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The redox evolution of Earth’s interior, as inferred from V/Sc (Fig. 2.3a), is central to the debate on the role of the mantle in the transition from an anoxic to an oxygenated atmosphere during the so‐called Great Oxidation Event (GOE) around 2.4–2.2 Ga, which was preceded by “whiffs of oxygen” (Lyons et al., 2014) as shown in Fig. 2.3b. The mantle–asthenosphere connection was hypothesized early (Kasting et al., 1993; Holland, 2002), but subsequently dismissed by various workers finding only small or no difference in the redox state of Archean and post‐Archean magmas (e.g., Canil, 1997; Delano, 2001; Li & Lee, 2004; Trail et al., 2011; Rollinson et al., 2017). In contrast, the data shown in Fig. 3.3c document a redox evolution based on samples derived from both ambient mantle and deeper “plume” mantle, which crosses the fO₂ region where volcanic gases become sources as opposed to sinks of O₂ when first whiffs of oxygen appeared (highlighted by the bar F_in = F_out after Holland, 2002) at ca. 3.5–3.2 Ga, reaffirming a role for the mantle in atmospheric oxygenation. Although the relationship between the redox state of a magma and the gases released to the atmosphere at any point in time during magmatic activity is controlled by multiple parameters (e.g., Gaillard et al., 2011; Moussallam et al., 2019), it is inescapable that the oxidation state of the sum of the gases emitted over the course of volcanism must reflect that of the magma with which they were once in equilibrium. The cause of this apparent mantle redox evolution possibly goes back to Earth’s origins. Once sufficient mass had been accreted, FeO disproportionated into Fe metal at high pressure, about 10% of which was extracted into the core, and Fe₂O₃, which was left behind in the magma ocean (Armstrong et al., 2019) and, thus, inherited by the rocky mantle where it partitioned into bridgmanite (Frost et al., 2004), corresponding to an increase in mantle O₂ (Wade & Wood 2005). This was followed by gradual exhumation of O₂‐enriched lowermost material by mantle convection processes. This was put forward by both Aulbach and Stagno (2016) and Nicklas et al. (2019) as one plausible explanation for the fO₂ trends in their data. Early subduction of oxidized surficial material to raise mantle fO₂ was offered as an alternative process to explain the fO₂ trend (Nicklas et al., 2019). Interestingly, Archean placer diamonds formed between 3.5 and 3.1 Ga show geochemical markers of an origin by reduction of oxidized fluids accompanied by input of Archean sediments (Smart et al., 2016). However, mantle oxidation by subduction implies that O₂ would have to be taken from the ocean–atmosphere system and cause a corresponding reduction in order to produce the oxidizing material carried down. Similarly, subduction of reduced material (Duncan & Dasgupta, 2017) may cause a transient increase in atmospheric O₂, but, if not permanently sequestered into a “hidden” reservoir, would have a reducing effect on the mantle and ultimately cause it to release more reducing gases upon melting.

Figure 2.3 (a) V/Sc and (B) calculated LogfO₂ (normalized to the FMQ buffer) corrected to 1 GPa of mid‐ocean ridge‐derived (meta)basalts sampling the ambient convecting mantle (modified from Aulbach and Stagno, 2016), where error bars on V/Sc represent 1σ of the mean per sample suite, those on ΔFMQ are propagated 1σ errors of V/Sc, and those on the age represent age ranges or 1σ errors for isochron ages reported in the literature. In two suites, samples with the lowest V/Sc were excluded for a conservative estimate. Range of V/Sc for continental Archean basalts in (a) from Li and Lee (2004). Shown for comparison in (b) are fO₂ estimated by Nicklas et al. (2018; 2019) for picritic and komatiitic systems, based on the redox‐dependent distribution of V between liquidus olivine and melt. Note that because of an unresolved inter‐calibration issue, their MORB fO₂ estimate is offset to higher values (ΔFMQ + 0.60±0.15) from those derived in other works (~–0.4±0.4; Li and Lee, 2004; Frost and McCammon, 2008; +0.1; Berry et al., 2018), and all results were shifted down by one log unit for comparability to the V/Sc‐derived MORB fO₂ of –0.4. Range of fO₂ in the magma ocean at ca. 4.5 Ga permitted based on chondritic D/H in the water ocean, which places an upper limit on H₂ escape from the atmosphere, from Pahlevan et al. (2019) is shown for comparison (vertical blue-grey arrow). Timing of the Great Oxidation Event (GOE) around 2.4 Ga and “whiffs of oxygen” from Lyons et al. (2014) (c) shows the speciation of continental and oceanic volcanic gases, with mixtures thereof lying between these two curves, as a function of fO₂ based on modern volcanic volatile fluxes (6.00 x 10¹² for C, 1.15 x 10¹⁴ for H, and 2.13 x 10¹² for S), illustrating the transition from such gases acting as sinks (reducing) and sources (oxidizing) of O₂ compared to the estimated average modern O₂ input (from burial of reduced components) and its upper and lower limit

