Evidence for post-nebula volatilisation in an exo-planetary body

The loss and gain of volatile elements during planet formation is key for setting their subsequent climate, geodynamics, and habitability. Two broad regimes of volatile element transport in and out of planetary building blocks have been identified: that occurring when the nebula is still present, and that occurring after it has dissipated. Evidence for volatile element loss in planetary bodies after the dissipation of the solar nebula is found in the high Mn to Na abundance ratio of Mars, the Moon, and many of the solar system's minor bodies. This volatile loss is expected to occur when the bodies are heated by planetary collisions and short-lived radionuclides, and enter a global magma ocean stage early in their history. The bulk composition of exo-planetary bodies can be determined by observing white dwarfs which have accreted planetary material. The abundances of Na, Mn, and Mg have been measured for the accreting material in four polluted white dwarf systems. Whilst the Mn/Na abundances of three white dwarf systems are consistent with the fractionations expected during nebula condensation, the high Mn/Na abundance ratio of GD362 means that it is not (>3 sigma). We find that heating of the planetary system orbiting GD362 during the star's giant branch evolution is insufficient to produce such a high Mn/Na. We, therefore, propose that volatile loss occurred in a manner analogous to that of the solar system bodies, either due to impacts shortly after their formation or from heating by short-lived radionuclides. We present potential evidence for a magma ocean stage on the exo-planetary body which currently pollutes the atmosphere of GD362

Can volcanism build hydrogen-rich early atmospheres?

Hydrogen in rocky planet atmospheres has been invoked in arguments for extending the habitable zone via N2-H2 and CO2-H2 greenhouse warming, and providing atmospheric conditions suitable for efficient production of prebiotic molecules. On Earth and Super-Earth-sized bodies, where H2-rich primordial envelopes are quickly lost to space, volcanic outgassing can act as a hydrogen source, provided it balances with the loss rate from the top of the atmosphere. Here, we show that both Earth-like and Mars-like planets can sustain atmospheric H2 fractions of several percent across relevant magmatic fO2 ranges. In general this requires hydrogen escape to operate somewhat less efficiently than the diffusion limit. We use a thermodynamical model of magma degassing to determine which combinations of magma oxidation, volcanic flux, and hydrogen escape efficiency can build up appreciable levels of hydrogen in a planet's secondary atmosphere. On a planet similar to the Archean Earth and with a similar magmatic fO2, we suggest that the mixing ratio of atmospheric hydrogen could have been in the range 0.2-3%. A planet erupting magmas around the Iron-Wustite (IW) buffer (i.e., ~3 log fO2 units lower than Archean Earth's), but with otherwise similar volcanic fluxes and H2 loss rates to early Earth, could sustain an atmosphere with approximately 10-20% H2. For an early Mars-like planet with magmas around IW, but a lower range of surface pressures and volcanic fluxes compared to Earth, an atmospheric H2 mixing ratio of 2-8% is possible. On early Mars, this H2 mixing ratio could be sufficient to deglaciate the planet. However, the sensitivity of these results to primary magmatic water contents and volcanic fluxes show the need for improved constraints on the crustal recycling efficiency and mantle water contents of early Mars

The temperature of the Icelandic mantle from olivine-spinel aluminum exchange thermometry

New crystallization temperatures for four eruptions from the Northern Volcanic Zone of Iceland are determined using olivine-spinel aluminum exchange thermometry. Differences in the olivine crystallization temperatures between these eruptions are consistent with variable extents of cooling during fractional crystallization. However, the crystallization temperatures for Iceland are systematically offset to higher temperatures than equivalent olivine-spinel aluminum exchange crystallization temperatures published for MORB, an effect that cannot be explained by fractional crystallization. The highest observed crystallization temperature in Iceland is 1399 ± 20°C. In order to convert crystallization temperatures to mantle potential temperature, we developed a model of multilithology mantle melting that tracks the thermal evolution of the mantle during isentropic decompression melting. With this model, we explore the controls on the temperature at which primary melts begin to crystallize, as a function of source composition and the depth from which the magmas are derived. Large differences (200°C) in crystallization temperature can be generated by variations in mantle lithology, a magma's inferred depth of origin, and its thermal history. Combining this model with independent constraints on the magma volume flux and the effect of lithological heterogeneity on melt production, restricted regions of potential temperature-lithology space can be identified as consistent with the observed crystallization temperatures. Mantle potential temperature is constrained to be math formula °C for Iceland and math formula °C for MORB

