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

Olivine-hosted melt inclusions as an archive of redox heterogeneity in magmatic systems

The redox state of volcanic products determines their leverage on the oxidation of Earth's oceans and atmosphere, providing a long-term feedback on oxygen accumulation at the planet's surface. An archive of redox conditions in volcanic plumbing systems from a magma's mantle source, through crustal storage, to eruption, is carried in pockets of melt trapped within crystals. While melt inclusions have long been exploited for their capacity to retain information on a magma's history, their permeability to fast-diffusing elements such as hydrogen is now well documented and their retention of initial oxygen fugacities () could be similarly diffusion-limited. To test this, we have measured Fe3+/ΣFe by micro-XANES spectroscopy in a suite of 65 olivine-hosted melt inclusions and 9 matrix glasses from the AD 1783 Laki eruption, Iceland. This eruption experienced pre-eruptive mixing of chemically diverse magmas, syn-eruptive degassing at the vent, and post-eruptive degassing during lava flow up to 60 km over land, providing an ideal test of whether changes in the of a magma may be communicated through to its cargo of crystal-hosted melt inclusions. Melt inclusions from rapidly quenched tephra samples have Fe3+/ΣFe of (ΔQFM of +0.7 ± 0.1), with no correlation between their and degree of trace element enrichment or differentiation. These inclusions preserve the redox conditions of the mixed pre-eruptive Laki magma. When corrected for fractional crystallisation to 10 wt.% MgO, these inclusions record a parental magma [Fe3+/ΣFe](10) of 0.18 (ΔQFM of +0.4), significantly more oxidised than the Fe3+/ΣFe of 0.10 that is often assumed for Icelandic basalt magmas. Melt inclusions from quenched lava selvages are more reduced than those from the tephra, having Fe3+/ΣFe between 0.133 and 0.177 (ΔQFM from −0.4 to +0.4). These inclusions have approached equilibrium with their carrier lava, which has been reduced by sulfur degassing. The progressive re-equilibration of between inclusions and carrier melts occurs on timescales of hours to days, causing a drop in the sulfur content at sulfide saturation (SCSS) and driving the exsolution of immiscible sulfide globules in the inclusions. Our data demonstrate the roles of magma mixing, progressive re-equilibration, and degassing in redox evolution within magmatic systems, and the open-system nature of melt inclusions to during these processes. Redox heterogeneity present at the time of inclusion trapping may be overprinted by rapid re-equilibration of melt inclusion with the external environment, both in the magma chamber and during slow cooling in lava at the surface. This can decouple the melt inclusion archives of , major and trace element chemistry, and mask associations between , magmatic differentiation and mantle source heterogeneity unless the assembly of diverse magmas is rapidly followed by eruption. Our tools for understanding the redox conditions of magmas are thus limited; however, careful reconstruction of pre- and post-eruptive magmatic history has enabled us to confirm the relatively oxidised nature of ocean island-type mantle compared to that of mid-ocean ridge mantle

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 1480−30+37 °C for Iceland and 1318−32+44 °C for MORB.O.S. was supported by a Title A Fellowship from Trinity College Cambridge and a Geology Option Postdoctoral Fellowship at Caltech

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

A Statistical description of concurrent mixing and crystallisation during MORB differentiation: Implications for trace element enrichment

The pattern of trace element enrichment and variability found in differentiated suites of basalts is a sim- ple observable, which nonetheless records a wealth of information on processes occurring from the mantle to crustal magma chambers. The incompatible element contents of some mid-ocean ridge basalt (MORB) sample suites show progressive enrichment beyond the predictions of simple models of fractional crystalli- sation of a single primary melt. Explanations for this over-enrichment have focused on the differentiation processes in crustal magma chambers. In this paper we consider an additional mechanism, and focus instead on the deviation from simple fractionation trends that is possible by mixing of diverse mantle-derived melts supplied to magma chambers. A primary observation motivating this strategy is that there is significant chemical diversity in primitive high MgO basalts, which single liquid parent models cannot match. Models were developed to simulate the compositional effects of concurrent mixing and crystallisation (CMC): diverse parental melts were allowed to mix, with a likelihood that is proportional to the extent of fractional crys- tallisation. Using a simple statistical model to explore the effects of concurrent mixing and crystallisation on apparent liquid lines of descent, we show how significant departure from Rayleigh fractionation is possible as a function of the diversity of trace elements in the incoming melts, their primary MgO, and the relative proportion of enriched to depleted melts. The model was used to make predictions of gradients of trace element enrichment in log[trace element]– MgO space. These predictions were compared with observations from a compilation of global MORB and provide a test of the applicability of CMC to natural systems. We find that by considering the trace element variability of primitive MORB, its MgO content and degree of enrichment, CMC accurately predicts the pattern of trace element over-enrichment seen in global MORB. Importantly, this model shows that the relationship between over-enrichment and incompatibility can derive from mantle processes: the fact that during mantle melting maximum variability is generated in those elements with the smallest bulk K d . Magma chamber processes are therefore filtering the signal of mantle-derived chemical diversity to produce trace element over-enrichment during differentiation. Finally, we interrogate the global MORB dataset for evidence that trace element over-enrichment varies as a function of melt supply. There is no correlation between over-enrichment and melt supply in the global dataset. Trace element over-enrichment occurs at slow-spreading ridges where extensive steady-state axial magma chambers, the most likely environment for repeated episodes of replenishment, tapping and crystallisation, are very rarely detected. This supports a model whereby trace element over-enrichment is an inevitable consequence of chemically heterogeneous melts delivered from the mantle, a process that may operate across all rates of melt supply

