The structures of albite and jadeite composition glasses quenched from high pressure

The structures of jadeite and albite composition glasses quenched from 10 and 15 kbar, respectively, have been studied using radial distribution analysis. It is found that aluminum does not undergo a coordination increase at these pressures, in agreement with recent Raman and NMR studies of these glass compositions. Radial distribution functions (RDF's) indicate that the structural response of albite and Jadeite composition melts to pressure up to 10–15 kbar has to do primarily with a distortion of the tetrahedral sites, a slight collapse of the tetrahedral rings forming the framework, and a small loss of short range order resulting in a more densely packed framework structure. The RDF's do not provide any clues concerning T-O-T angular changes at these pressures. It is suggested that the observed structural changes should be closely related to those that take place in melts of rhyolitic composition. Such changes in rhyolitic melts would result in a density increase and viscosity decrease with increasing pressure similar to that observed for melts of albite and jadeite composition.     

Petrogenesis of a basalt-rhyolite tephra from the west-central Afar,Ethiopia

The Cindery Tuff is an unusual tephra fall deposit that contains evidence for the mixing of basaltic and rhyolitic liquids prior to eruption. It contains clear rhyolitic glass shards together with brown basaltic glass spheres and a broadly bimodal phenocryst assemblage. Brown glasses are ferrobasaltic in composition and are similar to the voluminous Pliocene tholeiites of the surrounding west-central Afar volcanic field; both are enriched in the light rare earth and incompatible elements and possess higher ⁸⁷Sr/⁸⁶Sr and lower ¹⁴³Nd/¹⁴⁴Nd than MORB. Rhyolitic glasses are subalkaline and, compared to the basaltic glasses, are strongly depleted in the compatible elements and enriched in the incompatible elements. Both glass types have similar incompatible element and isotopic ratios, and with the rhyolite glass showing a 2-fold parallel enrichment in rare earth element abundances over the basaltic glass. These observations suggest that the two glasses are genetically related.Rare glasses with intermediate compositions occur as phenocryst melt inclusions, as mantles on phenocrysts and as free pumice clasts. Their major element contents do not point to an origin by simple hybrid mixing of the basaltic and rhyolitic melts. Rather, major element mixing calculations indicate formation of the intermediate and rhyolite melts by fractionation of the observed phenocryst assemblage, using a starting composition of the observed basaltic glass. Model calculations from trace element data, though lacking from the intermediate glasses, support fractional crystallization. The bimodal mineral assemblage argues against an immiscible liquid origin for the contrasting glass compositions.     

Experimental study of Cl solubility in hydrous alkaline melts: constraints on the theoretical maximum amount of Cl in trachytic and phonolitic melts

. Cl solubility in evolved alkaline melts was investigated at 860-930 °C and pressures of 25 to 250 MPa using natural trachytes and a synthetic phonolite equilibrated with subcritical fluids in the H₂O-(Na,K)Cl system (i.e. silicate melt coexisted with water-rich aqueous fluid and a saline brine). Fluid phase characteristics were identified by examination of fluid inclusions present in the run product glasses and the fluid bulk composition was calculated by mass balance. The Cl contents of trachytic glasses coexisting with subcritical fluids increase linearly with decreasing pressure from 250 to 25 MPa and range from 0.37 to 0.90 wt%; Cl in the phonolitic glass ranges from 0.35 to 0.59 wt%. These values are approximately twice those found in metaluminous rhyolitic melts under similar conditions. Variations from peralkaline to peraluminous composition has little effect on Cl solubility in trachytes, whereas it is a more important factor in phonolites. More generally, melt structure, in particular non-bringing oxygen, appears to strongly influence Cl solubility in silicate melts. The negative correlation between pressure and melt Cl content is governed by the large negative partial volume of NaCl in the vapour phase. No change in Cl solubility is observed between 200 and 250 MPa. Comparison of our experimental results with Cl abundance in glass inclusion and matrix glass from Italian volcanoes can be used to identify those eruptive products preserved in the geologic record which may have been associated with large Cl emissions.     

