Volcanic emissions link the oxidation state of the Earth's mantle to the composition of the atmosphere. Whether the oxidation state of an ascending magma follows a redox buffer – hence preserving mantle conditions – or deviates as a consequence of degassing remains under debate. Thus, further progress is required before erupted basalts can be used to infer the redox state of the upper mantle or the composition of their co-emitted gases to the atmosphere. Here we present the results of X-ray absorption near-edge structure (XANES) spectroscopy at the iron K-edge carried out for a series of melt inclusions and matrix glasses from ejecta associated with three eruptions of Kīlauea volcano (Hawai‘i). We show that the oxidation state of these melts is strongly correlated with their volatile content, particularly in respect of water and sulfur contents. We argue that sulfur degassing has played a major role in the observed reduction of iron in the melt, while the degassing of H2O and CO2 appears to have had a negligible effect on the melt oxidation state under the conditions investigated. Using gas–melt equilibrium degassing models, we relate the oxidation state of the melt to the composition of the gases emitted at Kīlauea. Our measurements and modelling yield a lower constraint on the oxygen fugacity of the mantle source beneath Kīlauea volcano, which we infer to be near the nickel nickel-oxide (NNO) buffer. Our findings should be widely applicable to other basaltic systems and we predict that the oxidation state of the mantle underneath most hotspot volcanoes is more oxidised than that of the associated lavas. We also suggest that whether the oxidation states of a basalt (in particular MORB) reflects that of its source, is primarily determined by the extent of sulfur degassing

Emission of volcanic gas is thought to be the dominant process by which volatiles transit from the deep earth to the atmosphere. Volcanic gas emissions, remain poorly constrained, and volcanoes of Peru are entirely absent from the current global dataset. In Peru, Sabancaya and Ubinas volcanoes are by far the largest sources of volcanic gas. Here, we report the first measurements of the compositions and fluxes of volcanic gases emitted from these volcanoes. The measurements were acquired in November 2015. We determined an average SO2 flux of 15.3 ± 2.3 kg s− 1 (1325-ton day− 1) at Sabancaya and of 11.4 ± 3.9 kg s− 1 (988-ton day− 1) at Ubinas using scanning ultraviolet spectroscopy and dual UV camera systems. In-situ Multi-GAS analyses yield molar proportions of H2O, CO2, SO2, H2S and H2 gases of 73, 15, 10 1.15 and 0.15 mol% at Sabancaya and of 96, 2.2, 1.2 and 0.05 mol% for H2O, CO2, SO2 and H2S at Ubinas. Together, these data imply cumulative fluxes for both volcanoes of 282, 30, 27, 1.2 and 0.01 kg s− 1 of H2O, CO2, SO2, H2S and H2 respectively. Sabancaya and Ubinas volcanoes together contribute about 60% of the total CO2 emissions from the Central Volcanic zone, and dominate by far the total revised volatile budget of the entire Central Volcanic Zone of the Andes.SCOPUS: ar.jinfo:eu-repo/semantics/publishe

The continuous measurement of molecular hydrogen (H₂) emissions from passively degassing volcanoes has recently been made possible using a new generation of low-cost electrochemical sensors. We have used such sensors to measure H₂, along with SO₂, H₂O and CO₂, in the gas and aerosol plume emitted from the phonolite lava lake at Erebus volcano, Antarctica. The measurements were made at the crater rim between December 2010 and January 2011. Combined with measurements of the long-term SO₂ emission rate for Erebus, they indicate a characteristic H₂ flux of 0.03 kg s^–1 (2.8 Mg day^–1). The observed H₂ content in the plume is consistent with previous estimates of redox conditions in the lava lake inferred from mineral compositions and the observed CO₂/CO ratio in the gas plume (∼0.9 log units below the quartz–fayalite–magnetite buffer). These measurements suggest that H₂ does not combust at the surface of the lake, and that H₂ is kinetically inert in the gas/aerosol plume, retaining the signature of the high-temperature chemical equilibrium reached in the lava lake. We also observe a cyclical variation in the H₂/SO₂ ratio with a period of ∼10 min. These cycles correspond to oscillatory patterns of surface motion of the lava lake that have been interpreted as signs of a pulsatory magma supply at the top of the magmatic conduit.