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]source) 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](source) content. Propagating uncertainty through these steps, we obtain a range of [Fe2O3](source) 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

A Surface Hydrothermal Source of Nitriles and Isonitriles

Giant impacts can generate transient hydrogen-rich atmospheres, reducing atmospheric carbon. The reduced carbon will form hazes that rain out onto the surface and can become incorporated into the crust. Once heated, a large fraction of the carbon would be converted into graphite. The result is that local regions of the Hadean crust were plausibly saturated with graphite. We explore the consequences of such a crust for a prebiotic surface hydrothermal vent scenario. We model a surface vent fed by nitrogen-rich volcanic gas from high-temperature magmas passing through graphite-saturated crust. We consider this occurring at pressures of 1-1000 bar and temperatures of 1500-1700 degC. The equilibrium with graphite purifies the left-over gas, resulting in substantial quantities of nitriles (0.1% HCN and 1 ppm HC3N) and isonitriles (0.01% HNC) relevant for prebiotic chemistry. We use these results to predict gas-phase concentrations of methyl isonitrile of ~ 1 ppm. Methyl isocyanide can participate in the non-enzymatic activation and ligation of the monomeric building blocks of life, and surface, or shallow, hydrothermal environments provide its only known equilibrium geochemical source.Comment: 26 pages, 17 figures, 2 tables. Accepted for publication in Life (MDPI Journal

Scum of the Earth: A Hypothesis for Prebiotic Multi-Compartmentalised Environments.

Compartmentalisation by bioenergetic membranes is a universal feature of life. The eventual compartmentalisation of prebiotic systems is therefore often argued to comprise a key step during the origin of life. Compartments may have been active participants in prebiotic chemistry, concentrating and spatially organising key reactants. However, most prebiotically plausible compartments are leaky or unstable, limiting their utility. Here, we develop a new hypothesis for an origin of life environment that capitalises upon, and mitigates the limitations of, prebiotic compartments: multi-compartmentalised layers in the near surface environment-a 'scum'. Scum-type environments benefit from many of the same ensemble-based advantages as microbial biofilms. In particular, scum layers mediate diffusion with the wider environments, favouring preservation and sharing of early informational molecules, along with the selective concentration of compatible prebiotic compounds. Biofilms are among the earliest traces imprinted by life in the rock record: we contend that prebiotic equivalents of these environments deserve future experimental investigation

Post-main sequence thermal evolution of planetesimals

White dwarfs that have accreted planetary materials provide a powerful tool to probe the interiors and formation of exoplanets. In particular, the high Fe/Si ratio of some white dwarf pollutants suggests that they are fragments of bodies that were heated enough to undergo large-scale melting and iron core formation. In the solar system, this phenomenon is associated with bodies that formed early and so had short-lived radionuclides to power their melting, and/or grew large. However, if the planetary bodies accreted by white dwarfs formed during the (pre)-main sequence lifetime of the host star, they will have potentially been exposed to a second era of heating during the star's giant branches. This work aims to quantify the effect of stellar irradiation during the giant branches on planetary bodies by coupling stellar evolution to thermal and orbital evolution of planetesimals. We find that large-scale melting, sufficient to form an iron core, can be induced by stellar irradiation, but only in close-in small bodies: planetesimals with radii $\lesssim$ 30 km originally within $\sim$ 2 AU orbiting a 1$-$3$\,M_{\odot}$ host star with solar metallicity. Most of the observed white dwarf pollutants are too massive to be explained by the accretion of these small planetesimals that are melted during the giant branches. Therefore, we conclude that those white dwarfs that have accreted large masses of materials with enhanced or reduced Fe/Si remain an indicator of planetesimal's differentiation shortly after formation, potentially linked to radiogenic heating.Comment: 19 pages, 18 figure