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Mantle plume-related magmas typically have higher chalcophile and siderophile element (CSE) contents than mid-ocean ridge basalts (MORB). These differences are often attributed to sulfide-under-saturation of plume-related melts. However, because of eruption-related degassing of sulfur (S) and the compositional, pressure, temperature and redox effects on S-solubility, understanding the magmatic behavior of S is challenging. Using CSE data for oceanic plateau basalts (OPB), which rarely degas S, we show that many OPB are sulfide-saturated. Differences in the timing of sulfide-saturation between individual OPB suites can be explained by pressure effects on sulfur solubility associated with ascent through over-thickened crust. Importantly, where S-degassing does occur, OPB have higher CSE contents than S-undegassed melts at similar stages of differentiation. This can be explained by resorption of earlier-formed sulfides, which might play an important role in enriching degassed melts in sulfide-compatible CSE and potentially contributes to anomalous enrichments of CSE in the crust.

The geochemistry of global mantle melts suggests that both mid-ocean ridge basalts (MORB) and ocean island basalts (OIB) sample lithological and temperature heterogeneities originating in both the upper and lower mantle. Recently, non-traditional stable isotopes have been suggested as a new tool to complement existing tracers of mantle heterogeneity (e.g., major and trace elements, radiogenic isotopes), because mineral- and redox-specific equilibrium stable isotope fractionation effects can link the stable isotope ratios of melts to their source mineralogy and melting degree. Here, we investigate five stable isotope systems (Mg-Ca-Fe-V-Cr) that have shown promise in models or natural samples as tracers of mantle temperature and/or lithological heterogeneity. We use a quantitative model, combining thermodynamically self-consistent mantle melting and equilibrium isotope fractionation models, to explore the behaviour of the isotope ratios of these elements during melting of three mantle lithologies (peridotite, and silica-excess and silica-deficient pyroxenites), responding to changes in mantle mineralogy, oxygen fugacity, temperature and pressure.We find that, given current analytical precision, the stable isotope systems examined here are not predicted to be sensitive to mantle potential temperature variations through equilibrium isotope fractionation processes. By contrast, source lithological heterogeneity is predicted to be detectable in some cases in the stable isotope ratios of erupted basalts, although generally only at proportions of > 10% MORB-like pyroxenite in the mantle source, given current analytical precision. Magnesium and Ca stable isotopes show most sensitivity to a garnet-bearing source lithology, and Fe and Cr stable isotopes are potentially sensitive to the presence of MORB-like pyroxenite in the mantle source, although the behaviour of Cr isotopes is comparatively under-constrained and requires further work to be applied with confidence to mantle melts. When comparing the magnitude and direction of predicted equilibrium isotopic fractionation of peridotite and pyroxenite melts to natural MORB and OIB data, we find that aspects of the natural data (including the mean Mg-Ca-Fe-V isotopic composition of MORB, the range of Mg-Ca isotopic compositions seen in MORB data, the mean Mg-Ca-Cr isotopic composition of OIB, and the range of Mg-V-Cr isotopic compositions in OIB data) can be matched by equilibrium isotope fractionation during partial melting of peridotite and pyroxenite sources -- with pyroxenite required even for some MORB data. However, even when considering analytical uncertainty on natural sample measurements, the range in stable isotope compositions seen across the global MORB and OIB datasets suggests that kinetic isotope fractionation, or processes modifying the isotopic composition of recycled crustal material such that it is distinct from MORB, may be required to explain all the natural data. We conclude that the five stable isotope systems considered here have potential to be powerful complementary tracers to other geochemical tracers of the source lithology of erupted basalts. However, continued improvements in analytical precision in conjunction with experimental and theoretical predictions of isotopic fractionation between mantle minerals and melts are required before these novel stable isotopes can be unambiguously used to understand source heterogeneity in erupted basalts.

The extent of lithological heterogeneity in the Earth’s convecting mantle is highly debated. Whilst the presence of pyroxenite in the mantle source regions of Ocean Island Basalts (OIBs) has traditionally been constrained using the minor-element chemistry of olivine phenocrysts, recent studies have shown that the Ni and Mn contents of primitive olivines are influenced by the conditions of mantle melting, as well as magma chamber processes. Nevertheless, constraining the lithological properties of the mantle is important due to it’s influence on the P-T path followed by solid mantle material during adiabatic ascent, as well as the density of upwelling mantle plumes. We have therefore explored the use of Fe-isotopes as a novel method of tracing lithological heterogeneity in the mantle source regions beneath plume-influenced segments of the global Mid-Ocean Ridge system as well as OIBs. We present new Fe-isotope (δ56Fe) and trace-element data for 26 basaltic glasses from the plume-influenced Galápagos Spreading Centre to investigate the relative roles of pyroxenite and peridotite in the mantle source region of oceanic basalts. Our data reveals significant heterogeneity in the Fe-isotope composition of the Galápagos Spreading Centre basalts (+0.05 - +0.25‰ δ56Fe), which correlates with key major- and trace-element parameters (e.g. CaO(8)/Al2O3(8), [La/Sm]n). Application of new models developed to calculate Fe-isotope fractionation during mantle melting, alongside Monte Carlo simulations for melting of a 2-component peridotite mantle, show that this variation cannot be caused by changes in melting processes and/or oxygen fugacity of a peridotitic mantle. Instead, our new δ56Fe data is best explained by variations in the proportion of isotopically-heavy pyroxenite-derived melt that contributes to the GSC basalts, and conclusively shows that lithological heterogeneity exists in the Galápagos mantle plume. Our findings have implications for the moderately-heavy δ56Fe compositions measured in plume-influenced basalts from the Society Islands, Rochambeau Ridges of the Lau back-arc basin, and the FAMOUS segment of the Mid-Atlantic Ridge, which we suggest may also represent contribution from pyroxenite-derived melts.

