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The oxidation state of Hadean magmas and implications for early Earth’s atmosphere


Magmatic outgassing of volatiles from Earth’s interior probably played a critical part in determining the composition of the earliest atmosphere, more than 4,000 million years (Myr) ago1. Given an elemental inventory of hydrogen, carbon, nitrogen, oxygen and sulphur, the identity of molecular species in gaseous volcanic emanations depends critically on the pressure (fugacity) of oxygen. Reduced melts having oxygen fugacities close to that defined by the iron–wüstite buffer would yield volatile species such as CH4, H2, H2S, NH3 and CO, whereas melts close to the fayalite–magnetite–quartz buffer would be similar to present-day conditions and would be dominated by H2O, CO2, SO2 and N2 (refs 14). Direct constraints on the oxidation state of terrestrial magmas before 3,850 Myr before present (that is, the Hadean eon) are tenuous because the rock record is sparse or absent. Samples from this earliest period of Earth’s history are limited to igneous detrital zircons that pre-date the known rock record, with ages approaching 4,400 Myr (refs 58). Here we report a redox-sensitive calibration to determine the oxidation state of Hadean magmatic melts that is based on the incorporation of cerium into zircon crystals. We find that the melts have average oxygen fugacities that are consistent with an oxidation state defined by the fayalite–magnetite–quartz buffer, similar to present-day conditions. Moreover, selected Hadean zircons (having chemical characteristics consistent with crystallization specifically from mantle-derived melts) suggest oxygen fugacities similar to those of Archaean and present-day mantle-derived lavas2,3,4,9,10 as early as 4,350 Myr before present. These results suggest that outgassing of Earth’s interior later than 200 Myr into the history of Solar System formation would not have resulted in a reducing atmosphere.

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Figure 1: Experimental calibration, relating melt oxygen fugacity to zircon Ce anomalies and temperature.
Figure 2: Oxygen fugacity and oxygen isotope plots for natural samples using the experimental calibration.
Figure 3: Oxygen fugacities of Hadean melts plotted against zircon crystallization age.


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This work was supported by the NASA Astrobiology Institute (grant no. NNA09DA80A to The New York Center for Astrobiology).

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Authors and Affiliations



E.B.W. identified the importance of investigating redox sensitive elements in zircon. D.T. designed the experiments and took measurements. D.T. wrote the manuscript and interpreted the data with significant contributions from E.B.W. and N.D.T.

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Correspondence to Dustin Trail.

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Supplementary information

Supplementary Figures

This file contains Supplementary Figure 1 and legend. (PDF 170 kb)

Supplementary Tables

This file contains Supplementary Tables 1-5 comprising: 1) Starting oxide compositions for experiments; 2) Glass compositions analyzed by electron microprobe for Experiments; 3) Zircon compositions analyzed by electron microprobe for experiments; 4) Calculated zircon-melt partition coefficients using the data in Tables 3 and 4 and 5) Compiled literature data used to construct Figures 2 and 3. (XLS 121 kb)

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Trail, D., Watson, E. & Tailby, N. The oxidation state of Hadean magmas and implications for early Earth’s atmosphere. Nature 480, 79–82 (2011).

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