Formation of U-depleted rhyolite from a basanite at El Hierro, Canary Islands

Phonolite and trachyte are the felsic magmas of the alkaline magma suites, which characterize the Canary Islands. The October 2011 submarine eruption off El Hierro, the westernmost island, nevertheless, produced a small volume of rhyolitic magma. The rhyolite occurred as highly vesicular, white coloured pumices enveloped in and mingled with darker coloured basanitic pumice. The basanitic pumice is relatively crystal poor with a few euhedral olivines (mostly Fo_77–79), clinopyroxenes and Fe-rich spinels, whereas very rare olivine of same composition is found together with equally rare Fe-sulphide and FeTi-rich oxides in the rhyolite. The Fe–Mg exchange equilibrium in the oxides permits to calculate an equilibrium temperature of 970–890 °C for the rhyolite, in agreement with quartz-melt equilibrium at ca. 930 °C. A striking mineralogical feature of the rhyolite is the presence of rounded to contorted grains of milky quartz, which are xenocrysts incorporated and partly dissolved into the magma. Analyses of residual volatile concentrations in the glasses show that the rhyolite melt was highly degassed, whereas the basanitic glass still has important halogen concentrations. Trace element patterns of the mafic glasses and their elevated incompatible element concentrations are typical of the western Canary Island basanites. In contrast, the trace element composition of the rhyolite shows surprisingly low concentrations for all elements except the most incompatible ones (e.g. Rb, Ba, K and Th). All other measured LILE, HFSE and REE have significantly lower concentration than the basanitic counterpart that can be explained by fractionation of accessory phases (1 % apatite, 1 % sphene and 0.1 % zircon). Surprisingly, low U concentration is presumably related to elevated oxygen fugacity in the rhyolite, causing U to be in a hexavalent state, and fluxing of F-rich gas leading to volatilization of UF₆, known to emanate at low temperature. The results suggest that a gas-rich basanitic melt remobilized a small volume of stagnant rhyolitic melt formed by incorporation of approximately 10 % quartz-rich sediment into a late differentiate of trachytic composition. Sediments at the interface of an old oceanic crust adjacent to a continental shield and younger volcanic island are likely to act as magma traps were sediment assimilation may alter the mantle-derived magma composition. Quartz assimilation thus explains the production of rhyolite magma in a volcanic island characterized by an alkaline magma series from primitive basanites to trachytes.     

Bubble nucleation in rhyolite and dacite melts: temperature dependence of surface tension

Surface tension (σ) profoundly influences the ability of gas bubbles to nucleate in silicate melts. To determine how temperature impacts σ, experiments were carried out in which high-silica rhyolite melts with 5 wt% dissolved water were decompressed at temperatures that ranged from 775 to 1,085°C. Decompressions were also carried out using dacite melts with 4.3 wt% dissolved water at 1,150°C. Water bubbles nucleated in rhyolite only when decompressions exceeded 95 MPa at all temperatures. Bubbles nucleated in number densities that increased as decompression increased and at hotter temperatures at a given amount of decompression. After correcting decompression amounts for temperature differences, values for σ were estimated from nucleation rates and found to vary between 0.081 and 0.093 N m⁻¹. Surface tension decreases as temperature increases from 775 to 875°C, but then increases as temperature increases to 1,085°C. Those values overlap previous results, but only when melt viscosity is less than 10⁴ Pa s. For low-viscosity rhyolite, there is a strong correlation of σ with temperature, in which σ increases by 6.9 × 10⁻⁵ N m⁻¹ C⁻¹. That variation is robust for 5–9 wt% dissolved water, as long as melt viscosity is ≤10⁴ Pa s. More viscous rhyolite deviates from that correlation probably because nucleation is retarded in stiffer melts. Bubbles nucleated in dacite when decompressions exceeded 87 MPa, and occured in one or more events as decompression increased. Surface tension is estimated to be 0.083 (±0.001) N m⁻¹ and when adjusted for temperature agrees well with previous results for colder and wetter dacite melts. At a given water content, dacite melts have lower surface tensions than rhyolite melts, when corrected to a fixed temperature.     