(modified from Li & Lee, 2004).

Regardless of the extent and timing of mantle oxidation, both the eclogite and the komatiite datasets contain outliers testifying to redox heterogeneity in the convecting mantle, possibly inherited from the aforementioned accretion and magma ocean processes and preserved in mantle regions that had not been remixed at the time of melt generation (Nicklas et al., 2019). This raises the question of the timescales needed to mix deep oxidized mantle regions into the upper convecting mantle. Gu et al. (2016) showed that an oxidized lower mantle assemblage left over after core formation would be less dense than its reduced equivalent, facilitating its ascent, which they modelled to be completed by 3.6 Ga ago, although the exact magnitude of the density contrast is debated (Liu et al., 2018). In contrast, the data shown in Fig. 3a–c suggest that this remixing occurred over longer timescales and into the Late Paleoproterozoic. Such long‐lived heterogeneity is supported also from the preservation of anomalous compositions of the short‐lived isotopes, which must date back to processes occurring during the first several 100 Ma, in magmas erupted throughout the Archean and even to this day (e.g., Rizo et al., 2016; Horan et al., 2018). Factors possibly contributing to retarded mantle homogenization include grain size (Foley & Rizo, 2017) and the strength of bridgmanite under lower mantle conditions (Girard et al., 2016). Vertical mixing of oxidized material left after core formation would eventually have been aided by the establishment of plate tectonics (Andrault et al., 2018), bearing in mind that the transition to sustained plate tectonics occurred late (3.2–2.5 Ga; Cawood et al., 2019) relative to the onset of upward mixing, sometime between the post‐core formation establishment of fO₂ in the uppermost mantle of ~ΔFMQ‐4.5 (Frost and McCammon, 2008) and the significantly more oxidizing source fO₂ recorded by 3.5 Ga komatiites (Fig. 2.3b; Nicklas et al., 2018).

Superposed on the upward mixing of post‐core formation oxidized mantle regions would be heterogeneities due to late accretion and associated downward mixing of late‐accreted material, which are difficult to quantify. For example, the abundance and partitioning of moderately siderophile elements apparently requires addition of increasingly oxidized material (Wood et al., 2006), whereas late meteoritic bombardment with reduced components has been inferred based on the Ce‐in‐zircon redox proxy (Yang et al., 2014). Wang and Becker (2013) suggest that volatile‐rich objects were involved based on Se–Te systematics, whereas Fischer‐Gödde and Kleine (2017) call for a reduced inner solar system source based on Ru isotopes. Thus, more work is required to quantitatively model the effects of downward mixing of late‐accreted material on mantle fO₂ and to accurately capture the rise of post‐core formation oxidized lower mantle regions in numerical models. Pinpointing this evolution is critical to constraining the composition of gases released from Hadaean and Archean magmas to the atmosphere, which has implications for a multitude of issues affecting habitability on Earth, from the production of prebiotic molecules to the Faint Young Sun paradox and finally, the transition to an oxygenated atmosphere.