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International audienceThe conventional view holds that the oxidation state of a mantle-derived degassed magma reflects its source. During magma ascent and degassing the oxidation state is thought to follow a redox buffer. While this view has been challenged by petrological data, geochemical models and volcanic gas measurements, the fingerprints of such redox changes and their driving forces have not hitherto been captured by an integrated study. Here, we track the redox evolution of an alkaline magmatic suite at Erebus volcano, Antarctica, from the mantle to the surface, using X-ray absorption near-edge structure (XANES) spectroscopy at the iron and sulphur K-edges. We find that strong reduction of Fe and S dissolved in the melt accompanies magma ascent. Using a model of gas-melt chemical equilibria, we show that sulphur degassing is the driving force behind this evolutionary trend, which spans a wide compositional and depth range. Our results explain puzzling shifts in the oxidation state of gases emitted from Erebus volcano, and indicate that, where sulphur degassing occurs, the oxidation states of degassed volcanic rocks may not reflect their mantle source or co-eruptive gas phase. This calls for caution when inferring the oxidation state of the upper mantle from extrusive rocks and a possible re-assessment of the contribution of volcanic degassing to the early Earth's atmosphere and oceans. The relationship between magma redox conditions and pressure (depth) emphasises the value of measuring redox couples in gases emitted from volcanoes for the purposes of operational forecasting

We present here the first volcanic gas compositional time‐series taken prior to a paroxysmal eruption of Villarrica volcano (Chile). Our gas plume observations were obtained using a fully autonomous Multi‐component Gas Analyser System (Multi‐GAS) in the 3 month‐long phase of escalating volcanic activity that culminated into the 3 March 2015 paroxysm, the largest since 1985. Our results demonstrate a temporal evolution of volcanic plume composition, from low CO2/SO2 ratios (0.65‐2.7) during November 2014‐January 2015 to CO2/SO2 ratios up to ≈ 9 then after. The H2O/CO2 ratio simultaneously declined to <38 in the same temporal interval. We use results of volatile saturation models to demonstrate that this evolution toward CO2‐enriched gas was likely caused by unusual supply of deeply sourced gas bubbles. We propose that separate ascent of over‐pressured gas bubbles, originating from at least 20‐35 MPa pressures, was the driver for activity escalation toward the 3 March climax.

Editor: T.A. MatherKeywords: mantle f O 2 XANES oxygen mantle heterogeneity pyroxenite 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 longand short-wavelength heterogeneity in the Iceland plume. We present new high-precision Fe-XANES measurements of Fe 3+ / Fe on a suite of 64 basalt glasses from the Reykjanes Ridge. These basalts exhibit positive correlations between Fe 3+ / Fe and trace element and isotopic signals of enrichment, and become progressively oxidised towards Iceland: fractionation-corrected Fe 3+ / Fe increases by ∼ 0.015 and QFM 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 ([Fe 2 O 3 ] source ) we project observed liquid compositions to an estimate of Fe 2 O 3 in the pure enriched endmember melt, and then apply simple fractional melting models, considering lherzolitic and pyroxenitic source mineralogies, to estimate [Fe 2 O 3 ] (source) content. Propagating uncertainty through these steps, we obtain a range of [Fe 2 O 3 ] (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 lherzolitebasalt (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.

From oxic atmosphere to metallic core, the Earth's components are broadly stratified with respect to oxygen fugacity. A simple picture of reducing oxygen fugacity with depth may be disrupted by the accumulation of oxidised crustal material in the deep lower mantle, entrained there as a result of subduction. While hotspot volcanoes are fed by regions of the mantle likely to have incorporated such recycled material, the oxygen fugacity of erupted hotspot basalts had long been considered comparable to slightly more oxidised than that of mid-ocean ridge basalt (MORB) and more reduced than subduction zone basalts. Here we report measurements of the redox state of glassy crystal-hosted melt inclusions from tephra and quenched lava samples from the Canary and Cape Verde Islands, that we can independently show were entrapped prior to extensive sulfur degassing. We find high ferric iron to total iron ratios (Fe 3+ /∑Fe) of up to 0.27-0.30, indicating that mantle plume primary melts are significantly more oxidised than those at mid-ocean ridges and even subduction zone contexts. These results, together with previous investigations from the Erebus, Hawaiian and Icelandic hotspots, confirm that mantle upwelling provides a return flow from the deep Earth for components of oxidised subducted lithosphere and suggest that highly oxidised material accumulates or is generated in the lower mantle. The oxidation state of the Earth's interior must therefore be highly heterogeneous and potentially locally inversely stratified.

Eruptive activity shapes volcanic edifices. The formation of broad caldera depressions is often associated with major collapse events, emplacing conspicuous pyroclastic deposits. However, caldera subsidence may also proceed silently by magma withdrawal at depth, more difficult to detect. Ambrym, a basaltic volcanic island, hosts a 12-km wide caldera and several intensely-degassing lava lakes confined to intra-caldera cones. Using satellite remote sensing of deformation, gas emissions and thermal anomalies, combined with seismicity and ground observations, we show that in December 2018 an intra-caldera eruption at Ambrym preceded normal faulting with >2 m of associated uplift along the eastern rift zone and 2.5 m of caldera-wide subsidence. Deformation was caused by lateral migration of >0.4 cubic kilometers of magma into the rift zone, extinguishing the lava lakes, and feeding a submarine eruption in the rift edge. Recurring rifting episodes, favored by stress induced by the D’Entrecasteaux Ridge collision against the New Hebrides arc, lead to progressive subsidence of Ambrym’s caldera and concurrent draining of the lava lakes. Although counterintuitive, convergent margin systems can induce rift zone volcanism and subsequent caldera subsidence.

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