Sulfur partition coefficient between apatite and rhyolite: the role of bulk S content

Experimental studies have been performed to constrain sulfur behavior during apatite crystallization and to determine sulfur partition coefficient between apatite and melt (Kd_S^apatite/melt) at oxidizing conditions. Crystallization experiments have been conducted with a hydrous rhyolitic melt and different bulk sulfur contents (0.15 to 2 wt.% S) at 900 and 1,000°C, 200 MPa and Δlog =NNO+3.6. The sulfur content in the glass increases with increasing amount of added S. Anhydrite crystallizes for S added = 0.75 wt.% (0.10 and 0.13 wt.% SO₃ in glass at 900 and 1,000°C, respectively). The amount of anhydrite increases and the amount of apatite decreases with increasing amount of added sulfur. The sulfur exchange reaction in apatite is influenced by the bulk composition of the melt (e.g., P content). However, changing melt composition has only little effect on Kd_S^apatite/melt for the investigated rhyolitic composition. The Kd_S^apatite/melt does not depend directly on temperature, decreases from 14.2 to 2.7 with increasing S content in glass from SO₃=0.03 to 0.19 wt.%, respectively, and can be predicted from the following equation: ln Kd = −0.0025×S in melt (in ppm)+2.9178. The combination of experimental data obtained for rhyolitic and andesitic melts reveals that the sulfur partition coefficient tends toward a value of 2 for high-sulfur content in the glass (>0.2 wt.% SO₃). Using S in apatite as proxy for determining S content in melt is promising but additional experimental data are needed to clarify the individual effects of T, , and P and Ca content in the melt on S partitioning.     

Heterogeneous bubble nucleation in highly viscous silicate melts during instantaneous decompression from high pressure

The nucleation of H₂O bubbles in magmas has been proposed as a trigger for volcanic eruptions. To determine how bubbles nucleate heterogeneously in silicate melts, experiments were carried out in which high-silica rhyolitic melts were hydrated at 800 °C and either 50 or 125 MPa, and then decompressed by 20–91 MPa at temperatures that ranged between 550 and 700 °C, and held at the lower pressures for 10–720 s before being quenched. Bubbles nucleated in number densities (N_B) that vary between 3 × 10⁷ and 2 × 10⁸ cm^− 3. Blocky shaped magnetite or the ends of needle-shaped hematite acted as sites for nucleation, but only if a minimum super-saturation was exceeded, which increases with increasing melt viscosity. Bubbles did not nucleate along the lengths of hematite needles nor on plagioclase. Both the beginning and ending times of the nucleation event increases with increasing melt viscosity. Using nucleation theory predictions, neither the slower nucleation rates nor the changing activation of nucleation sites can be adequately explained by the differences in temperature, water diffusivity, or viscosity. Instead, the variations in nucleation kinetics are best explained by changes in surface tension between melt and vapor, resulting from the increasing polymerization of the melt at lower temperatures and water contents. Because only ∼ 10⁸ bubbles cm^− 3 nucleate on magnetite in the rhyolite melt used, almost regardless of experimental conditions, results from this study may not be directly comparable to vesicle numbers in volcanic pumice of different compositions.     