The global melt inclusion C/Ba array: Mantle variability, melting process, or degassing?

The Earth’s mantle holds more carbon than its oceans, atmosphere and con- tinents combined, yet the distribution of carbon within the mantle remains uncertain. Our best constraints on the distribution of carbon within the up- per mantle are derived from the carbon-trace element systematics of ultra- depleted glasses and melt inclusions from mid-ocean ridge basalts. How- ever, carbon-trace element systematics are susceptible to modification by crustal processes, including concurrent degassing and mixing, and melt in- clusion decrepitation. In this study we explore how the influence of these processes varies systematically with both the mantle source and melting pro- cess, thereby modulating both global and local carbon-trace element trends. We supplement the existing melt inclusion data from Iceland with four new datasets, significantly enhancing the spatial and geochemical coverage of melt inclusion datasets from the island. Within the combined Iceland dataset there is significant variation in melt inclusion C/Ba ratio, which is tightly correlated with trace element enrichment. The trends in C/Ba- Ba space displayed by our new data coincide with the same trends in data compiled from global ocean islands and mid-ocean ridges, forming a global array. The overall structure of the global C/Ba-Ba array is not a property of the source, instead it is controlled by CO2 vapour loss pre- and post-melt inclusion entrapment; i.e., the array is a consequence of degassing creating near-constant maximum melt-inclusion carbon contents over many orders of magnitude of Ba concentration. On Iceland, extremely high C/Ba (>100) and C/Nb (>1000) ratios are found in melt inclusions from the most depleted eruptions. The high C/Ba and C/Nb ratios are unlikely to be either analytical artefacts, or to be the product of extreme fractionation of the most incompatible elements during silicate melting. Whilst high C/Ba and C/Nb ratios could be generated by regassing of melt inclusions by CO2 vapour, or by mantle melting occurring in the presence of residual graphite, we suggest the high values most likely derive from an intrinsically high C/Ba and C/Nb mantle component that makes up a small fraction of the Icelandic mantle

Constraining mantle carbon: CO2-trace element systematics in basalts and the roles of magma mixing and degassing

Our present understanding of the mantle carbon budget is in part built upon measurements of carbon concentrations in olivine hosted melt inclusions. Only a small number of such datasets are thought to have avoided degassing, having been entrapped prior to CO2 vapour saturation, and are therefore able to constrain primary CO2 concentrations. The absence of degassing in melt inclusion datasets has been inferred from the presence of strong correlations between CO2 and trace elements. In this contribution, we demonstrate that partial degassing followed by magma mixing not only retains such positive correlations, but can enhance them. Simple models of magma mixing and degassing are used to characterise how CO2-trace element systematics respond to CO2 vapour saturation in primary mantle melts entering the crust, followed by magma mixing. Positive correlations are expected between CO2 and most trace elements, and the average CO2/Ba and CO2/Nb ratios are controlled by the pressure of magma storage, rather than the CO2 concentration in the mantle. We find that the best estimates of mantle CO2 are the maximum CO2/Ba ratios observed in melt inclusion datasets, though a large number of analyses are required to adequately characterise the maximum of the CO2/Ba distribution. Using the mixing and degassing models we estimate the number of analyses required to obtain a maximum CO2/Ba observation within 10% of the mantle value. In light of our results, we reassess existing melt inclusion datasets, and find they exhibit systematics associated with partial degassing and mixing. We argue that all the data presently available is consistent with a depleted mantle CO2/Ba ratio of ~140, and there is as yet no evidence for heterogeneity in the CO2/Ba ratio of the depleted mantle

