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In this study, we use micro-X-ray absorption near-edge structures (µ-XANES) spectroscopy at the S K-edge to investigate the oxidation state of S in natural magmatic-hydrothermal apatite (Durango, Mexico, and Mina Carmen, Chile) and experimental apatites crystallized from volatile-saturated lamproitic melts at 1000 °C and 300 MPa over a broad range of oxygen fugacities [log(fO2)=FMQ, FMQ+1.2, FMQ+3; FMQ = fayalite-magnetite-quartz solid buffer]. The data are used to test the hypothesis that S oxidation states other than S6+ may substitute into the apatite structure. Peak energies corresponding to sulfate S6+ (∼2482 eV), sulfite S4+ (∼2478 eV), and sulfide S2- (∼2470 eV) were observed in apatite, and the integrated areas of the different sulfur peaks correspond to changes in fO2 and bulk S content. Here, multiple tests confirmed that the S oxidation state in apatite remains constant when exposed to the synchrotron beam, at least for up to 1 h exposure (i.e., no irradiation damages). To our knowledge, this observation makes apatite the first mineral to incorporate reduced (S2-), intermediate (S4+), and oxidized (S6+) S in variable proportions as a function of the prevailing fO2 of the system. Apatites crystallized under oxidizing conditions (FMQ+1.2 and FMQ+3), where the S6+/STotal peak area ratio in the coexisting glass (i.e., quenched melt) is ∼1, are dominated by S6+ with a small contribution of S4+, whereas apatites crystallizing at reduced conditions (FMQ) contain predominantly S2-, lesser amounts of S6+, and possibly traces of S4+. A sulfur oxidation state vs. S concentration analytical line transect across hydrothermally altered apatite from the Mina Carmen iron oxide-apatite (IOA) deposit (Chile) demonstrates that apatite can become enriched in S4+ relative to S6+, indicating metasomatic overprinting via a SO2-bearing fluid or vapor phase. This XANES study demonstrates that as the fO2 increases from FQM to FMQ+1.2 to FMQ+3 the oxidation state of S in igneous apatite changes from S2- dominant to S6+ > S4+ to S6+ >> S4+ Furthermore, these results suggest that spectroscopic studies of igneous apatite have potential to trace the oxidation state of S in magmas. The presence of three S oxidations states in apatite may in part explain the non-Henrian partitioning of S between apatite and melt. Our study reveals the potential to use the S signature of apatite to elucidate both oxygen and sulfur fugacity in magmatic and hydrothermal systems.

Crystallization experiments of a dacitic composition were conducted in a temperature range of 675–775 °C at 200 MPa in order to determine the evolution of the trace element partitioning between residual melts and coexisting mineral assemblages with ongoing crystallization. The starting composition was doped with ∼100 ppm of a series of incompatible trace elements. The adopted experimental approach consisted of performing two-step experiments. In a first step, long-time crystallization experiments were performed, starting with glass powder to obtain a mineral assemblage in equilibrium with residual melt. The phase assemblage was composed of melt, plagioclase, amphibole, biotite, and a few oxides. Because of the small size of crystal-free melt pools, a separation of glass from minerals was achieved by the use of the mineral grain trap technique in second-step experiments. The melts from first-step experiments were rhyolitic, allowing quartz to be used as a mineral trap. The following elements were analysed by means of laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analysis: P, Y, Zr, Nb, Cs, Ce, Yb, and U. Although the initial trace element concentrations were low, only Cs and U show a clearly incompatible behaviour, with a systematic enrichment in the melt with decreasing melt fraction from ∼85 area % to 65 area %. We demonstrate that the other elements are controlled either by the crystallization of accessory phases for P (apatite) and Zr (zircon) and/or by their incorporation into mineral phases (mainly amphibole, biotite, and oxide). In particular, changes in the relative proportions of mafic phases vs. plagioclase during ongoing crystallization may lead to changes in bulk mineral / melt partition coefficients from >1 to <1. At constant temperature (T), the proportions of mafic phases vs. plagioclase are strongly controlled by water activity, and the meltwater content is therefore a crucial parameter that controls the evolution of trace element concentrations in residual melts. The comparison of our data with published partitioning coefficients is in good agreement for Cs, U, and Y. However, Kdamph/melt and Kdbiot/melt may be higher than estimated previously for Yb, Ce, and Zr. Nb is less compatible than predicted, with a bulk partitioning value in the range of 1.5 to 2.

