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The study of the oxidation state of lithospheric mantle-derived rocks allows modelling the deep cycle of volatiles (e.g., C, H, O, N and S) in the Earth's interior, which in turn plays a role in magma genesis, metasomatism and volcanic degassing. At the oxygen fugacity (i.e., fO2) recorded by residual abyssal peridotites, volatile elements like carbon are predicted to be in the immobile form of graphite. However, the compilation of the redox state of worldwide-distributed continental xenoliths shows evidence of their oxidation and refertilization through time by deeply formed subduction-related metasomatic fluids. The analyses of fluid inclusions in mantle-derived minerals like olivine (or pyroxenes) represent a snapshot of the volatile circulation in depth, whose noble gases signature (He, Ar, Ne) is used to identify their possible source. This study aims to reconstruct the origin of mantle metasomatism underneath the Hyblean Plateau (Sicily, Italy) and its redox history through the investigation of spinel-peridotite nodules, combining fO2 estimates with noble gases and fluid inclusions chemistry from hand-picked olivine grains. We analyzed eight mantle xenoliths classified as spinel lherzolites and spinel harzburgites from the Valle Guffari (Hyblean Plateau, Sicily). The calculated logfO2 is higher than that of most cratonic xenoliths worldwide ranging between 0.28 and 1.27 log units above to the fayalite-magnetite-quartz (FMQ) reference buffer. Micro-Raman measurements on olivine grains with dendritic trails of (metasomatic) fluid inclusions reveal an assemblage made of Mg-Ca carbonates ± sulfide ± elemental sulfur ± CO2 in the most reduced sample, and Mg-Ca carbonates ± sulfates ± CO2 in the most oxidized sample, the latter associated with a silicate glass and (secondary) hydrous phases. Both assemblages are taken as evidence of the product of crystallization of deeply originated volatile-bearing silicate melts. Analyses of He, Ar, and Ne in olivine grains confi

In this study, we performed leaching experiments for timescales of hours-to-months in deionized water on fresh volcanic ash from Mt. Etna (Italy) and Popocatépetl (Mexico) volcanos to monitor Fe release as a function of ash mineral chemistry and size, with the aim of clarifying Fe release mechanisms and eventually evaluating the impact of volcanic ash on marine and lacustrine environments. To define sample mineralogy and Fe speciation, inclusive characterization was obtained by means of XRF, SEM, XRPD, EELS and Mössbauer spectroscopies. For Etna and Popocatépetl samples, glass proportions were quantified at 73 and 40%, Fe2O3 total contents at 11.6–13.2 and 5.8 wt%, and Fe3+/FeTot ratios at 0.33 and 0.23, respectively. Leaching experiments showed that significant amounts of iron, ~ 30 to 150 and ~ 750 nmol g−1 l−1 for pristine Etna and Popocatépetl samples, respectively, are released within the first 30 min as a function of decreasing particle size (from 1 to 0.125 mm). The Popocatépetl sample showed a very sustained Fe release (up to 10 times Etna samples) all along the first week, with lowest values never below 400 nmol g−1 l−1 and a maximum of 1672 nmol g−1 l−1 recorded after 5 days. This sample, being composed of very small particles (average particle size 0.125 mm) with large surface area, likely accumulated large quantities of Fe-bearing sublimates that quickly dissolved during leaching tests, determining high Fe release and local pH decrease (that contributed to release more Fe from the glass) at short timescale (hours-to-days). The fractional Fe solubility (FeS) was 0.004–0.011 and 0.23% for Etna and Popocatépetl samples, respectively, but no correlation was found between Fe released in solution and either ash Fe content, glass/mineral ratio or mineral assemblage. Results obtained suggest that volcanic ash chemistry, mineralogy and particle size assume a relevant role on Fe release mostly in the medium-to-long timescale, while Fe release in the short ti