Experimental investigation of H2O and Cl− solubilities in F-enriched silicate liquids; implications for volatile saturation of topaz rhyolite magmas

To interpret the degassing of F-bearing felsic magmas, the solubilities of H₂O, NaCl, and KCl in topaz rhyolite liquids have been investigated experimentally at 2000, 500, and ≈1 bar and 700° to 975 °C. Chloride solubility in these liquids increases with decreasing H₂O activity, increasing pressure, increasing F content of the liquid from 0.2 to 1.2 wt% F, and increasing the molar ratio of ((Al + Na + Ca + Mg)/Si). Small quantities of Cl⁻ exert a strong influence on the exsolution of magmatic volatile phases (MVPs) from F-bearing topaz rhyolite melts at shallow crustal pressures. Water- and chloride-bearing volatile phases, such as vapor, brine, or fluid, exsolve from F-enriched silicate liquids containing as little as 1 wt% H₂O and 0.2 to 0.6 wt% Cl at 2000 bar compared with 5 to 6 wt% H₂O required for volatile phase exsolution in chloride-free liquids. The maximum solubility of Cl⁻ in H₂O-poor silicate liquids at 500 and 2000 bar is not related to the maximum solubility of H₂O in chloride-poor liquids by simple linear and negative relationships; there are strong positive deviations from ideality in the activities of each volatile in both the silicate liquid and the MVP(s). Plots of H₂O versus Cl⁻ in rhyolite liquids, for experiments conducted at 500 bar and 910°–930 °C, show a distinct 90° break-in-slope pattern that is indicative of coexisting vapor and brine under closed-system conditions. The presence of two MVPs buffers the H₂O and Cl⁻ concentrations of the silicate liquids. Comparison of these experimentally-determined volatile solubilities with the pre-eruptive H₂O and Cl⁻ concentrations of five North American topaz and tin rhyolite melts, determined from melt inclusion compositions, provides evidence for the exsolution of MVPs from felsic magmas. One of these, the Cerro el Lobo magma, appears to have exsolved alkali chloride-bearing vapor plus brine or a single supercritical fluid phase prior to entrapment of the melt inclusions and prior to eruption. Received: 6 November 1995 / Accepted: 29 January 1998     

Concentrations and behavior of oxygen and oxide ion in melts of composition CaO · MgO · xSiO2

The concentrations and behavior of oxygen and oxide ion were studied in silicate melts of composition CaO · MgO · xSiO₂ (1.25 ≤ x ≤ 3) in the temperature range 1425 to 1575°C by cyclic voltammetry and chronopotentiometry. Electroreduction of oxygen is a reversible, 2 electron process involving dissociated oxygen atoms. The Henry's Law constant for O₂ in molten diopside (CaO · MgO · 2SiO₂) is 0.023 ± 0.004 mole/l atm at 1450°C. The diffusion coefficient for molecular oxygen in diopside melt is 4.5 ± .5 × 10^?6 cm²/sec at 1450°C and the activation energy of diffusion is 80 ± 2 kcal/mole. Oxide ions produced by electroreduction of oxygen, rapidly dissociate silicate polymers, causing the concentration of free oxide ions in diopside melt to be buffered at a low level (4.7 ± .8 × 10^?5 mole/l). The concentration of free oxide ion increases at higher proportions of metal oxides but remains at this value in more silicic melts. The rate of formation of oxide ions by polymerization in diopside melt is 0.021 ± .007 mole/l sec. Thermodynamic parameters (the standard free energy, enthalpy and entropy) for the oxidation of Ni, Co, and Zn in diopside melt in equilibrium with gaseous oxygen agree with those for solid oxide systems. The platinum reference electrode in molten diopside is a reversible, oxygen electrode.     