Lascar volcano, located in northern Chile, is among the most active volcanoes of the Andean Central Volcanic Zone (CVZ). Its activity culminated in the last major explosive eruption in April 1993. Lascar andesites which erupted in April 1993 have a phase assemblage composed of plagioclase, clinopyroxene, orthopyroxene, Fe–Ti oxides, and rhyolitic glass. To better constrain storage conditions and mechanisms of magmatic differentiation for andesitic magmas in a thick continental crust, crystallization experiments were performed in internally heated pressure vessels at 300 and 500 MPa, in the temperature (T) range of 900–1050 °C, at various water activities (aH2O) and oxygen fugacities (logfO2 between QFM+1.5 and QFM+3.3 at aH2O =1; QFM is quartz–fayalite–magnetite oxygen buffer). The comparison of experimental products with natural phase assemblages, phase compositions, and whole-rock compositions was used to estimate magma storage conditions and to reconstruct the magma plumbing system. We estimate that Lascar two-pyroxene andesitic magmas were stored at 975±25 °C, 300±50 MPa, and logfO2 of QFM+1.5±0.5, under H2O-undersaturated conditions with 2.5 wt % to 4.5 wt % H2O in the melt. The geochemical characteristics of the entire suite of Lascar volcanics indicates that a fractionating magmatic system located at a depth of 10–13 km is periodically replenished with less evolved magma. Some eruptive stages were dominated by volcanic products resulting most probably from the mixing of a mafic andesitic magma with a felsic component, whereas compositional variations in other eruptive stages are better explained by crystal fractionation processes. The relative importance of these two mechanisms (mixing vs. crystal fractionation) may be related to the amount and frequency of magma recharge in the reservoir.

Halogens show a range from moderate (F) to highly (Cl, Br, I) volatile and incompatible behavior, which makes them excellent tracers for volatile transport processes in the Earth’s mantle. Experimentally determined fluorine and chlorine partitioning data between mantle minerals and silicate melt enable us to estimate Mid Ocean Ridge Basalt (MORB) and Ocean Island Basalt (OIB) source region concentrations for these elements. This study investigates the effect of varying small amounts of water on the fluorine and chlorine partitioning behavior at 1280 °C and 0.3 GPa between olivine and silicate melt in the Fe-free CMAS+F–Cl–Br–I–H 2 O model system. Results show that, within the uncertainty of the analyses, water has no effect on the chlorine partitioning behavior for bulk water contents ranging from 0.03 (2) wt% H 2 O (D Cl ol/melt = 1.6 ± 0.9 × 10 −4 ) to 0.33 (6) wt% H 2 O (D Cl ol/melt = 2.2 ± 1.1 × 10 −4 ). Consequently, with the effect of pressure being negligible in the uppermost mantle (Joachim et al. Chem Geol 416:65–78, 2015 ), temperature is the only parameter that needs to be considered for the determination of chlorine partition coefficients between olivine and melt at least in the simplified iron-free CMAS+F–Cl–Br–I–H 2 O system. In contrast, the fluorine partition coefficient increases linearly in this range and may be described at 1280 °C and 0.3 GPa with ( R 2  = 0.99): D F ol/melt = 3.6 ± 0.4 × 10 - 3 × X H 2 O wt % + 6 ± 0.4 × 10 - 4 . The observed fluorine partitioning behavior supports the theory suggested by Crépisson et al. (Earth Planet Sci Lett 390:287–295, 2014 ) that fluorine and water are incorporated as clumped OH/F defects in the olivine structure. Results of this study further suggest that fluorine concentration estimates in OIB source regions are at least 10% lower than previously expected (Joachim et al. Chem Geol 416:65–78, 2015 ), implying that consideration of the effect of water on the fluorine partitioning behavior between Earth’s mantle minerals and silicate melt is vital for a correct estimation of fluorine abundances in OIB source regions. Estimates for MORB source fluorine concentrations as well as chlorine abundances in both mantle source regions are within uncertainty not affected by the presence of water.

