Crystallization temperatures of primitive olivine crystals have been widely used as both a proxy for, or an intermediate step in calculating, mantle temperatures. The olivine-spinel aluminum-exchange thermometer has been applied to samples from mid-ocean ridges and large igneous provinces, yielding considerable variability in olivine crystallization temperatures. We supplement the existing data with new crystallization temperature estimates for Hawaii, between 1282±21 and 1375±19°C. Magmatic temperatures may be linked to mantle temperatures if the thermal changes during melting can be quantified. The magnitude of this temperature change depends on melt fraction, itself controlled by mantle temperature, mantle lithology and lithosphere thickness. Both mantle lithology and lithosphere thickness vary spatially and temporally, with systematic differences between mid-ocean ridges, ocean islands and large igneous provinces. For crystallization temperatures to provide robust evidence of mantle temperature variability, the controls of lithosphere thickness and mantle lithology on crystallization temperature must be isolated. We develop a multi-lithology melting model for predicting crystallization temperatures of magmas in both intra-plate volcanic provinces and mid-ocean ridges. We find that the high crystallization temperatures seen at mantle plume localities do require high mantle temperatures. In the absence of further constraints on mantle lithology or melt productivity, we cannot robustly infer variable plume temperatures between ocean-islands and large igneous provinces from crystallization temperatures alone; for example, the extremely high crystallization temperatures obtained for the Tortugal Phanerozoic komatiite could derive from mantle of comparable temperature to modern-day Hawaii. This work demonstrates the limit of petrological thermometers when other geodynamic parameters are poorly known.
Abstract Decades of study have documented several orders of magnitude variation in the oxygen fugacity (fO2) of terrestrial magmas and of mantle peridotites. This variability has commonly been attributed either to differences in the redox state of multivalent elements (e.g., Fe3+/Fe2+) in mantle sources or to processes acting on melts after segregation from their sources (e.g., crystallization or degassing). We show here that the phase equilibria of plagioclase, spinel, and garnet lherzolites of constant bulk composition (including whole-rock Fe3+/Fe2+) can also lead to systematic variations in fO2 in the shallowest ~100 km of the mantle. Two different thermodynamic models were used to calculate fO2 vs. pressure and temperature for a representative, slightly depleted peridotite of constant composition (including total oxygen). Under subsolidus conditions, increasing pressure in the plagioclase-lherzolite facies from 1 bar up to the disappearance of plagioclase at the lower pressure limit of the spinel-lherzolite facies leads to an fO2 decrease (normalized to a metastable plagioclase-free peridotite of the same composition at the same pressure and temperature) of ~1.25 orders of magnitude. The spinel-lherzolite facies defines a minimum in fO2 and increasing pressure in this facies has little influence on fO2 (normalized to a metastable spinel-free peridotite of the same composition at the same pressure and temperature) up to the appearance of garnet in the stable assemblage. Increasing pressure across the garnet-lherzolite facies leads to increases in fO2 (normalized to a metastable garnet-free peridotite of the same composition at the same pressure and temperature) of ~1 order of magnitude from the low values of the spinel-lherzolite facies. These changes in normalized fO2 reflect primarily the indirect effects of reactions involving aluminous phases in the peridotite that either produce or consume pyroxene with increasing pressure: Reactions that produce pyroxene with increasing pressure (e.g., forsterite + anorthite ⇄ Mg-Tschermak + diopside in plagioclase lherzolite) lead to dilution of Fe3+-bearing components in pyroxene and therefore to decreases in normalized fO2, whereas pyroxene-consuming reactions (e.g., in the garnet stability field) lead initially to enrichment of Fe3+-bearing components in pyroxene and to increases in normalized fO2 (although this is counteracted to some degree by progressive partitioning of Fe3+ from the pyroxene into the garnet with increasing pressure). Thus, the variations in normalized fO2 inferred from thermodynamic modeling of upper mantle peridotite of constant composition are primarily passive consequences of the same phase changes that produce the transitions from plagioclase → spinel → garnet lherzolite and the variations in Al content in pyroxenes within each of these facies. Because these variations are largely driven by phase changes among Al-rich phases, they are predicted to diminish with the decrease in bulk Al content that results from melt extraction from peridotite, and this is consistent with our calculations. Observed variations in FMQ-normalized fO2 of primitive mantle-derived basalts and peridotites within and across different tectonic environments probably mostly reflect variations in the chemical compositions (e.g., Fe3+/Fe2+ or bulk O2 content) of their sources (e.g., produced by subduction of oxidizing fluids, sediments, and altered oceanic crust or of reducing organic material; by equilibration with graphite- or diamond-saturated fluids; or by the effects of partial melting). However, we conclude that in nature the predicted effects of pressure- and temperature-dependent phase equilibria on the fO2 of peridotites of constant composition are likely to be superimposed on variations in fO2 that reflect differences in the whole-rock Fe3+/Fe2+ ratios of peridotites and therefore that the effects of phase equilibria should also be considered in efforts to understand observed variations in the oxygen fugacities of magmas and their mantle sources.
