Hydrogen emissions from Erebus volcano, Antarctica

International audienceThe 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

Experimental Phase-equilibrium Constraints on the Phonolite Magmatic System of Erebus Volcano, Antarctica

International audienceField observations and petrological studies have recently advanced understanding of the magmatic system of Erebus volcano, renowned for its sustained CO2-rich degassing, and long-lived phonolitic lava lake. However, this body of work has highlighted uncertainty in several key parameters, including the magma temperature, redox state and the depth of the reservoir presumed to maintain the lava lake. Here, we use experimentally determined phase equilibria to constrain these unknowns. The experiments ranged in temperature from 900 to 1025°C, in pressure from atmospheric to 300 MPa, in water content from 0 to 8 wt %, and in oxygen fugacity from NNO + 4 (where NNO is nickel-nickel oxide) to QFM - 2 (where QFM is quartz-fayalite-magnetite). The natural system was experimentally reproduced at 950 ± 25°C, a pressure below 200 MPa, redox conditions between QFM and QFM - 1, and remarkably low water contents of less than 0*5 wt %. These findings help in understanding petrological observations, including melt inclusion data, as well as the measured composition of gas emissions from the lava lake. Biotite and amphibole appear in the crystallization sequence at around 925°C, even under very dry conditions (biotite). Both biotite and amphibole are absent in the phonolites erupted over the last 20 kyr at Erebus. The constant abundance of anorthoclase observed in the erupted lavas and bombs indicates that the shallow magmatic system feeding the Erebus lava lake (below pressures of 200 MPa) has been thermally buffered at 950 ± 25°C over this time period, possibly reflecting steady-state connection with the deep feeding system rooted in the mantle. Combined with recent seismological data, our results suggest that if a large phonolitic reservoir exists, then it should lie in the depth range 4-7*5 km. The tight constraints on temperature and redox conditions will be valuable for future thermodynamical and rheological modelling

Magmatic carbon outgassing and uptake of CO2 by alkaline waters

Much of Earth's carbon resides in the “deep” realms of our planet: sediments, crust, mantle, and core. The interaction of these deep reservoirs of carbon with the surface reservoir (atmosphere and oceans) leads to a habitable surface environment, with an equitable atmospheric composition and comfortable range in temperature that together have allowed life to proliferate. The Earth in Five Reactions project (part of the Deep Carbon Observatory program) identified the most important carbon-bearing reactions of our planet, defined as those which perhaps make our planet unique among those in our Solar System, to highlight and review how the deep and surface carbon cycles connect. Here we review the important reactions that control the concentration of carbon dioxide in our atmosphere: outgassing from magmas during volcanic eruptions and during magmatic activity; and uptake of CO2 by alkaline surface waters. We describe the state of our knowledge about these reactions and their controls, the extent to which we understand the mass budgets of carbon that are mediated by these reactions, and finally, the implications of these reactions for understanding present-day climate change that is driven by anthropogenic emission of CO2

CO 2 Solubility in Kimberlite melts CO 2 Solubility in Kimberlite melts

International audienceCarbon dioxide is the most abundant volatile in kimberlite melts and its solubility exerts a prime influence on the melt structure, buoyancy, transport rate and hence eruption dynamics. The actual primary composition of kimberlite magma is the matter of some debate but the solubility of CO2 in kimberlitic melts is also poorly constrained due to difficulties in quenching these compositions to a glass that retains the equilibrium CO2 content. In this study we used a range of synthetic, melt compositions with broadly kimberlitic to carbonatitic characteristics which can, under certain conditions, be quenched fast enough to produce a glass. These materials are used to determine the CO2 solubility as a function of chemical composition and pressure (0.05-1.5 GPa). Our results suggest that the solubility of CO2 decreases steadily with increasing amount of network forming cations from ~ 30 wt% CO2 at 12 wt% SiO2 down to ~ 3 wt% CO2 at 40 wt% SiO2. For low silica melts, CO2 solubility correlates non-linearly with pressure showing a sudden increase from 0.1 to 100 MPa and a smooth increase for pressure > 100 MPa. This peculiar pressure-solubility relationship in low silica melts implies that CO2 degassing must mostly occur within the last 3 km of ascent to the surface having potential links with the highly explosive nature of kimberlite magmas and some of the geo-morphological features of their root zone. We present an empirical CO2 solubility model covering a large range of melt composition from 11 to 55 wt% SiO2 spanning the transition from carbonatitic to kimberlitic at pressures from 1500 to 50 MPa