The viscosity of a series of six synthetic dacitic liquids, containing up to 5.04 wt% dissolved water, was measured above the glass transition range by parallel-plate viscometry. The temperature of the 10 11  Pa s isokom decreases from 1065 K for the anhydrous liquid, to 864 K and 680 K for water contents of 0.97 and 5.04 wt% H 2 O. Including additional measurements at high temperatures by concentric-cylinder and falling-sphere viscometry, the viscosity ( η ) can be expressed as a function of temperature and water content w according to: where η is in Pa s, T is temperature in K, and w is in weight percent. Within the conditions of measurement, this parameterization reproduces the 76 viscosity data with a root-mean square deviation (RMSD) of 0.16 log units in viscosity, or 7.8 K in temperature. The measurements show that water decreases the viscosity of the dacitic liquids more than for andesitic liquids, but less than for rhyolites. At low temperatures and high water contents, andesitic liquids are more viscous than the dacitic liquids, which are in turn more viscous than rhyolitic liquids, reversing the trend seen for high temperatures and low water contents. This suggests that the relative viscosity of different melts depends on temperature and water content as much as on bulk melt composition and structure. At magmatic temperatures, rhyolites are orders of magnitude more viscous than dacites, which are slightly more viscous than andesites. During degassing, all three liquids undergo a rapid viscosity increase at low water contents, and both dacitic and andesitic liquids will degas more efficiently than rhyolitic liquids. During cooling and differentiation, changing melt chemistry, decreasing temperature and increasing crystal content all lead to increases in the viscosity of magma (melt plus crystals). Under closed system conditions, where melt water content can increase during crystallization, viscosity increases may be small. Conversely, viscosity increases are very abrupt during ascent and degassing-induced crystallization.

In this study, we use micro-X-ray absorption near-edge structures (μ-XANES) spectroscopy at the S K-edge to investigate the oxidation state of S in natural magmatic-hydrothermal apatite (Durango, Mexico, and Mina Carmen, Chile) and experimental apatites crystallized from volatile-saturated lamproitic melts at 1000 °C and 300 MPa over a broad range of oxygen fugacities [( Embedded Image , FMQ+1.2, FMQ+3; FMQ = fayalite-magnetite-quartz solid buffer]. The data are used to test the hypothesis that S oxidation states other than S6+ may substitute into the apatite structure. Peak energies corresponding to sulfate S6+ ( 2482 eV), sulfite S4+ ( 2478 eV), and sulfide S2- ( 2470 eV) were observed in apatite, and the integrated areas of the different sulfur peaks correspond to changes in Embedded Image and bulk S content. Here, multiple tests confirmed that the S oxidation state in apatite remains constant when exposed to the synchrotron beam, at least for up to 1 h exposure (i.e., no irradiation damages). To our knowledge, this observation makes apatite the first mineral to incorporate reduced (S2-), intermediate (S4+), and oxidized (S6+) S in variable proportions as a function of the prevailing Embedded Image of the system. Apatites crystallized under oxidizing conditions (FMQ+1.2 and FMQ+3), where the S6+/STotal peak area ratio in the coexisting glass (i.e., quenched melt) is 1, are dominated by S6+ with a small contribution of S4+, whereas apatites crystallizing at reduced conditions (FMQ) contain predominantly S2-, lesser amounts of S6+, and possibly traces of S4+. A sulfur oxidation state vs. S concentration analytical line transect across hydrothermally altered apatite from the Mina Carmen iron oxide-apatite (IOA) deposit (Chile) demonstrates that apatite can become enriched in S4+ relative to S6+, indicating metasomatic overprinting via a SO2-bearing fluid or vapor phase. This XANES study demonstrates that as the Embedded Image increases from FQM to FMQ+1.2 to FMQ+3 the oxidation state of S in igneous apatite changes from S2- dominant to S6+ > S4+ to S6+ >> S4+. Furthermore, these results suggest that spectroscopic studies of igneous apatite have potential to trace the oxidation state of S in magmas. The presence of three S oxidations states in apatite may in part explain the non-Henrian partitioning of S between apatite and melt. Our study reveals the potential to use the S signature of apatite to elucidate both oxygen and sulfur fugacity in magmatic and hydrothermal systems.