Erebus hydrogen emissions, oxidation state, phase equilibria, and anorthoclase megacrystals

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 condi- tions 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.

Field 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 1025C, in pressure from atmospheric to 300 MPa, in water content from 0 to 8wt %, 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 +/- 25C, a pressure below 200 MPa, redox conditions between QFM and QFM - 1, and re- markably 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 925C, 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 +/- 25C 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.

The 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.

Active volcanoes are typically fed by magmatic reservoirs situated within the upper crust. The development of thermal and/or compositional gradients in such magma chambers may lead to vigorous convection as inferred from theoretical models and evidence for magma mixing recorded in volcanic rocks. Bi-directional flow is also inferred to prevail in the conduits of numerous persistently-active volcanoes based on observed gas and thermal emissions at the surface, as well as experiments with analogue models. However, more direct evidence for such exchange flows has hitherto been lacking. Here, we analyse the remarkable oscillatory zoning of anorthoclase feldspar megacrystals erupted from the lava lake of Erebus volcano, Antarctica. A comprehensive approach, combining phase equilibria, solubility experiments and melt inclusion and textural analyses shows that the chemical profiles are best explained as a result of multiple episodes of magma transport between a deeper reservoir and the lava lake at the surface. Individual crystals have repeatedly travelled up-and-down the plumbing system, over distances of up to several kilometers, presumably as a consequence of entrainment in the bulk magma flow. Our findings thus corroborate the model of bi-directional flow in magmatic conduits. They also imply contrasting flow regimes in reservoir and conduit, with vigorous convection in the former (regular convective cycles of ∼150 days at a speed of ∼0.5 mm s^−1) and more complex cycles of exchange flow and re-entrainment in the latter. We estimate that typical, 1-cm-wide crystals should be at least 14 years old, and can record several (from 1 to 3) complete cycles between the reservoir and the lava lake via the conduit. This persistent recycling of phonolitic magma is likely sustained by CO2 fluxing, suggesting that accumulation of mafic magma in the lower crust is volumetrically more significant than that of evolved magma within the edifice.