Aluminosilicate melts: structure, composition and temperature

The anionic structure of aluminosilicate melts of intermediate degree of polymerization (NBO/T = 0.5) and with along the composition join (LS4-LA4) has been examined in-situ to ˜1480 °C, and compared with recent data for melts along the analog composition join and with less polymerized melts along the join and O_{_5}. With , the anionic equilibrium, (1) , adequately describes the structure. With , a second expression, (2) , is required because an additional structural unit, Q¹, is stabilized in the melts. The enthalpy, , of reaction (1) increases from − 36 ±4 kJ/mol in the absence of aluminum to 34± 5 kJ/mol at and 64 ± 4 kJ/mol at Al/(Al + Si) = 0.45. Similar trends are reported for other alkali aluminosilicate melts. Least-squares fitting of abundance of structural units as a function of temperature and bulk composition has been conducted. The unit abundance is dominantly a function of temperature, Al/(Al +Si), and bulk melt polymerization. Configurational entropy and heat capacity of mixing of melts above their glass transition temperatures have been calculated with the aid of the least-squares fitted equations. The values of these parameters indicate that as the ionization potential of the metal cations increases, configurational heat capacity of alkali aluminosilicate melts becomes temperature dependent. As a result, transport properties (viscosity, diffusivity, and conductivity) of such melts will not show Arrhenian behavior even in the high-temperature range. Further, discontinuous changes in entropy and heat capacity of mixing results from temperature-induced changes in types of structural units in the melts. Such discontinuous changes would also be reflected in discontinuous changes of temperature-dependent transport properties. Received: 26 September 1996 / Accepted: 18 October 1996     

Experimental studies of the distribution of rare earths as trace elements among silicate minerals and liquids and water

The distribution of the REE between synthetic diopside, forsterite, enstatite, and gaseous water and between natural plagioclase, 2 rhyolite obsidian melts and gaseous water have been measured. Values for distribution coefficients (D) for the REE between the minerals and aqueous fluid vary significantly over the temperature range of 550°C to 850°C, but little variation was found for the values of D between the silicate liquids and aqueous fluid over a temperature range of 100°C. By assuming that the values of D for the silicate liquids are independent of major element composition and temperature, it is possible to calculate values of D for REE between silicate minerals and silicate liquid. The values obtained for diopside, forsterite, enstatite and plagioclase compare favorably with those obtained for the natural materials clinopyroxene, olivine, orthopyroxene and plagioclase (except for Eu). The values of D for diopside were found to increase and those for forsterite and enstatite to decrease with increasing temperatuie. Values of temperature of equilibration for natural minerals obtained by extrapolation of graphs for experimental data of In D against 1/T for the systems diopside-silicate liquid, forsterite-silicate liquid, and forsterite-diopside fall within a reasonable range, suggesting the possibility of geothermometry using REE concentrations of minerals.     

Argon and CO2 on the race track in silicate melts: A tool for the development of a CO2 speciation and diffusion model

We have analysed the kinetics of Argon and CO₂ diffusion in simplified iron free rhyolitic to hawaiitic melts using the diffusion couple technique. The concentration distance profiles of Ar and CO₂ were measured with electron microprobe analysis and Fourier Transform Infrared Spectroscopy, respectively. Error functions were fitted to the symmetrical concentration distance profiles to extract the diffusion coefficients.In the temperature range 1373 to 1773 K the activation energies for Ar diffusion range from 169 ± 20 to 257 ± 62 kJ mol⁻¹. Ar diffusivity increases exponentially with the degree of depolymerisation. In contrast, the mobility of total CO₂, that is identical to Ar mobility in rhyolitic melt, keeps constant with changing bulk composition from rhyolite to hawaiite. CO₂ speciation at 1623 K and 500 MPa was modeled for the range of compositions studied using the diffusion data of Ar and total CO₂ in combination with network former diffusion calculated from viscosity data. Within error this model is in excellent agreement with CO₂ speciation data extrapolated from temperatures near the glass transition temperature for dacitic melt composition. This model shows that even in highly depolymerised hawaiitic and tholeiitic melts molecular CO₂ is a stable species and contributes 70 to 80% to the total CO₂ diffusion, respectively.     

