Nicholas D. Tailby

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) 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 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 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.

Al diffusion in quartz

Abstract Aluminum diffusion in synthetic and natural quartz was characterized under anhydrous conditions at 1 atm and temperatures from 700 to 950 °C. Experiments were carried out on polished quartz slabs immersed in fine-grained powder of spodumene or K-feldspar. Diffusion profiles were measured using Nuclear Reaction Analysis (NRA) and yield the following Arrhenius parameters: DAl = 2.48 × 10–11 exp(−199 ± 10 kJ/mol/RT)m2s–1, where log D0 = –10.6 ± 0.55. The diffusivity of Al through the quartz lattice is sufficiently slow (e.g., akin to Ti) that diffusive modification or loss of Al in magmatic or metamorphic quartz is unlikely in all but the most extreme temperature-time conditions seen in natural systems. In other words, core to rim Al zonation produced during crystal fractionation from a granitoid, or metamorphic overgrowths on quartz during metamorphism, are likely to be preserved at the crystal scale but may show some diffusive relaxation at sub-micrometers to tens of micrometers in scale. The similar diffusivities of Al and Ti also suggest that diffusive modification of Al/Ti is highly unlikely to occur at all but the smallest length scales (e.g., sub-micrometers to tens of micrometers). These observations indicate that the two most abundant impurities in quartz (Al and Ti) are likely to record primary information regarding the crystallization conditions in most geological environments.

Insights into the Hadean Earth from Experimental Studies of Zircon

Geologists investigate the evolution of the atmosphere, crust, and mantle through time by direct study of the rock record. However, the Hadean eon (>3.85 Ga) has been traditionally viewed as inaccessible due to the absence of preserved rocks. The discovery of >4.0 Ga detrital zircons from Western Australia in the 1980s — coupled with the development of new micro-analytical capabilities — made possible new avenues of early Earth research. The prevailing view that emerged is that the early Earth may have contained a stable hydrosphere, water-saturated or (near watersaturated) granitic magmas, and volcanic emanations dominated by neutral gas species (e.g., CO2, H2O, and SO2). The Hadean Earth may have been capable of supporting life ∼200 Ma after accretion and perhaps earlier. Many of these models are formulated — or have been subsequently supported — by laboratory experiments of zircon. Important petrological variables such as temperature, pressure, oxygen fugacity, and component activities (e.g., SiO2/TiO2-activities) can be controlled. These experiments are fundamental for extrapolation to ‘deep time’ because they provide a means to understand primary chemistry preserved in ancient zircons. This review paper specifically focuses on zircon experimental studies (oxygen isotope fractionations, Ti-thermometry, and redox sensitive element incorporation into zircon), which have influenced our view of the very early Earth.

Trace elements in quartz shed light on sediment provenance

Quartz is one of the most common minerals on the surface of the earth, and is a primary rock-forming 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 well-constrained 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.

Variation in XANES in biotite as a function of orientation, crystal composition, and metamorphic history

Abstract Microscale analysis of ferrous:ferric iron ratios in silicate minerals has the potential to constrain geological processes but has proved challenging because textural information and spatial resolution are limited with bulk techniques, and in situ methods have limited spatial resolution. Synchrotron methods, such as XANES, have been hampered by the sensitivity of spectra to crystal orientation and matrix effects. In an attempt to break this nexus, biotites from Tanzania were characterized with a combination of optical microscopy, electron microprobe, Mössbauer analysis, electron backscatter diffraction (EBSD) and X-ray absorption near edge structure (XANES) spectroscopy. Pre-edge and edge characteristics of the FeKα absorption feature were compared to orientation information derived by EBSD and ferric iron content derived from Mössbauer analysis. Statistically significant correlations between measured spectral features and optic/crystallographic orientation were observed for individual samples. However, orientation corrections derived from these correlations did not reduce the uncertainty in Fe3+/Fetot. The observations are consistent with matrix- and ordering-dependency of the XANES features, and further work is necessary if a general formulation for orientation corrections is to be devised.

Aluminum in zircon as evidence for peraluminous and metaluminous melts from the Hadean to present

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.

Experimental investigation into the substitution mechanisms and solubility of Ti in garnet

Abstract Garnet is a common and important mineral in metamorphic systems, but the mechanisms by which it incorporates Ti—one of the major elements in the crust—are not well constrained. This study draws upon garnets synthesized at a range of temperatures and pressures to understand Ti solubility and the substitution mechanisms that govern its incorporation into garnet at eclogite and granulite facies conditions. Garnets from these synthesis experiments can incorporate up to several wt% TiO2. Comparison of Ti content with deficits in Al and Si in garnet indicates that Ti is incorporated by at least two substitution mechanisms (VITi4+ + VIM2+ ↔ 2VIAl3+, and VITi4+ + IVAl3+ ↔ VIAl3+ + IVSi4+). Increasing Ti solubility is correlated with increasing Ca and Fe/Mg ratios in garnet, clinopyroxene and melt. The complexity of the substitution mechanisms involved in Ti solubility in garnet makes practical Ti-in- garnet thermobarometry infeasible at present. However, a model fit to Ti partitioning between garnet and melt can be used to predict melt compositions in high-grade metamorphic systems. Additionally, the solubility and substitution mechanisms described here can help explain the presence of crystallographically aligned rutile needles in high-grade metamorphic systems.

XAFS spectroscopic study of Ti coordination in garnet

Abstract Titanium can be incorporated either tetrahedrally (IVTi) or octahedrally (VITi) in most silicate minerals. Ti K-edge X-ray absorption fine structure (XAFS) spectroscopy enables observation of Ti coordination in minerals and melts. In this study, XAFS is used to determine the coordination of Ti in synthetic and natural garnets. Garnets grown synthetically at eclogite- and granulite-facies conditions can contain several wt% TiO2, most of which is incorporated as VITi. This observation aligns with major element trends in these garnets. In natural garnets grown at lower temperatures and pressures, on the other hand, Ti is observed to occupy both the octahedral and tetrahedral sites in garnet—in some cases Ti is almost entirely fourfold coordinated. Combined with previous research (see Ackerson et al. 2017, this issue) on substitution mechanisms for VITi, the results of this study demonstrate that Ti is incorporated on two crystallographic sites in garnet by at least three primary substitution mechanisms. In both natural and synthetic garnets, there is a discernible increase in VITi content in garnet with increasing temperature and pressure, suggesting a significant role for these two parameters in determining Ti solubility. However, a continuous increase in VITi with increasing grossular content also suggests that the Ca content of the garnet plays a critical role.