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Published August 22, 2017 | Published + Supplemental Material
Journal Article Open

Redox variations in Mauna Kea lavas, the oxygen fugacity of the Hawaiian plume, and the role of volcanic gases in Earth's oxygenation


The behavior of C, H, and S in the solid Earth depends on their oxidation states, which are related to oxygen fugacity (fO_2). Volcanic degassing is a source of these elements to Earth's surface; therefore, variations in mantle fO_2 may influence the fO2 at Earth's surface. However, degassing can impact magmatic fO_2 before or during eruption, potentially obscuring relationships between the fO_2 of the solid Earth and of emitted gases and their impact on surface fO_2. We show that low-pressure degassing resulted in reduction of the fO_2 of Mauna Kea magmas by more than an order of magnitude. The least degassed magmas from Mauna Kea are more oxidized than midocean ridge basalt (MORB) magmas, suggesting that the upper mantle sources of Hawaiian magmas have higher fO_2 than MORB sources. One explanation for this difference is recycling of material from the oxidized surface to the deep mantle, which is then returned to the surface as a component of buoyant plumes. It has been proposed that a decreasing pressure of volcanic eruptions led to the oxygenation of the atmosphere. Extension of our findings via modeling of degassing trends suggests that a decrease in eruption pressure would not produce this effect. If degassing of basalts were responsible for the rise in oxygen, it requires that Archean magmas had at least two orders of magnitude lower fO_2 than modern magmas. Estimates of fO_2 of Archean magmas are not this low, arguing for alternative explanations for the oxygenation of the atmosphere.

Additional Information

© 2017 National Academy of Sciences. Edited by Donald J. DePaolo, Lawrence Berkeley National Laboratory, Berkeley, CA, and approved July 7, 2017 (received for review November 28, 2016). Published online before print August 7, 2017. We thank A. Lanzirotti and M. Newville for assistance in beamline operations at Advanced Photon Source Argonne National Laboratory (APS ANL). We thank Woody Fisher and Oliver Shorttle for commenting on early versions of this manuscript. This research used resources of APS, a US Department of Energy (DOE) Office of Science user facility operated for the DOE Office of Science by ANL under Contract DE-AC02-06CH11357. We thank the Department of Mineral Sciences, Smithsonian Institute, for access to sample NMNH 117393. Author contributions: M.B., E.S., and J.E. designed research; M.B. performed research; M.B. contributed new reagents/analytic tools; M.B., E.S., and J.E. analyzed data; and M.B., E.S., and J.E. wrote the paper. The authors declare no conflict of interest. This article is a PNAS Direct Submission. This article contains supporting information online at www.pnas.org/lookup/suppl/doi:10.1073/pnas.1619527114/-/DCSupplemental.

Attached Files

Published - PNAS-2017-Brounce-8997-9002.pdf

Supplemental Material - pnas.1619527114.sapp.pdf

Supplemental Material - pnas.1619527114.sd01.xlsx


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August 22, 2023
October 17, 2023