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Crystallization experiments on two pantellerites from Pantelleria, Italy, provide new evidence for the relationships between mineral phases in pantelleritic rocks as well as the influence of temperature and redox conditions on mineral assemblages. Experiments were performed at 1 kbar with temperature ranging between 750–900°C, and fluid saturation conditions with XH2O (=H2O/H2O+CO2) between 0 and 1. Redox conditions were fixed at, or slightly below, the FMQ buffer. Results show that at temperature of 900 °C pantelleritic magmas are well above the liquidus regardless their water content; we also observed a decrease in liquidus temperature (800°C) with increasingly reducing conditions. Mineral assemblages of the natural rocks have been successfully reproduced, particularly the relationship between fayalite and aenigmatite, which appear to be strongly controlled by melt peralkalinity, temperature and redox conditions. This is the first time that fayalitic olivine have been synthetized in experimental studies on pantellerites, which was found to be stable only for temperatures ≥750°C while amphibole can be stable at temperatures as high as 800°C at high fF2. Experimental results have been compared with the composition of mineral phases as well as with the results obtained from mineral equilibrium, geothermometry, and oxygen barometry studies on pantelleritic lava and tuffs from Pantelleria (Italy), Eburru (Kenya) and Menengai (Kenya). Petrological characteristics appear similar at different locations worldwide, with typical assemblages of anorthoclase and sodian clinopyroxene with variable fayalite, aenigmatite, Fe-Ti oxides and amphibole.

Erratum to: Bull Volcanol (2017) 79: 36DOI 10.1007/s00445-017-1114-zDuring the steps of corrections, the publisher inadvertently changed the author affiliations so that they were no longer correct. The correct information is given below. The publisher regrets this mistake.; International audience; Volcanic gas emission measurements inform predictions of hazard and atmospheric impacts. For these measurements, Multi-Gas sensors provide low-cost in situ monitoring of gas composition but to date have lacked the ability to detect halogens. Here, two Multi-Gas instruments characterized passive outgassing emissions from Mt. Etna’s (Italy) three summit craters, Voragine (VOR), North-east Crater (NEC) and Bocca Nuova (BN) on 2 October 2013. Signal processing (Sensor Response Model, SRM) approaches are used to analyse H2S/SO2 and HCl/SO2 ratios. A new ability to monitor volcanic HCl using miniature electrochemical sensors is here demonstrated. A “direct-exposure” Multi-Gas instrument contained SO2, H2S and HCl sensors, whose sensitivities, cross-sensitivities and response times were characterized by laboratory calibration. SRM analysis of the field data yields H2S/SO2 and HCl/SO2 molar ratios, finding H2S/SO2 = 0.02 (0.01–0.03), with distinct HCl/SO2 for the VOR, NEC and BN crater emissions of 0.41 (0.38–0.43), 0.58 (0.54–0.60) and 0.20 (0.17–0.33). A second Multi-Gas instrument provided CO2/SO2 and H2O/SO2 and enabled cross-comparison of SO2. The Multi-Gas-measured SO2-HCl-H2S-CO2-H2O compositions provide insights into volcanic outgassing. H2S/SO2 ratios indicate gas equilibration at slightly below magmatic temperatures, assuming that the magmatic redox state is preserved. Low SO2/HCl alongside low CO2/SO2 indicates a partially outgassed magma source. We highlight the potential for low-cost HCl sensing of H2S-poor HCl-rich volcanic emissions elsewhere. Further tests are needed for H2S-rich plumes and for long-term monitoring. Our study brings two new advances to volcano hazard monitoring: real-time in situ measurement of HCl and improved Multi-Gas SRM measurements of gas ratios.