Iron-bearing silicate melts: Relations between pressure and redox equilibria

Mossbauer spectroscopy has been used to determine the redox equilibria of iron and structure of quenched melts on the composition join Na₂Si₂O₅-Fe₂O₃ to 40 kbar pressure at 1400° C. The Fe³⁺/ΣFe decreases with increasing pressure. The ferric iron appears to undergo a gradual coordination transformation from a network-former at 1 bar to a network-modifier at higher (≧10 kbar) pressure. Ferrous iron is a network-modifier in all quenched melts. Reduction of Fe³⁺ to Fe²⁺ and coordination transformation of remaining Fe³⁺ result in depolymerization of the silicate melts (the ratio of nonbridging oxygens per tetrahedral cations, NBO/T, increases). It is suggested that this pressure-induced depolymerization of iron-bearing silicate liquids results in increasing NBO/T of the liquidus minerals. Furthermore, this depolymerization results in a more rapid pressure-induced decrease in viscosity and activation energy of viscous flow of iron-bearing silicate melts than would be expected for iron-free silicate melts with similar NBO/T.     

Ferric/ferrous ratio in silicate melts: a new model for 1 atm data with special emphasis on the effects of melt composition

The effect of MgO and total FeO on ferric/ferrous ratio in model multicomponent silicate melts was investigated experimentally in the temperature range 1300–1500 °C at 1 atm total pressure in air. We demonstrate that the addition of these weak network modifier cations results in an increase of Fe³⁺/Fe²⁺ ratio in both mafic and silicic melts. Based on present and published experimental data, a new empirical equation is proposed to predict the ferric/ferrous ratio as a function of oxygen fugacity, temperature and melt composition. In contrast to previous equations, the compositional effect of melts on the Fe³⁺/Fe²⁺ ratio is not only modeled by the sum of the molar fraction of the individual oxide components. Additional interactions terms have also been incorporated. The main advantage of the proposed model is its applicability for a wide compositional range. However, its application to felsic melts (>?68 wt% SiO₂) is not recommended. Other advantages of this equation and differences when compared with previous models are discussed.     

Mineral/melt partitioning of trace elements during hydrous peridotite partial melting

This experimental study examines the mineral/melt partitioning of incompatible trace elements among high-Ca clinopyroxene, garnet, and hydrous silicate melt at upper mantle pressure and temperature conditions. Experiments were performed at pressures of 1.2 and 1.6 GPa and temperatures of 1,185 to 1,370 °C. Experimentally produced silicate melts contain up to 6.3 wt% dissolved H ₂O, and are saturated with an upper mantle peridotite mineral assemblage of olivine+orthopyroxene+clinopyroxene+spinel or garnet. Clinopyroxene/melt and garnet/melt partition coefficients were measured for Li, B, K, Sr, Y, Zr, Nb, and select rare earth elements by secondary ion mass spectrometry. A comparison of our experimental results for trivalent cations (REEs and Y) with the results from calculations carried out using the Wood-Blundy partitioning model indicates that H ₂O dissolved in the silicate melt has a discernible effect on trace element partitioning. Experiments carried out at 1.2 GPa, 1,315 °C and 1.6 GPa, 1,370 °C produced clinopyroxene containing 15.0 and 13.9 wt% CaO, respectively, coexisting with silicate melts containing ~1–2 wt% H ₂O. Partition coefficients measured in these experiments are consistent with the Wood-Blundy model. However, partition coefficients determined in an experiment carried out at 1.2 GPa and 1,185 °C, which produced clinopyroxene containing 19.3 wt% CaO coexisting with a high-H ₂O (6.26±0.10 wt%) silicate melt, are significantly smaller than predicted by the Wood-Blundy model. Accounting for the depolymerized structure of the H ₂O-rich melt eliminates the mismatch between experimental result and model prediction. Therefore, the increased Ca ²⁺ content of clinopyroxene at low-temperature, hydrous conditions does not enhance compatibility to the extent indicated by results from anhydrous experiments, and models used to predict mineral/melt partition coefficients during hydrous peridotite partial melting in the sub-arc mantle must take into account the effects of H ₂O on the structure of silicate melts.     

