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The conditions under which halogens partition in favor of an exsolved fluid relative to the coexisting melt are key for understanding many magmatic processes, including volcanic degassing, evolution of crustal melt bodies, and ore formation. We report new F, Cl, and Br fluid/melt partition coefficients for intermediate to silicic melts, for which F and Br data are particularly lacking; and for varying CO2- H2O contents to assess the efects of changing fluid composition (XH2O) on Br fluid/melt partitioning for the first time. The experiments were conducted at pressures 50–120 MPa, temperatures 800–1100 °C, and volatile compositions [molar XH2O = H2O/(H2O +CO2)] of 0.55 to 1, with redox conditions around the Nickel-Nickel Oxygen bufer (ƒO2 ≈ NNO). Experiments were not doped with Cl, Br, or F and were conducted on natural crystal-bearing volcanic products at conditions close to their respective pre-eruptive state. The experiments therefore provide realistic constraints on halogen partitioning at naturally occurring, brine-undersaturated conditions. Measurements of Br, Cl, and F were made by Secondary Ion Mass Spectrometry (SIMS) on 13 experimental glass products spanning andesite to rhyolitic compositions, together with their natural starting materials from Kelud volcano, Indonesia, and Quizapu volcano, Chile. Fluid compositions were constrained by mass balance. Average bulk halogen fluid/melt partition coefficients and standard deviations are: DClfluid/melt = 3.4 (±3.7 1 s.d.), DFfluid/melt = 1.7 (±1.7), and DBrfluid/melt = 7.1 (±6.4) for the Kelud starting material (bulk basaltic andesite), and DClfluid/melt = 11.1 (±3.5), DFfluid/melt = 0.8 (±0.8), and DBrfluid/melt = 31.3 (±20.9) for Quizapu starting material (bulk dacite). The large range in average partition coeficients is a product of changing XH2O, pressure and temperature. In agreement with studies on synthetic melts, our data show an exponential increase of halogen Dfluid/melt with increasing ionic radius, with partitioning behavior controlled by melt composition according to the nature of the complexes forming in the melt (e.g., SiF4, NaCl, KBr). The fundamental chemistry of the diferent halogens (differing ionic size and electronegativities) controls the way in which partitioning responds to changes in melt composition and other variables. Experimental results confirm that more Cl partitions into the fluid at higher bulk Cl contents, higher melt Na, higher fluid XH2O ratios, and lower temperatures. Bromine shows similar behavior, though it seems to be more sensitive to temperature and less sensitive to Na content and XH2O. In contrast, F partitioning into the fluid increases as the melt silica content decreases (from 72 to 56 wt% SiO2), which we attribute to the lower abundance of Si available to form F complexes in the melt. These new data provide more insights into the conditions and processes that control halogen degassing from magmas and may help to inform the collection and interpretation of melt inclusions and volcano gas data. [ABSTRACT FROM AUTHOR]

Electron-beam irradiation causes permanent damage to hydrous, silica-rich glasses. The extent of electron-beam damage is quantified using data generated by SIMS analysis of points subjected to previous electron microprobe analysis (EPMA). Even optimum EPMA conditions cause damage to the glass, manifest as a marked depletion in alkali ions at the surface of an irradiated sample. Deeper in the sample, an enrichment in alkali ions to above-baseline levels is followed by a decay back to baseline. The depth of the final decay correlates with species diffusivity and increases in the order K-Li-Na. H-bearing species are also affected by electron beam irradiation, but in the opposite sense to the alkalis, i.e., they are enriched at the surface. Migration of alkaline earth cations is not observed because of their low diffusivities. Ion depletion or enrichment results from simple migration of ions toward or away from electrons implanted by the beam. Migration depth depends on species diffusivity and heating caused by the electron beam, and therefore increases with increasing electron beam current. Because of the reverse behavior of H, the mobile hydrous species in the presence of an electric field is probably O[H.sup.-]. The extent of electron beam damage to glasses may increase with total water content. Critically, SIMS measurements of H, Li, Na, D/H, and [sup.6]Li/[sup.7]Li after electron-probe analysis are compromised by the damage. Despite the damage caused by the electron beam, use of appropriate electron-beam conditions (e.g., 2 nA, 15 kV) gives volatiles by difference accurate to ~0.6 wt%. Keywords: Electron-probe microanalysis, rhyolite glass, melt inclusions, secondary ion mass spectrometry, diffusion

The article explains the volcanic history of the Uturuncu volcano, a dormant stratovolcano situated in Bolivia, which is completely dominated by the domes and flows of dacitic lava. The volcano is shown to exhibit an unrest situation, which proves the prolonged period of intrusion of the magmatic system.

We present the first integrated study of carbonate, hydroxyl, fluoride, and chloride ion partitioning in the apatite-melt system. We determined volatile partitioning behavior between apatite and silicate melt for both haplobasaltic andesite and trachyte bulk compositions at 0.5–1 GPa and 1250 °C using the piston-cylinder apparatus. All volatile species were analyzed directly in both apatite and glass using secondary ion mass spectrometry (SIMS) and electron probe microanalysis. Distribution coefficients for OH-halogen exchange are similar to those from previous studies, and together with literature data, reveal a significant log-linear relationship with temperature, while the effects of pressure and melt composition are minimal. Meanwhile, halogen-free experiments generate very high C contents (up to 5000 ppm) in apatite. Stoichiometry calculations and infrared spectra indicate that this C is mainly incorporated onto the channel volatile site together with hydroxyl. In halogen-bearing experiments, apatite crystals contain significantly lower C (≤500 ppm), which may be partly incorporated onto the phosphate site while the channel volatile site is filled by OH+F+Cl+C. Our experiments give the first constraints on H2O-CO2 exchange between apatite and silicate melt, with a KD of 0.355 ± 0.05 for the trachyte and 0.629 ± 0.08 for the haplobasaltic andesite. The new constraints on the temperature-dependence of partitioning will enable quantitative modeling of apatite-volatile exchange in igneous systems, while this new partitioning data and method for direct, in situ analysis of C in apatite mark a significant advance that will permit future studies of magmatic C and other volatiles. This has a broad range of potential applications including magmatic differentiation, fractionation, and degassing; quantification of volatile budgets in extraterrestrial and deep earth environments; and mineralization processes. [ABSTRACT FROM AUTHOR]

Abstract: The pre-fragmentation velocity of magma ascending during explosive volcanic eruptions remains difficult to quantify. Here we present a new technique for using syn-eruptive volatile diffusion in imperfectly trapped melt inclusions to obtain a direct estimate of such ascent velocities. H2O diffusion profiles are obtained from back-scattered electron images of synthetic, partially hydrated glasses and tube-shaped melt inclusions. The greyscale intensity of glass in the images shows a good negative linear correlation with melt H2O concentration. Greyscale intensity profiles, extracted using image-processing software, can therefore be calibrated against H2O measured at discrete points by ion microprobe. An advantage of the technique is that concentration profiles can be determined in melt tubes that are too small to analyse directly, with a spatial resolution (≤1 μm) that is considerably better than that obtainable by ion microprobe or FTIR. A finite element model, which incorporates previously published estimates of concentration-dependent H2O diffusivity, is used to fit the resulting continuous concentration profiles. We apply the technique to tube-shaped melt inclusions from the May 18th, 1980 Plinian eruption of Mount St Helens, Washington, USA. The model produces good fits to the data, indicating very rapid ascent times of between 102 and 166 s, which correspond to mean ascent velocities of 37-64 m/s, or mean decompression rates of 0.9-1.6 MPa/s. These are in agreement with previous estimates from petrological studies and numerical modelling. [Copyright &y& Elsevier]