International audience; To interpret primitive magma compositions in the Aeolian arc and contribute to a better experimental characterization of ultra-calcic arc melts, equilibrium phase relations have been determined experimentally for the La Sommata basalt (Som-1, Vulcano, Aeolian arc). Som-1 (Na2O + K2O = 4.46 wt.%, CaO = 12.97 wt.%, MgO = 8.78 wt.%, CaO/Al2O3 = 1.03) is a reference primitive ne-normative arc basalt with a strong ultra-calcic affinity. The experiments have been performed between 44 and 154 MPa, 1050 and 1150 °C and from NNO + 0.2 to NNO + 1.9. Fluid-present conditions were imposed with H2O–CO2 mixtures yielding melt H2O concentrations from 0.7 to 3.5 wt.%. Phases encountered include clinopyroxene, olivine, plagioclase and Fe-oxide. Clinopyroxene is slightly earlier than olivine in the crystallization sequence. It is the liquidus phase at 150 MPa, being joined by olivine on the liquidus between 44 and 88 MPa. Plagioclase is the third phase to appear in the crystallization sequence and orthopyroxene was not found. Experimental clinopyroxenes (Fs7–16) and olivines (Fo78–92) partially reproduce the natural phenocryst compositions (respectively Fs5–7 and Fo87–91). Upon progressive crystallization, experimental liquids shift towards higher SiO2 (up to ~ 55 wt.%), Al2O3 (up to ~ 18 wt.%) and K2O (up to ~ 5.5 wt.%) and lower CaO, MgO and CaO/Al2O3. Experimental glasses and natural whole-rock compositions overlap, indicating that progressive crystallization of Som-1 type melts can generate differentiated compositions such as those encountered at Vulcano. The low pressure cotectic experimental glasses reproduce glass inclusions in La Sommata clinopyroxene but contrast with glass inclusions in olivine which preserve basaltic melts more primitive than Som-1. Phase relations for the La Sommata basalt are identical in all critical aspects to those obtained previously on a synthetic ultra-calcic arc composition. In particular, clinopyroxene + olivine co-saturation occurs at very low pressures (≤ 100 MPa). Ultra-calcic arc compositions do not represent primary mantle melts but result from the interaction between a primary mantle melt and clinopyroxene-bearing rocks in the arc crust. At Vulcano, primitive ultra-calcic end-member melts were generated between 250 and 350 MPa in the lower magma accumulation zone by reaction between hot primitive melts and wehrlitic or gabbroic lithologies. At Stromboli, golden pumices and glass inclusions with an ultra-calcic affinity were also generated at shallow pressures, between 150 and 250 MPa, suggesting that the interaction model is of general significance in the Aeolian arc.

International audience; To test mechanisms of basaltic ma gma degassing, continuous decompressions of volatile-bearing (2.7-3.8 wt% H2O, 600-1300 ppm CO2) Stromboli melts were performed from 250-200 to 50-25 MPa at 1180-1140°C. Ascent rates were varied from 0.25 to ~ 1.5 m/s. Glasses after decompression show a wide range of textures, from totally bubble-free to bubble-rich, the latter with bubble number densities from 104 to 106/cm3, similar to Stromboli pumices. Vesicularities range from 0 to ~ 20 vol%. Final melt H2O concentrations are homogeneous and always close to solubilities. In contrast, the rate of vesiculation controls the final melt CO2 concentration. High vesicularity charges have glass CO2 concentrations that follow theoretical equilibrium degassing paths whereas glasses from low vesicularity charges show marked deviations from equilibrium, with CO2 concentrations up to one order of magnitude higher than solubilities. FTIR profiles and maps reveal glass CO2 concentration gradients near the gas-melt interface. Our results stress the importance of bubble nucleation and growth, and of volatile diffusivities, for basaltic melt degassing. Two characteristic distances, the gas interface distance (distance either between bubbles or to gas-melt interfaces) and the volatile diffusion distance control the degassing process. Melts containing numerous and large bubbles have gas interface distances shorter than volatile diffusion distances, and degassing proceeds by equilibrium partitioning of CO2 and H2O between melt and gas bubbles. For melts where either bubble nucleation is inhibited or bubble growth is limited, gas interface distances are longer than volatile diffusion distances. Degassing proceeds by diffusive volatile transfer at the gas-melt interface and is kinetically limited by the diffusivities of volatiles in the melt. Our experiments show that CO2-oversaturated melts can be generated as a result of magma decompression. They provide a new explanation for the occurrence of CO2-rich natural basaltic glasses and open new perspectives for understanding explosive basaltic volcanism.

