Redox behavior of degassing magmas: critical review and comparison of glass-based oxybarometers with application to Etna volcano

Glass/melt inclusions are repositories of polybaric magma physiochemical interactions. They are fundamental to retrieve the conditions of fluid saturation and magma oxidation state. The latter is usually reported as oxygen fugacity, which is a key thermodynamic variable: involved in such polybaric p...

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Main Author: Moretti, Roberto
Format: Article
Language:English
Published: Académie des sciences 2022-07-01
Series:Comptes Rendus. Géoscience
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Online Access:https://comptes-rendus.academie-sciences.fr/geoscience/articles/10.5802/crgeos.135/
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author Moretti, Roberto
author_facet Moretti, Roberto
author_sort Moretti, Roberto
collection DOAJ
description Glass/melt inclusions are repositories of polybaric magma physiochemical interactions. They are fundamental to retrieve the conditions of fluid saturation and magma oxidation state. The latter is usually reported as oxygen fugacity, which is a key thermodynamic variable: involved in such polybaric physiochemical interactions, $f\mathrm{O}_{2}$ affects melt saturation properties and fixes the speciation of fluids discharged by magmatic systems either up to volcanic craters or feeding hydrothermal systems. Several oxybarometers have been proposed, based on iron and sulfur oxidation states. In this study I summarize their main features and show their performances for 1-bar and fluid-saturated andesitic and basaltic melts. I then show that any assessment of magma redox behavior that does not account for the melt reactivity, driven by melt polymerization and the so-called oxygen electrode in association with iron or sulfur redox couples, may fail in determining the actual contribution of the composition to the observed variations of iron and sulfur oxidation states, resulting in potentially biased $f\mathrm{O}_{2}$ estimates. In the case of Etna volcano, by using a well-established ionic-polymeric approach we show that a major control is the dehydration taking place during magmatic differentiation and magma ascent. Dehydration determines a slight iron oxidation down to around 2.5 wt% in dissolved water, but further dehydration taking place up to the surface results in iron reduction. This dual behavior, related to a change of trivalent iron speciation, is reproduced by reactive ionic-polymeric approaches and for the Etna basalt it is predicted also for constant $f\mathrm{O}_{2}$. Such a modulation of the redox state due to water dissolution cannot be reproduced by empirical formulations.
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spelling doaj-art-78651185bf504cd9894e735ac5ccff2b2025-08-20T03:05:03ZengAcadémie des sciencesComptes Rendus. Géoscience1778-70252022-07-01354S124928010.5802/crgeos.13510.5802/crgeos.135Redox behavior of degassing magmas: critical review and comparison of glass-based oxybarometers with application to Etna volcanoMoretti, Roberto0https://orcid.org/0000-0003-2031-5192Observatoire volcanologique et sismologique de Guadeloupe, Institut de physique du globe de Paris, Le Houelmont, 97113 Gourbeyre, France; Université de Paris Cité, Institut de physique du globe de Paris, UMR 7154 CNRS, 1 rue Jussieu, 75238 Paris, FranceGlass/melt inclusions are repositories of polybaric magma physiochemical interactions. They are fundamental to retrieve the conditions of fluid saturation and magma oxidation state. The latter is usually reported as oxygen fugacity, which is a key thermodynamic variable: involved in such polybaric physiochemical interactions, $f\mathrm{O}_{2}$ affects melt saturation properties and fixes the speciation of fluids discharged by magmatic systems either up to volcanic craters or feeding hydrothermal systems. Several oxybarometers have been proposed, based on iron and sulfur oxidation states. In this study I summarize their main features and show their performances for 1-bar and fluid-saturated andesitic and basaltic melts. I then show that any assessment of magma redox behavior that does not account for the melt reactivity, driven by melt polymerization and the so-called oxygen electrode in association with iron or sulfur redox couples, may fail in determining the actual contribution of the composition to the observed variations of iron and sulfur oxidation states, resulting in potentially biased $f\mathrm{O}_{2}$ estimates. In the case of Etna volcano, by using a well-established ionic-polymeric approach we show that a major control is the dehydration taking place during magmatic differentiation and magma ascent. Dehydration determines a slight iron oxidation down to around 2.5 wt% in dissolved water, but further dehydration taking place up to the surface results in iron reduction. This dual behavior, related to a change of trivalent iron speciation, is reproduced by reactive ionic-polymeric approaches and for the Etna basalt it is predicted also for constant $f\mathrm{O}_{2}$. Such a modulation of the redox state due to water dissolution cannot be reproduced by empirical formulations.https://comptes-rendus.academie-sciences.fr/geoscience/articles/10.5802/crgeos.135/Melt/glass inclusionsOxygen fugacitySulfur speciationIron amphoteric behaviorPolymerizationEtnaMelt dehydration
spellingShingle Moretti, Roberto
Redox behavior of degassing magmas: critical review and comparison of glass-based oxybarometers with application to Etna volcano
Comptes Rendus. Géoscience
Melt/glass inclusions
Oxygen fugacity
Sulfur speciation
Iron amphoteric behavior
Polymerization
Etna
Melt dehydration
title Redox behavior of degassing magmas: critical review and comparison of glass-based oxybarometers with application to Etna volcano
title_full Redox behavior of degassing magmas: critical review and comparison of glass-based oxybarometers with application to Etna volcano
title_fullStr Redox behavior of degassing magmas: critical review and comparison of glass-based oxybarometers with application to Etna volcano
title_full_unstemmed Redox behavior of degassing magmas: critical review and comparison of glass-based oxybarometers with application to Etna volcano
title_short Redox behavior of degassing magmas: critical review and comparison of glass-based oxybarometers with application to Etna volcano
title_sort redox behavior of degassing magmas critical review and comparison of glass based oxybarometers with application to etna volcano
topic Melt/glass inclusions
Oxygen fugacity
Sulfur speciation
Iron amphoteric behavior
Polymerization
Etna
Melt dehydration
url https://comptes-rendus.academie-sciences.fr/geoscience/articles/10.5802/crgeos.135/
work_keys_str_mv AT morettiroberto redoxbehaviorofdegassingmagmascriticalreviewandcomparisonofglassbasedoxybarometerswithapplicationtoetnavolcano