Major Element Composition of Sediments in Terms of Weathering and Provenance: Implications for Crustal Recycling

The elemental composition of a sediment is set by the composition of its protolithand modified by weathering, sorting, and diagenesis. An important problem is deconvolving these contributions to a sediment’s composition to arrive at information about processesthat operate on the Earth’s surface. We approach this problem by developing a predictive andinvertible model of sedimentary major-element composition. We compile a dataset of sedimentary rock, river sediment, soil, and igneous rock compositions. Principal componentanalysis of the dataset shows that most variation can be simplified to a small number of variables. We thus show that any sediment’s composition can be described with just two vectorsof igneous evolution and weathering. We hence define a model for sedimentary compositionas a combination of these processes. A 1:1 correspondence is observed between predictionsand independent data. The log-ratios ln(K 2 O/MgO) and ln(Al 2 O 3 /Na 2 O) are found to besimple proxies for respectively the model’s protolith and weathering indices. Significant deviations from the model can be explained by sodium-calcium exchange. Using this approach,we show that the major-element composition of the upper continental crust has been modified by weathering and we calculate the amount of each element that it must have lost tomodify it to its present composition. By extrapolating modern weathering rates over the ageof the crust we conclude that it has not retained a significant amount of the necessarily produced weathering restite. This restite has likely been subducted into the mantle, indicating acrust-to-mantle recycling rate of 1.33 ± 0.89 × 10 13 kg yr −1 .</p

Oxidised micrometeorites as evidence for low atmospheric pressure on the early Earth

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.PBR thanks the Simons Foundation and Kavli Foundation for funding, specifically Simons Foundation SCOL awards 59963

Fe-XANES analyses of Reykjanes Ridge basalts: Implications for oceanic crust's role in the solid Earth oxygen cycle

The cycling of material from Earth's surface environment into its interior can couple mantle oxidation state to the evolution of the oceans and atmosphere. A major uncertainty in this exchange is whether altered oceanic crust entering subduction zones can carry the oxidised signal it inherits during alteration at the ridge into the deep mantle for long-term storage. Recycled oceanic crust may be entrained into mantle upwellings and melt under ocean islands, creating the potential for basalt chemistry to constrain solid Earth–hydrosphere redox coupling. Numerous independent observations suggest that Iceland contains a significant recycled oceanic crustal component, making it an ideal locality to investigate links between redox proxies and geochemical indices of enrichment. We have interrogated the elemental, isotope and redox geochemistry of basalts from the Reykjanes Ridge, which forms a 700 km transect of the Iceland plume. Over this distance, geophysical and geochemical tracers of plume influence vary dramatically, with the basalts recording both long- and short-wavelength heterogeneity in the Iceland plume. We present new high-precision Fe-XANES measurements of Fe³⁺/∑Fe on a suite of 64 basalt glasses from the Reykjanes Ridge. These basalts exhibit positive correlations between Fe³⁺/∑Fe and trace element and isotopic signals of enrichment, and become progressively oxidised towards Iceland: fractionation-corrected Fe³⁺/∑Fe increases by ∼0.015 and ΔQFM by ∼0.2 log units. We rule out a role for sulfur degassing in creating this trend, and by considering various redox melting processes and metasomatic source enrichment mechanisms, conclude that an intrinsically oxidised component within the Icelandic mantle is required. Given the previous evidence for entrained oceanic crustal material within the Iceland plume, we consider this the most plausible carrier of the oxidised signal. To determine the ferric iron content of the recycled component ([Fe₂O₃]) we project observed liquid compositions to an estimate of Fe₂O₃ in the pure enriched endmember melt, and then apply simple fractional melting models, considering lherzolitic and pyroxenitic source mineralogies, to estimate [Fe₂O₃] content. Propagating uncertainty through these steps, we obtain a range of [Fe₂O₃] for the enriched melts (0.9–1.4 wt%) that is significantly greater than the ferric iron content of typical upper mantle lherzolites. This range of ferric iron contents is consistent with a hybridised lherzolite–basalt (pyroxenite) mantle component. The oxidised signal in enriched Icelandic basalts is therefore potential evidence for seafloor–hydrosphere interaction having oxidised ancient mid-ocean ridge crust, generating a return flux of oxygen into the deep mantle.OS was supported by a Title A Fellowship from Trinity College, JM through NERC grant NE/J021539/1 and MH acknowledges a Junior Research Fellowship from Murray Edwards College, Cambridge. We acknowledge Diamond Light Source for time on beamline I18 under proposals SP9446, SP9456 and SP12130 and the support during our analytical sessions from beamline scientist Konstantin Ignatyev and principal beamline scientist Fred Mosselmans. The Smithsonian Institution National Museum of Natural History is thanked for their loan of NMNH 117393.This is the final version of the article. It first appeared from Elsevier via http://dx.doi.org/10.1016/j.epsl.2015.07.01