International audience; New experimental data of Ar and Ne solubility at pressures up to 360 MPa in alkali-basaltic (Mt. Etna, Italy) and rhyolitic (Vulcano Island, Italy) melts are presented. Solubility experiments have been conducted in internally heated pressure vessels at 1200 °C under nominally anhydrous conditions. Ar and Ne contents dissolved in the experimental glasses were then measured by quadrupole mass spectrometry. Over the pressure range investigated, Ar and Ne solubilities vary linearly with Ar and Ne pressures and can be described by Henry's constant (kAr,Ne = PAr, Ne / xAr, Ne, where PAr, Ne is the partial pressure of Ar or Ne and xAr, Ne is the molar fraction of Ar or Ne in the melt) of 7.6 ± 0.8 × 105 and 1.9 ± 0.4 × 105 MPa, respectively for Ar and Ne in the basaltic melt and 1.5 ± 0.2 × 105 and 3.8 ± 0.2 × 104 MPa, respectively for Ar and Ne in the rhyolitic melt. In accordance with existing models, rhyolitic melts show higher noble gas solubilities than basaltic melts, Ne solubility being higher than that of Ar in a given composition. We propose a semi-empirical model of noble gas (Ar, Ne and He) solubility calibrated on a very large set of measurements in natural and synthetic silicate melts. The model expands the concept of ionic porosity in terms of porosity accessible for noble gas dissolution in melt, taking into account the large-scale structural effects of cations, as well as temperature and pressure. The model is valid over a wide range of temperatures (800–1600 °C), pressures (up to 3 GPa) and compositions, being useful for both geological and physico-chemical studies.

International audience; New experiments have been performed on a high-K basalt (PST-9) from Stromboli volcano, Italy, to constrain the physical conditions of golden pumice magmas at their storage level and discuss their petrogenesis. Fluid-present, H2O- and CO2-bearing, near-liquidus experiments were performed at 11508C between 100 and 400MPa and under oxidizing conditions. Glasses were analyzed by Fourier transform IR spectroscopy and their H2O and CO2 concentrations compared with those in glass inclusions.Most glass inclusions cluster near the 200MPa isobar, suggesting entrapment at a depth of ~8 km. Golden pumice magmas have viscosities of 7.9 Pa s and densities of 2.48-2.57 g/cm3. Compositions of experimental fluids coexisting with melts along the liquidus have been estimated by mass balance. They range from CO2-rich (XH2O~0.2) at 400MPa to H2O-rich (XH2O~0.8) at 100MPa.The free fluid phase present at the reservoir level has an XH2O of ~0.6, consistent with equilibration with a near-liquidus golden pumice magma below 300MPa. Clinopyroxene is the liquidus phase in all highpressure experiments, either fluid-absent (H2O) or fluid-present (H2O-CO2). In contrast, at 0.1MPa, cpx and ol appear together on the liquidus and olivines are more Fo-rich (up to 89.1) than those crystallizing at high pressures (up to 87.3).The composition of cotectic liquids multiply saturated in cpx and ol has been experimentally determined. Most pumices and a majority of melt inclusions have compositions of cotectic melts. In contrast, PST-9 plots in the cpx field and is representative of less evolved ankaramitic magmas parental to golden pumices. Melt inclusions trapped in Fo 487 olivines form a group of ultra-calcic compositions plotting in the cpx field, interpreted as boundary layer melts locally generated by cpx dissolution in the deep reservoir. Ankaramitic melts in the Stromboli feeding system are proposed to derive from primitive mantle melts by combined crystallization, mixing, wall-rock interaction and assimilation.

Partitioning experiments between a basaltic melt from Mt. Etna and a low-density hydrous fluid or vapor containing H(2)O or H(2)O-CO(2) were performed at 1200-1260 degrees C, at pressures between 1 and 200 MPa, either near the nickel-nickel oxide (NNO) buffer or at two log units above it (NNO + 2), and with different chloride concentrations. Most of the experiments were done at chloride-brine-undersaturated conditions, although at the highest Cl concentrations explored brine saturation might have been reached. The average partition coefficients (D(Cl)(fluid/melt)) over the range of Cl concentrations were derived on a weight basis by plotting the calculated concentrations of Cl in the fluid phase versus the measured ones in the melt. For H(2)O-Cl experiments in which the Cl concentration in the melt was = 2. Addition of CO(2) at NNO yields lower partition coefficients than in CO(2)-free conditions over the pressure range investigated. The negative pressure dependence observed for H(2)O-Cl experiments disappears when CO(2) is present in the system. Overall, once CO(2) is introduced in the system, Cl fugacity in the silicate melt tends to increase, thus resulting in a decrease of D(Cl)(f/m). Application to Mt. Etna shows that the composition of the volcanic plume in terms of Cl records very shallow pressures of magma equilibration with its exsolved fluid.

