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Abstract: The volatile saturation surface in H2O–CO2–silicate melt systems is modeled by applying thermodynamic equilibrium between gaseous and liquid volatile components. The whole database of existing saturation data in the C–O–H–silicate liquid systems has allowed us to re-calibrate a previously developed fully multicomponent H2O–CO2 saturation model [Papale, P., 1999. Modeling of the solubility of a two-component H2O+CO2 fluid in silicate liquid. Am. Mineral., 84, 477–492]. The new database nearly doubles the previous one, greatly improving the performances of the whole model, which now adopts a significantly lower number of model parameters with respect to the previous calibration. The multicomponent H2O+CO2 saturation model is fully non-ideal, the only assumption being that the excess Gibbs free energy of the silicate mixture can be represented by an expansion of first-order symmetric interaction terms. No a-priori assumption is made on the P–T dependence of the volatile–oxide interaction terms, meaning that no assumption is made on the partial molar volume and enthalpy of the dissolved volatiles. The whole treatment is evaluated by restrictive statistical algorithms, which confirm the model validity on an extended database. The model allows to investigate extensively the dependence of the complex volatile saturation surface on composition. In order to explore the non-linear behaviors implicit in the physics of the dissolution process, the model is employed in a series of calculations aimed at illustrating some of the compositional features of the volatile saturation surface in both one-component and two-component volatile conditions. The results show compositional-dependent minima and maxima, some of which are known from the experiments. Non-ideal behavior is enhanced in two-component fluid phase conditions and pressures above a few hundreds MPa, where calculated isobaric H2O–CO2 saturation curves reveal the possible existence of a maximum in CO2 saturation at non-zero H2O contents. Due to the compositional dependence of the volatile saturation surface, it is outlined the important role played by redox conditions, especially in iron-rich melt systems like basalts. [Copyright &y& Elsevier]

Presents information on a study which modeled the solubility of a two-component, water + carbon dioxide fluid in silicate liquids. Description of the model; Re-derivation of the carbon dioxide-related model parameters; Results of the study.

Abstract: The recent eruption of Stromboli in February–April 2007 offered a unique chance to test our current understanding of processes driving the transition from ordinary (persistent Strombolian) to effusive activity, and the ability of instrumental geophysical and geochemical networks to interpret and predict these events. Here, we report on the results of two years of in-situ sensing of the CO2/SO2 ratio in Stromboli''s volcanic gas plume, in the attempt to put constraints on the trigger mechanisms and dynamics of the eruption. We show that large variations of the plume CO2/SO2 ratio (range, 0.9–26) preceded the onset of the eruption (since December 2007), interrupting a period of relatively-steady and low ratios (time-averaged ratio, 4.3) lasting from at least May to November 2006. By contrasting our observations with numerical simulations of volcanic degassing at Stromboli, derived by use of an equilibrium saturation model, we suggest that the pre-eruptive increase of the ratio reflected an enhanced supply of deeply-derived CO2-rich gas bubbles to the shallow-plumbing system. This larger-than-normal ascent of gas bubbles was likely sourced by a 1–3 km deep gas–melt separation region (probably a magma storage zone), and caused faster convective overturning of magmas in the shallow conduit; an increase in the explosive rate and in seismic tremor, and finally the collapse of the la Sciara del Fuoco sector triggering the effusive phase. The high CO2/SO2 ratios (up to 21) observed during the effusive phase, and particularly in the days and hours before a paroxysmal explosion on March 15, 2007, indicate the persistence of the same gas source; and suggest that de-pressurization of the same 1–3 km deep magma storage zone could have been the trigger mechanism for the paroxysm itself. [Copyright &y& Elsevier]