Young (61 Ma) unaltered picrites from Baffin Island, northwest Canada, possess some of the highest 3He/4He (up to 50 Ra) seen on Earth, and provide a unique opportunity to study primordial mantle that has escaped subsequent chemical modification. These high-degree partial melts also record anomalously high 182W/184W ratios, but their Sr-Nd-Hf-Pb isotopic compositons (including 142Nd) are indistinguishable from those of North Atlantic mid-ocean ridge basalts. New high precision Fe and Zn stable isotope analyses of Baffin Island picrites show limited variability with δ56Fe ranging from −0.03‰ to 0.13‰ and δ66Zn varying from 0.18‰ to 0.28‰. However, a clear inflection is seen in both sets of isotope data around the composition of the parental melt (MgO = 21 wt %; δ56Fe = 0.08 ± 0.04‰; and δ66Zn = 0.24 ± 0.03‰), with two diverging trends interpreted to reflect the crystallisation of olivine and spinel in low-MgO samples and the accumulation of olivine at higher MgO. Olivine mineral separates are significantly isotopically lighter than their corresponding whole rocks (δ56Fe ≥ −0.62‰ and δ66Zn ≥ −0.22‰), with analyses of individual olivine phenocrysts having extremely variable Fe isotope compositions (δ56Fe = −0.01‰ to −0.80‰). By carrying out modelling in three-isotope space, we show that the very negative Fe isotope compositions of olivine phenocryst are the result of kinetic isotope fractionation from disequilibrium diffusional processes. An excellent correlation is observed between δ56Fe and δ66Zn, demonstrating that Zn isotopes are fractionated by the same processes as Fe in simple systems dominated by magmatic olivine. The incompatible behaviour of Cu during magmatic evolution is consistent with the sulfide- undersaturated nature of these melts. Consequently Zn behaves as a purely lithophile element, and estimates of the bulk Earth Zn isotope composition based on Baffin Island should therefore be robust. The ancient undegassed lower mantle sampled at Baffin Island possesses a δ56Fe value that is within error of previous estimates of bulk mantle δ56Fe, however, our estimate of the Baffin mantle δ66Zn (0.20 ± 0.03‰) is significantly lower than some previous estimates. Comparison of our new data with those for Archean and Proterozoic komatiites is consistent with the Fe and Zn isotope composition of the mantle remaining constant from at least 3 Ga to the present day. By focusing on large-degree partial melts (e.g. komatiites and picrites) we are potenitally biasing our record to samples that will inevitably have interacted with, entrained and melted the ambient shallow mantle during ascent. For a major element such as Fe, that will continuosly participate in melting as it rises through the mantle, the final isotopic compositon of the magama will be a weighted average of the complete melting column. Thus it is unsuprising that minimal Fe isotope variation are seen between localities. In contrast, the unique geochemical signatures (e.g. He and W) displayed by the Baffin Island picrites are inferred to solely originate from the lowermost mantle and will be continuously diluted upon magma ascent.

A novel 76Se–78Se double spike allows for rapid and precise selenium isotope measurements in geological samples.

Phosphorus availability is considered a limiting factor in many scenarios for the origin of life. The concentration of P in environments of prebiotic interest will have been governed by the available mineral sources of P on the early Earth. A knowledge of early Earth P mineralogy and prevailing global and local environmental conditions is therefore needed to understand which scenarios for prebiotic chemistry are most plausible. Here, we review the plausible diversity of P-bearing phases at Earth’s surface during the emergence of life. We consider phases that were delivered by meteorites (exogenous phases), as well as those that developed solely as a result of Earth system processes (endogenous phases). We take into account the known formation conditions of individual phases, as well as the observed temporal distributions of P-bearing minerals found at Earth’s surface today. Our approach allows us to leverage what is known about changes in the Earth system in order to rule out the prebiotic relevance of many P-bearing phases. Meanwhile, we highlight a small number of phases that are of possible prebiotic relevance; specifically, exogenous schreibersite, merrillite, and apatite, and endogenous apatite, olivine, and glass. Prebiotic mineral-chemical scenarios can be formulated for each phase, with distinct requirements for the environmental and tectonic state of early Earth. We can therefore relate the plausibility of mineral-chemical scenarios to the nature of early Earth, bridging the fields of geoscience and prebiotic chemistry.