International audience; The near-liquidus crystallization of a high-K basalt (PST-9 golden pumice, 49·4 wt % SiO2, 1·85 wt % K2O, 7·96 wt % MgO) from the present-day activity of Stromboli (Aeolian Islands, Italy) has been experimentally investigated between 1050 and 1175°C, at pressures from 50 to 400 MPa, for melt H2O concentrations between 1·2 and 5·5 wt % and {Delta}NNO ranging from –0·07 to +2·32. A drop-quench device was systematically used. AuPd alloys were used as containers in most cases, resulting in an average Fe loss of 13% for the 34 charges studied. Major crystallizing phases include clinopyroxene, olivine and plagioclase. Fe–Ti oxide was encountered in a few charges. Clinopyroxene is the liquidus phase at 400 MPa down to at least 200 MPa, followed by olivine and plagioclase. The compositions of all major phases and glass vary systematically with the proportion of crystals. Ca in clinopyroxene sensitively depends on the H2O concentration of the coexisting melt, and clinopyroxene Mg-number shows a weak negative correlation with {Delta}NNO. The experimental data allow the liquidus surface of PST-9 to be defined. When used in combination with melt inclusion data, a consistent set of pre-eruptive pressures (100–270 MPa), temperatures (1140–1160°C) and melt H2O concentrations is obtained. Near-liquidus phase equilibria and clinopyroxene Ca contents require melt H2O concentrations

This paper reports the results of hydrothermal synthesis in the system Na 2 O-MgO-FeO-Fe 2 O 3 -SiO 2 -H 2 O. Four samples of stoichiometric magnesioriebeckite composition, ideally □Na 2 Mg 3 Fe 3+ 2 Si 8 O 22 (OH) 2 , were run at 700–800 °C, 0.4 GPa, and redox conditions varying from NNO (Nickel–Nickel Oxide) to NNO + 2.3 log f O 2 . Powder XRD and SEM-EDX show a high (>85%) amphibole yield for all samples; however, in no case was the end-member composition attained. EMP analyses show that the amphiboles obtained deviate strongly from nominal stoichiometry toward magnesio-arfvedsonite [NaNa 2 Mg 4 Fe 3+ Si 8 O 22 (OH) 2 ]. Powder XRD patterns were indexed in the space group C 2/ m ; refined cell-parameters reflect variations in the amphibole composition, and the cell volume is correlated linearly with the A-site occupancy. Mossbauer spectra show that in all samples, Fe 3+ is completely ordered at M2, whereas Fe 2+ occurs at the M1, M3, and M4 sites. The Fe 3+ /Fe 2+ ratio is a function of f O 2 : for increasing oxidation conditions, there is significant increase in M2 Fe 3+ and decrease in Fe 2+ , notably in M4 Fe 2+ . Mossbauer spectra also show significant variation in M1 Fe 2+ and M3 Fe 2+ quadrupole splitting as a function of the Fe 3+ content in the amphibole. IR spectra in the OH-stretching region show a well-resolved quadruplet at frequencies −1 , assigned to octahedral M1,3 (Mg, Fe 2+ )-OH- A □ configurations, and a broad band consisting of four overlapping components related to M1,3 (Mg, Fe 2+ ) configurations associated with occupied A-sites. Quantitative evaluation of the relative band intensities suggests a linear increase of A-site occupancy with decreasing f O 2 of synthesis. The composition of the amphiboles synthesized, can be best described by a combination of the C (Mg,Fe 2+ ) 1 B (Mg,Fe 2+ ) 1 C Fe 3+ −1 B Na −1 and the A Na 1 C (Mg,Fe 2+ ) 1 A □ −1 C Fe 3+ −1 exchange vectors. The experimental trend is in accord with the trend documented for natural amphiboles, and suggests that the amphibole composition can in fact be used to monitor changes in f O 2 during crystallization.