Estimating the carbon content of the deep mantle with Icelandic melt inclusions

Earth’s carbon budget is central to our understanding of the long-term co-evolution of life and the planet. Direct observations of surface reservoirs allow for the detailed quantification of their carbon content. However, the carbon content of Earth’s deep interior remains poorly constrained. Here we study olivine-hosted melt inclusions from two Icelandic eruptions, with those from the Miðfell eruption allowing us to investigate the carbon content of the deep mantle. Comparison with the previously studied Borgarhraun eruption highlights the presence of deep, plume-sourced mantle material within the Miðfell source region. Miðfell contains trace element-depleted melt inclusions undersaturated in CO2, which have high CO2/Ba (= 396 ± 48) and CO2/Nb (= 1832 ± 316), though some inclusions preserve even greater relative carbon enrichment. These observations allow us to reconstruct the CO2 content of the bulk Miðfell source as being > 690 ppm. By identifying that Miðfell is a mixture of depleted and deep mantle components, we can estimate a CO2 content for the deep mantle component of 1350 ± 350 ppm; a concentration that is over ten times higher than depleted MORB mantle estimates. Assuming that the deep mantle component identified in Miðfell is representative of a global reservoir, then with our new CO2 estimate and by considering a range of representative mantle fractions for this reservoir, we calculate that it contains up to 14 times more carbon than that of the atmosphere, oceans, and crust combined. Our result of elevated CO2/Ba and CO2/Nb ratios, and carbon enrichment support geochemical bulk Earth carbon models that call for the presence of carbon-rich deep mantle domains to balance Earth’s relatively carbon-poor upper mantle and surface environment

Igneous rock area and age in continental crust

Abstract Rock quantity and age are fundamental features of Earth's crust that pertain to many problems in geoscience. Here we combine new estimates of igneous rock area in continental crust from the Macrostrat database (https://macrostrat.org/) with a compilation of detrital zircon ages in order to investigate rock cycling and crustal growth. We find that there is little or no decrease in igneous rock area with increasing rock age. Instead, igneous rock area in North America exhibits four distinct Precambrian peaks, remains low through the Neoproterozoic, and then increases only modestly toward the recent. Peaks in Precambrian detrital zircon age frequency distributions align broadly with peaks in igneous rock area, regardless of grain depositional age. However, detrital zircon ages do underrepresent a Neoarchean peak in igneous rock area; young grains and ca. 1.1 Ga grains are also overrepresented relative to igneous area. Together, these results suggest that detrital zircon age distributions contain signatures of continental denudation and sedimentary cycling that are decoupled from the cycling of igneous source rocks. Models of continental crustal evolution that incorporate significant early increase in volume and increased sedimentation in the Phanerozoic are well supported by these data.</jats:p