A novel approach to volcano surveillance using gas geochemistry

Identifying precursory phenomena is central to the short-range assessment and anticipation of volcanic hazards. The chemistry of gases, which may separate from magma at depth, is operationally monitored at many volcanoes worldwide to manage risk. However, owing to the complexity of volcanic degassing, decoding the message of gas geochemistry has proven challenging. Here, we report an approach to restoration of measured volcanic gas compositions that enables tracking of variations in the temperature and/or oxidation state of the source magma. We validate the approach with reference to independent estimates of melt oxidation state obtained by X-ray absorption near-edge structure (XANES) spectroscopy at the iron K-edge. We then apply the method to a global database of high temperature volcanic gases and to extended gas geochemical timeseries at Unzen, Aso, and Asama volcanoes, identifying hitherto unreported but significant changes in magma intensive parameters that preceded or accompanied changes in volcanic activity. Restoration of volcanic gas compositions offers a promising complement to monitoring strategies at active volcanoes, calling for more systematic operational surveillance of redox-sensitive gas species

Olivine-hosted melt inclusions as an archive of redox heterogeneity in magmatic systems

The redox state of volcanic products determines their leverage on the oxidation of Earth's oceans and atmosphere, providing a long-term feedback on oxygen accumulation at the planet's surface. An archive of redox conditions in volcanic plumbing systems from a magma's mantle source, through crustal storage, to eruption, is carried in pockets of melt trapped within crystals. While melt inclusions have long been exploited for their capacity to retain information on a magma's history, their permeability to fast-diffusing elements such as hydrogen is now well documented and their retention of initial oxygen fugacities () could be similarly diffusion-limited. To test this, we have measured Fe3+/ΣFe by micro-XANES spectroscopy in a suite of 65 olivine-hosted melt inclusions and 9 matrix glasses from the AD 1783 Laki eruption, Iceland. This eruption experienced pre-eruptive mixing of chemically diverse magmas, syn-eruptive degassing at the vent, and post-eruptive degassing during lava flow up to 60 km over land, providing an ideal test of whether changes in the of a magma may be communicated through to its cargo of crystal-hosted melt inclusions. Melt inclusions from rapidly quenched tephra samples have Fe3+/ΣFe of (ΔQFM of +0.7 ± 0.1), with no correlation between their and degree of trace element enrichment or differentiation. These inclusions preserve the redox conditions of the mixed pre-eruptive Laki magma. When corrected for fractional crystallisation to 10 wt.% MgO, these inclusions record a parental magma [Fe3+/ΣFe](10) of 0.18 (ΔQFM of +0.4), significantly more oxidised than the Fe3+/ΣFe of 0.10 that is often assumed for Icelandic basalt magmas. Melt inclusions from quenched lava selvages are more reduced than those from the tephra, having Fe3+/ΣFe between 0.133 and 0.177 (ΔQFM from −0.4 to +0.4). These inclusions have approached equilibrium with their carrier lava, which has been reduced by sulfur degassing. The progressive re-equilibration of between inclusions and carrier melts occurs on timescales of hours to days, causing a drop in the sulfur content at sulfide saturation (SCSS) and driving the exsolution of immiscible sulfide globules in the inclusions. Our data demonstrate the roles of magma mixing, progressive re-equilibration, and degassing in redox evolution within magmatic systems, and the open-system nature of melt inclusions to during these processes. Redox heterogeneity present at the time of inclusion trapping may be overprinted by rapid re-equilibration of melt inclusion with the external environment, both in the magma chamber and during slow cooling in lava at the surface. This can decouple the melt inclusion archives of , major and trace element chemistry, and mask associations between , magmatic differentiation and mantle source heterogeneity unless the assembly of diverse magmas is rapidly followed by eruption. Our tools for understanding the redox conditions of magmas are thus limited; however, careful reconstruction of pre- and post-eruptive magmatic history has enabled us to confirm the relatively oxidised nature of ocean island-type mantle compared to that of mid-ocean ridge mantle