Petrogenesis of Mafic Inclusions in Rhyolitic Lavas from Narugo Volcano, Northeastern Japan

Mafic inclusions present in the rhyolitic lavas of Narugo volcano,Japan, are vesiculated andesites with diktytaxitic texturesmainly composed of quenched acicular plagioclase, pyroxenes,and interstitial glass. When the mafic magma was incorporatedinto the silica-rich host magma, the cores of pyroxenes andplagioclase began to crystallize (>1000°C) in a boundarylayer between the mafic and felsic magmas. Phenocryst rim compositionsand interstitial glass compositions (average 78 wt % SiO₂) inthe mafic inclusions are the same as those of the phenocrystsand groundmass glass in the host rhyolite. This suggests thatthe host felsic melt infiltrated into the incompletely solidifiedmafic inclusion, and that the interstitial melt compositionin the inclusions became close to that of the host melt (c.850°C). Infiltration was enhanced by the vesiculation ofthe mafic magma. Finally, hybridized and density-reduced portionsof the mafic magma floated up from the boundary layer into thehost rhyolite. We conclude that the ascent of mafic magma triggeredthe eruption of the host rhyolitic magma. KEY WORDS: mafic inclusion; stratified magma chamber; magma mixing; mingling; Narugo volcano; Japan     

Mineral chemistry,crystallization conditions and magma mixing‐mingling at Orduzu volcano (Malatya), Eastern Anatolia,Turkey

The Middle Miocene Orduzu volcanic suite, which is a part of the widespread Neogene Yamadağ volcanism of Eastern Anatolia, consists of a rhyolitic lava flow, rhyolitic dykes, a trachyandesitic lava flow and basaltic trachyandesitic dykes. Existence of mafic enclaves and globules in some of the volcanic rocks, and microtextures in phenocrysts indicate that magma mingling and mixing between andesitic and basaltic melts played an important role in the evolution of the volcanic suite. Major and trace element characteristics of the volcanic rocks are similar to those formed in convergent margin settings. In particular, incompatible trace element patterns exhibit large depletions in high field strength elements (Nb and Ta) and strong enrichments in both large ion lithofile elements (Ba, Th and U) and light rare earth elements, indicating a strong subduction signature in the source of the volcanic rocks. Furthermore, petrochemical data obtained suggest that parental magmas of rhyolite lava and dykes, and trachyandesite lava and basaltic trachyandesite dykes were derived from subduction‐related enriched lithospheric mantle and metasomatized mantle (± asthenosphere), respectively. A detailed mineralogical study of the volcanic suite shows that plagioclase is the principal phenocryst phase in all of the rock units from the Orduzu volcano. The plagioclase phenocrysts are accompanied by quartz in the rhyolitic lava flows and by two pyroxenes in the trachyandesitic lava flows and basaltic trachyandesitic dykes. Oxide phases in all rocks are magnetite and ilmenite. Calculated crystallization temperatures range from 650°C to 800°C for plagioclase, 745°C–1054°C for biotite, 888°C–915°C for pyroxene and 736°C–841°C for magnetite–ilmenite pairs. Calculated crystallization pressures of pyroxenes vary between 1.24–5.81 kb, and oxygen fugacity range from −14.47 to −12.39. The estimates of magmatic intensive parameters indicate that the initial magma forming the Orduzu volcanic unit began to crystallize in a high‐level magma chamber and then was stored in a shallow reservoir where it underwent intermediate‐mafic mixing. The rhyolitic lava flow and dykes evolved in relatively shallower crustal magma chambers. Copyright © 2007 John Wiley & Sons, Ltd.     

