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) ago. 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 CH(4), H(2), H(2)S, NH(3) and CO, whereas melts close to the fayalite-magnetite-quartz buffer would be similar to present-day conditions and would be dominated by H(2)O, CO(2), SO(2) and N(2) (refs 1-4). 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 5-8). 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 lavas 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.
Zircon structurally accommodates a range of trace impurities into its lattice, a feature which is used extensively to investigate the evolution of silicate magmas. One key compositional boundary of magmas is defined by whether the molar ratio of Al2O3/(CaO + Na2O + K2O) is larger or smaller than unity. Here we report ∼800 Al in zircon concentrations from 19 different rocks from the Lachlan Fold Belt (southeastern Australia), New England (USA), and Arunachal leucogranites (eastern Himalaya) with Al2O3/(CaO + Na2O + K2O) whole rock values that range from 0.88 to 1.6. Zircons from peraluminous rocks yield an average Al concentration of ∼10 ppm, which distinguishes them from crystals found in metaluminous rocks (∼1.3 ppm). This difference is related to the materials involved in the melting, assimilation, and/or magma differentiation processes; for example, magmas that assimilate Al‐rich material such as metapelites are expected to produce melts with elevated alumina activities, and thus zircons with high Al concentrations. These observations are applied to the Archean and Hadean Jack Hills detrital zircon record. Detrital Archean zircons, with ages from about 3.30 to 3.75 Ga, yield Al in zircon concentrations consistent with origins in peraluminous rocks in ∼8% of the cases (n = 236). A single zircon from the pre‐3.9 Ga age group (n = 39) contains elevated Al contents, which suggests that metaluminous crustal rocks were more common than peraluminous rocks in the Hadean. Weathered material assimilated into these Hadean source melts was not dominated by Al‐rich source material.
Quartz is one of the most common minerals on the surface of the earth, and is a primary rockforming mineral across the rock cycle. These two factors make quartz an obvious target for sediment provenance studies. Observations from experimental and natural samples demonstrate that the trace element content of quartz often reflects the conditions of quartz formation. When quartz is weathered from its primary crystallization setting (i.e., quartz from a granitoid) it can retain many chemical signatures of formation throughout the sedimentation processes. These geochemical signatures can be used to understand the primary source of individual quartz grains within a sediment. Here we present a case study from the Bega River catchment to demonstrate that quartz grains in sediments at the mouth of the Bega River are sourced from granitoids within the drainage basin. Data presented here also indicate that a portion of the beach sediment is also derived from either (i) sedimentary rocks within the basin or; (ii) mixing with sediments at the mouth of the river. The Bega River catchment was selected for this study because it is both small and has a wellconstrained bedrock lithology, making it an ideal location to test the utility of this provenance technique. However, quartz trace element provenance has broad applications to modern and ancient sediments and can be used in lieu of, or in conjunction with, other provenance techniques to elucidate sediment transport through time.
The potential for zircon to record continuous and evolving magmatic redox conditions is investigated by quantifying Ce valence in natural and synthetic crystals by X-ray Absorption Near Edge Structure (XANES). Valence was determined at high spatial resolution (2x4 μm) by analysis of the Ce L 3 edge for synthetic zircons and crystals from the Bishop Tuff Ig2E sequence; analyses included both core-to-rim and cross-sector measurements. Core-to-rim zonation among natural grains reveals a systematic increase in Ce 4+ /ΣCe, with core regions that range from ~0.4 to 0.6 Ce 4+ /ΣCe (i.e., ~40-60 % Ce 4+), while zircon rims range from ~0.7 to 1.0 Ce 4+ /ΣCe (i.e., ~70-100 % Ce 4+). Repeat analysis on an individual point suggest, on average, a Ce 4+ /ΣCe reproducibility at the 5% level or less. Changes in spectral features with grain orientation were also investigated by rotating and analyzing synthetic zircons every 45 o. This resulted in changes to the calculated Ce valence of <5%, which is much smaller than the range observed in natural samples. The core-to-rim increase in Ce 4+ /ΣCe of Bishop Tuff samples may indicate a continuous crystal-melt evolution to more oxidizing conditions prior to eruption, but this cannot be uniquely decoupled from other effects that may influence Ce valence in zircon, which potentially include temperature changes or kinetic processes related to the mineral growth surface. Cathodoluminescence imaging couples with XANES spectra for Bishop Tuff samples reveal that different sectors yield notably different Ce 4+ /ΣCe, implying anisotropic decoupling of Ce 3+ and Ce 4+ in the zircon nearsurface during crystallization. Broadly correlative (albeit with lower spatial resolution) Ti-thermometry and light rare earth element LA-ICP-MS data are also reported for zircon grains; there is no correlation between measured Ce anomalies and Ce 4+ /ΣCe. Cerium valence measurements of zircon may be able to constrain magma redox evolution with 3 time, without relying on the nearly ubiquitous low concentrations of La and Pr, which are classically used to calculate Ce anomalies.
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