Isotopically (δ13C and δ18O) heavy volcanic plumes from Central Andean volcanoes: a field study

Stable isotopes of carbon and oxygen in volcanic gases are key tracers of volatile transfer between Earth’s interior and atmosphere. Although important, these data are available for few volcanoes because they have traditionally been difficult to obtain and are usually measured on gas samples collected from fumaroles. We present new field measurements of bulk plume composition and stable isotopes (δ13CCO2 and δ18OH2O+ CO2) carried out at three northern Chilean volcanoes using MultiGAS and isotope ratio infrared spectroscopy. Carbon and oxygen in magmatic gas plumes of Lastarria and Isluga volcanoes have δ13C in CO2 of +0.76‰ to +0.77‰ (VPDB), similar to slab carbonate; and δ18O in the H2O + CO2 system ranging from +12.2‰ to +20.7‰ (VSMOW), suggesting significant contributions from altered slab pore water and carbonate. The hydrothermal plume at Tacora has lower δ13CCO2 of −3.2‰ and δ18OH2O+CO2 of +7.0‰, reflecting various scrubbing, kinetic fractionation, and contamination processes. We show the isotopic characterization of volcanic gases in the field to be a practical complement to traditional sampling methods, with the potential to remove sampling bias that is a risk when only a few samples from accessible fumaroles are used to characterize a given volcano’s volatile output. Our results indicate that there is a previously unrecognized, relatively heavy isotopic signature to bulk volcanic gas plumes in the Central Andes, which can be attributed to a strong influence from components of the subducting slab, but may also reflect some local crustal contamination. The techniques we describe open new avenues for quantifying the roles that subduction zones and arc volcanoes play in the global carbon cycle.Published653V. Proprietà dei magmi e dei prodotti vulcaniciJCR Journa

Deep Earth carbon reactions through time and space

The authors acknowledge partial support from the Sloan Foundation grant G-2016-7157.Reactions involving carbon in the deep Earth have limited manifestation on Earth’s surface, yet they have played a critical role in the evolution of our planet. The metal-silicate partitioning reaction promoted carbon capture during Earth’s accretion and may have sequestered substantial carbon in Earth’s core. The freezing reaction involving iron-carbon liquid could have contributed to the growth of Earth’s inner core and the geodynamo. The redox melting/freezing reaction largely controls the movement of carbon in the modern mantle, and reactions between carbonates and silicates in the deep mantle also promote carbon mobility. The ten-year activity of the Deep Carbon Observatory has made important contributions to our knowledge of how these reactions are involved in the cycling of carbon throughout our planet, both past and present, and helped to identify gaps in our understanding that motivate and give direction to future studies.Publisher PDFPeer reviewe

Unrest at the Nevados de Chillán volcanic complex: a failed or yet to unfold magmatic eruption?

Resuming erupting activity at volcanoes that have been long quiescent poses a significant challenge to hazard assessment, as it require assessment of whether the change in activity is an isolated event or the beginning of a new eruptive sequence. Such inception is often poorly characterised as quiescent volcanoes tend to be poorly equipped and not extensively monitored, especially with respect to gas geochemistry. Here, we report gas composition and flux measurements from a newly opened vent at the very onset of eruptive activity at the Nevados de Chillán volcanic complex (Chile) in January-February 2016. The molar proportions of H2O, CO2, SO2, H2S and H2 gases are found to be 98.4, 0.97, 0.11, 0.01 and 0.5 mol% respectively. The mean SO2 flux recorded in early February 2016 during periods of eruptive discharge amounts to 0.4-0.6 kg s-1. Our results indicate that the new vent opening was propelled by magmatic gases, triggering repeated eruptions. Ash particles ejected by the first blast of 8 January are dominated by lithic fragments of dacitic composition. By contrast the ash ejected in a subsequent eruption contains both lithic fragments of dense dacite, and a fresher, sparsely vesicular material of basaltic andesite composition. By October 2017 the ejected ash is back to being dominated by the dense dacitic lithic material. Together with the seismic and deformation record, these observations point to the explosive activity resulting from a small intrusion of basaltic to andesitic magma at shallow level. The fate of this magma, whether stalling or eventually triggering a magmatic eruption, remains to be seen, but current observations suggest the former is most likely