The effects of solid-solid phase equilibria on the oxygen fugacity of the upper mantle

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.

Partitioning of Fe2O3 in peridotite partial melting experiments over a range of oxygen fugacities elucidates ferric iron systematics in mid-ocean ridge basalts and ferric iron content of the upper mantle

“…Several different methods of modeling f O2 in the mantle find that for a bulk mantle Fe 3+ /ΣFe ratio of 0.03 (Canil et al 1994) the shallow mantle should record f O2 of about QFM-1, which is in agreement with the continental xenolith record (e.g., Frost and McCammon 2008) but about one log unit more reduced than recorded by average MORB (Cottrell and Kelley 2011;O'Neill et al 2018;Zhang et al 2018). Jennings and Holland (2015) and Stolper et al (2020) used a THERMOCALCbased model, andStolper et al (2020) also used pMELTS, to calculate phase equilibria for a peridotite bulk composition with fixed Fe 3+ /ΣFe ratio = 0.03 at upper mantle pressures and temperatures. Jennings and Holland (2015) allowed melting to occur and Stolper et al (2020) suppressed melt formation, but both found that f O2 is lower in the spinel peridotite stability field than in the shallowest part of the garnet peridotite stability field.…”

“…Each predict that spinel-field f O2 is in the range QFM-2 to QFM-1. The implications of Jennings and Holland (2015) and Stolper et al (2020) is that mantle with continental lithosphere-like Fe 2 O 3 concentrations are more reduced at the depths of MORB generation than QFM, which is the f O2 of the MORB source inferred from MORB themselves (Fig. 1; Cottrell and Kelley 2011;O'Neill et al 2018).…”

“…Jennings and Holland (2015) and Stolper et al (2020) used a THERMOCALCbased model, andStolper et al (2020) also used pMELTS, to calculate phase equilibria for a peridotite bulk composition with fixed Fe 3+ /ΣFe ratio = 0.03 at upper mantle pressures and temperatures. Jennings and Holland (2015) allowed melting to occur and Stolper et al (2020) suppressed melt formation, but both found that f O2 is lower in the spinel peridotite stability field than in the shallowest part of the garnet peridotite stability field. Each predict that spinel-field f O2 is in the range QFM-2 to QFM-1.…”

The mantle source of basalts from Reunion Island is not more oxidized than the MORB source mantle

“…There are many factors that could influence the fO 2 of a partial melt of the mantle including: the major element composition of the source, which influences the mineralogy and phase equilbria under both subsolidus and supersolidus conditions as functions of P and T and could lead to variations of at least one order of magnitude in fO 2 (e.g., Jennings and Holland, 2015;Stolper et al 2020); the concentrations and oxidation states of heterovalent elements in the source, including not only Fe, but also H, C, S, and more (e.g., Frost and McCammon 2008 and references therein); and the flow of fluids through the source (e.g., Frost and McCammon 2008 and references therein). Given these and other possible factors that could influence the fO 2 levels of the mantle sources of magmas, it is difficult at this time to decode the significance of the essentially identical fO 2 levels of magmas from the C/FOZO/PREMA-rich Reunion plume source (as defined by this study and previous studies of different lavas from Reunion island, Fig.…”

Melting conditions and mantle source composition from probabilistic joint inversion of major and rare earth element concentrations

“…Although a detailed comparison between thermodynamic softwares and/or databases is beyond the scope of this paper (cf. Stolper et al, 2020), the electronic annex includes a comprehensive summary of the mineral distribution, solid and melt chemistry as a function of pressure, temperature and chemical composition used in this paper and obtained with Perple X using the thermodynamic model from the use of these thermodynamic models.…”