Sulphur behaviour and redox conditions in etnean magmas during magma differentiation and degassing
Authors: Gennaro Emanuela , Paonita Antonio , Iacono-Marziano Giada , Moussallam Yves , Pichavant Michel , Peters Nial , Martel Caroline 
Published: October 2020

Abstract
Sulphur behaviour and variations in redox conditions during magma differentiation and degassing in Mt. Etna (Italy) volcanic system have been explored by integrating the study of olivine-hosted melt inclusions (MIs) with an experimental survey of sulphur solubility in hydrous basaltic magmas.
Sulphur solubility experiments were performed at conditions relevant to the Etnean plumbing system (1200 °C, 200 MPa and oxygen fugacity between NNO + 0.2 and NNO + 1.7, with NNO being the Nickel-Nickel Oxide buffer), and their results confirm the important control of oxygen fugacity (fO2) on S abundance in mafic magmas and on S partitioning between fluid and melt phases (DSfluid/melt). The observed DSfluid/melt value increases from 51 ± 4 to 146 ± 6 when fO2 decreases from NNO + 1.7 ± 0.5 to NNO + 0.3.
Based on the calculated DSfluid/melt and a careful selection of previously published data, an empirical model is proposed for basaltic magmas in order to predict the variation of DSfluid/melt values upon variations in P (25–300 MPa), T (1030–1200 °C) and fO2 (between NNO-0.8 and NNO + 2.4).
Olivine-hosted melt inclusions (Fo89-91) from tephra of the prehistoric (4 ka BP) sub-plinian picritic eruption, named FS (“Fall Stratified”), have been investigated for their major element compositions, volatile contents and iron speciation (expressed as Fe3+/ƩFe ratio). These primitive MIs present S content from 235 ± 77 to 3445 ± 168 ppm, while oxygen fugacity values, estimated from Fe3+/ƩFe ratios, range from NNO + 0.7 ± 0.2 to NNO + 1.6 ± 0.2.
Iron speciation has also been investigated in more evolved and volatile-poorer Etnean MIs. The only primitive melt inclusion from Mt. Spagnolo eruption (4–15 ka BP) presents a S content of 1515 ± 49 ppm and an estimated fO2 of NNO + 1.4 ± 0.1. The more evolved MIs (from 2002/2003, 2006, 2008/2009 and 2013 eruptions) have S content lower than 500 ppm, and their Fe3+/ΣFe ratios result in fO2 between NNO-0.9 ± 0.1 and NNO + 0.4 ± 0.1.
Redox conditions and S behaviour in Etnean magmas during degassing and fractional crystallization were modelled coupling MELTS code with our empirical DSfluid/melt model. Starting from a FS-type magma composition and upon decrease of T and P, fractional crystallization of olivine, clinopyroxene, spinel and plagioclase causes a significant fO2 decrease. The fO2 reduction, in turn, causes a decrease in sulphur solubility and an increase in DSfluid/melt, promoting S exsolution during magma ascent, which further enhances the reduction of fO2. For the evolved melt inclusions of 2002–2013 eruptions, magma differentiation may therefore have played a crucial role in decreasing redox conditions and favouring efficient S degassing.
Differently, during the unusual FS eruption, only limited melt evolution is observed and S exsolution seems to have been triggered by a major pressure decrease accompanied by H2O and CO2 exsolution during fast magmatic ascent.