Volume 9

Abstract:
Understanding the distribution of halogens in rocks can potentially trace ancient lithosphere, hydrosphere, and atmosphere interactions. Although no sedimentary rocks older than 3.8 Ga are known, insights into sediment-atmosphere exchange on early Earth could be obtained from knowledge of halogen contents in ancient zircons. Here we present the first study of halogen abundances in Jack Hills zircons together with younger zircons of known provenance to provide geologic context. The relatively low (ca. 0.1-0.6 μg/g) chlorine concentrations in most Hadean and Archean Jack Hills zircons are similar to the average concentration in younger igneous zircons. In contrast, significant Cl enrichments are found in a subset of ca. 3.9–3.8 Ga zircons ([Cl]_average= 1.43 ± 0.27 μg/g) that appear to record halogen transport under hydrothermal conditions. Such Cl-bearing fluids in early Earth history may reflect extraction of halogens from the interior to near surface environments.

Abstract:
Reconstructing a record of the partial pressure of molecular oxygen in Earth’s atmosphere is key for understanding macroevolutionary and environmental change over geological history. Recently, the oxidation state of iron in micrometeorites has been taken to imply the presence of modern Earth concentrations of oxygen in the upper atmosphere at 2.7 Ga, and therefore a highly chemically stratified atmosphere (Tomkins et al., 2016). We here explore the possibility that the mixing ratio of oxygen in Earth’s upper atmosphere, that probed by micrometeorites, may instead be sensitive to the surface atmospheric pressure. We find that the concentrations of oxygen in the upper atmosphere required for micrometeorite oxidation are achieved for a 0.3 bar atmosphere. In this case, significant water vapour reaches high up in the atmosphere and is photodissociated, leading to the formation of molecular oxygen. The presence of oxidised iron in micrometeorites at 2.7 Ga may therefore be further evidence that the atmospheric pressure at the surface of the early Earth was substantially lower than it is today.

Abstract:
The primordial He budget of the Earth’s interior is commonly thought to have been set by full liquid metal-silicate equilibration in a terrestrial magma ocean. However, incomplete metal-silicate equilibration during accretion will have a substantial effect on this budget. Here we present liquid-solid partitioning experiments indicating that He behaves as a moderately siderophile element during percolative core formation in planetesimals. Mass balance considerations show that even minor disequilibrium will allow the Earth’s early core to incorporate sufficient primordial He—and possibly other noble gases—to supply the lower mantle throughout Earth’s history. We conclude that the high ³He/⁴He ratios in basalts may well represent primarily the last vestiges of metal-silicate disequilibrium in a terrestrial magma ocean preserved from the time of Earth’s formation.

Abstract:
Scandium is the subject of increasing interest and is even becoming critical for a number of institutions in Europe and the U.S.A. among others because of its economic value and supply risk. Despite this growing awareness, little is known about its geochemical behaviour. Recent studies have shown that Sc can be strongly associated with iron oxides including goethite but the mode of interaction is not yet fully understood. We investigated the incorporation of Sc in goethite structure in controlled batch systems. For the first time, we show the formation of a solid αFeOOH-αScOOH solution consistent with an ideal solution despite significant differences in atomic radii between Sc³⁺ and Fe³⁺. We believe that beyond this fundamental knowledge concerning the affinity of Sc for goethite, these results provide important insights into Sc speciation in primary or secondary sources, including Sc-rich lateritic deposits and bauxite residues after alumina extraction, for the future design of extraction processes with a low environmental footprint, as an alternative to current energy-intensive technologies.

Abstract:
The origin of the peridotites that form cratonic mantle roots is a central issue in understanding the history and survival of Earth’s oldest continents. A long-standing hypothesis holds that the unusual bulk compositions of some cratonic peridotites stem from their origin as subducted oceanic serpentinite, dehydrated during subduction to form rigid buoyant keels (Schulze, 1986; Canil and Lee, 2009). We present oxygen isotope data from 93 mantle peridotites from five different Archean cratons to evaluate their possible origin as serpentinites. Cratonic mantle peridotite shows remarkably uniform δ18O values, identical to modern MORB-source mantle, that do not vary with bulk rock Si-enrichment or Ca-depletion. These data clearly conflict with any model for cratonic lithosphere that invokes serpentinite as a protolith for cratonic peridotite, and place additional constraints on cratonic mantle origins. We posit that the uniform δ18O was produced by sub-arc and/or MOR depletion processes and that the Si-enriched nature of some samples is unlikely to be related to slab melt infiltration. Instead, we suggest a peridotitic source of Si-enrichment, derived from ascending mantle melts, or a water-fluxed depleted mantle. These variably Si-enriched, cratonic mantle protoliths were then collisionally compressed into the thick cratonic roots that have protected Earth’s oldest continental crust for over 2.5 Gyr.