's surface to the subarc mantle. It also indicates that the rise of atmospheric O-2 and marine sulfate to near-modern levels by the late Paleozoic influenced not only surface biogeochemical cycles and animal diversification but also influenced the redox state of island arc rocks, which are building blocks of continental crust.

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