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.
Abstract The geochemistry and textures of phosphate minerals can provide insights into the geological histories of parental asteroids, but the processes governing their formation and deformation remain poorly constrained. We assessed phosphorus‐bearing minerals in the three lithologies (light, dark, and melt) of the Chelyabinsk (LL5) ordinary chondrite using scanning electron microscope, electron microprobe, cathodoluminescence, and electron backscatter diffraction techniques. The majority of studied phosphate grains appear intergrown with olivine. However, microtextures of phosphates (apatite [Ca 5 (PO 4 ) 3 (OH,Cl,F)] and merrillite [Ca 9 NaMg(PO 4 ) 7 ]) are extremely variable within and between the differently shocked lithologies investigated. We observe continuously strained as well as recrystallized strain‐free merrillite populations. Grains with strain‐free subdomains are present only in the more intensely shocked dark lithology, indicating that phosphate growth predates the development of primary shock‐metamorphic features. Complete melting of portions of the meteorite is recorded by the shock‐melt lithology, which contains a population of phosphorus‐rich olivine grains. The response of phosphorus‐bearing minerals to shock is therefore hugely variable throughout this monomict impact breccia. We propose a paragenetic history for P‐bearing phases in Chelyabinsk involving initial phosphate growth via P‐rich olivine replacement, followed by phosphate deformation during an early impact event. This event was also responsible for the local development of shock melt that lacks phosphate grains and instead contains P‐enriched olivine. We generalize our findings to propose a new classification scheme for Phosphorus‐Olivine‐Assemblages (Type I–III POAs). We highlight how POAs can be used to trace radiogenic metamorphism and shock metamorphic events that together span the entire geological history of chondritic asteroids.
The pattern of trace element enrichment and variability found in differentiated suites of basalts is a simple 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 crystallization of a single primary melt. Explanations for this over-enrichment have focused on the differentiation processes in crustal magma chambers. Here 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 crystallization (CMC): diverse parental melts were allowed to mix, with a likelihood that is proportional to the extent of fractional crystallization. Using a simple statistical model to explore the effects of concurrent mixing and crystallization 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 content, 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, their MgO contents 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 result from mantle processes: the fact that during mantle melting maximum variability is generated in those elements with the smallest bulk Kd. 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 crystallization, 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.
In order to reconcile petrological and geophysical observations in the temporal domain, the uncertainties of diffusion timescales need to be rigorously assessed. Here we present a new diffusion chronometry method: Diffusion chronometry using Finite Elements and Nested Sampling (DFENS). This method combines a finite element numerical model with a nested sampling Bayesian inversion meaning the uncertainties of the parameters that contribute to diffusion timescale estimates can be rigorously assessed, and that observations from multiple elements can be used to better constrain a single timescale. By accounting for the covariance in uncertainty structure in the diffusion parameters, estimates on timescale uncertainties can be reduced by a factor of 2 over assuming that these parameters are independent of each other. We applied the DFENS method to the products of the Skuggafjöll eruption from the Bárðarbunga volcanic system in Iceland, which contains zoned macrocrysts of olivine and plagioclase that record a shared magmatic history. Olivine and plagioclase provide consistent pre-eruptive mixing and mush disaggregation timescales of less than 1 year. The DFENS method goes some way to improving our ability to rigorously address the uncertainties of diffusion timescales, but efforts still need to be made to understand other systematic sources of uncertainty such as crystal morphology, appropriate choice of diffusion coefficients, growth, and the petrological context of diffusion timescales.
Truong and Lunine (1), in PNAS, recently described a model of the production of phosphine on Venus, in which phosphine is proposed to be the result of interaction of deep-mantle phosphides with acid in the clouds. We believe that it has two quantitative flaws. The first is that erupted material will not reflect the chemistry of its deep-mantle source. Oxygen fugacity is a function of temperature, pressure, and rock composition (e.g., refs. 2 and 3). The oxygen fugacity of a rock of fixed bulk composition at the base of the lithosphere will be substantially different from the oxygen fugacity of the same rock in the deep mantle, even though they have the same intrinsic oxidizing capacity. … [↵][1] 1To whom correspondence may be addressed. Email: bains{at}mit.edu. [1]: #xref-corresp-1-1
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