Oxygen isotope and trace element evidence for three-stage petrogenesis of the youngest episode (260–79 ka) of Yellowstone rhyolitic volcanism

We report the first high-precision δ¹⁸O analyses of glass, δ¹⁸O of minerals, and trace element concentrations in glass and minerals for the 260–79 ka Central Plateau Member (CPM) rhyolites of Yellowstone, a >350 km³ cumulative volume of lavas erupted inside of 630 ka Lava Creek Tuff (LCT) caldera. The glass analyses of these crystal-poor rhyolites provide direct characterization of the melt and its evolution through time. The δ¹⁸O_glass values are low and mostly homogeneous (4.5 ± 0.14 ‰) within and in between lavas that erupted in four different temporal episodes during 200 ka of CPM volcanism with a slight shift to lower δ¹⁸O in the youngest episode (Pitchstone Plateau). These values are lower than Yellowstone basalts (5.7–6 ‰), LCT (5.5 ‰), pre-, and extracaldera rhyolites (~7–8 ‰), but higher than the earliest 550–450 ka post-LCT rhyolites (1–2 ‰). The glass δ¹⁸O value is coupled with new clinopyroxene analyses and previously reported zircon analyses to calculate oxygen isotope equilibration temperatures. Clinopyroxene records >900 °C near-liquidus temperatures, while zircon records temperatures <850 °C similar to zircon saturation temperature estimates. Trace element concentrations in the same glass analyzed for oxygen isotopes show evidence for temporal decreases in Ti, Sr, Ba, and Eu—related to Fe–Ti oxide and sanidine (±quartz) crystallization control, while other trace elements remain similar or are enriched through time. The slight temporal increase in glass Zr concentrations may reflect similar or higher temperature magmas (via zircon saturation) through time, while previosuly reported temperature decreases (e.g., Ti-in-quartz) might reflect changing Ti concentrations with progressive melt evolution. Multiple analyses of glass across single samples and in profiles across lava flow surfaces document trace element heterogeneity with compatible behavior of all analyzed elements except Rb, Nb, and U. These new data provide evidence for a three-stage geochemical evolution of these most recent Yellowstone rhyolites: (1) repeated batch melting events at the base of a homogenized low-δ¹⁸O intracaldera fill resulting in liquidus rhyolite melt and a refractory residue that sequesters feldspar-compatible elements over time. This melting may be triggered by conductive "hot plate" heating by basaltic magma intruding beneath the Yellowstone caldera resulting in contact rhyolitic melt that crystallizes early clinopyroxene and/or sanidine at high temperature. (2) Heterogeneity within individual samples and across flows reflects crystallization of these melts during preeruptive storage of magma at at lower, zircon-saturated temperatures. Compatible behavior and variations of most trace elements within individual lava flows are the result of sanidine, quartz, Fe–Ti oxide, zircon, and chevkinite crystallization at this stage. (3) Internal mixing immediately prior to and/or during eruption disrupts, these compositional gradients in each parental magma body that are preserved as melt domains distributed throughout the lava flows. These results based on the most recent and best-preserved volcanic products from the Yellowstone volcanic system provide new insight into the multiple stages required to generate highly fractionated hot spot and rift-related rhyolites. Our proposed model differs from previous interpretations that extreme Sr and Ba depletion result from long-term crystallization of a single magma body—instead we suggest that punctuated batch melting events generated a sanidine-rich refractory residue and a melt source region progressively depleted in Sr and Ba.     

Structure and Composition Effects on the Oxygen Isotope Fractionation in Silicate Melts

The influence of melt composition and structure on the oxygen isotope fractionation was studied for the multicomponent (SiO₂ ± TiO₂ + Al₂O₃ ± Fe₂O₃ + MgO ± CaO) system at 1500°C and 1 atm. The experiments show that significant oxygen isotope effects can be observed in silicate melts even at such high temperature. It is shown that the ability of silicate melt to concentrate ¹⁸O isotope is mainly determined by its structure. In particular, an increase of the NBO/T ratio in the experimental glasses from 0.11 to 1.34 is accompanied by a systematic change of oxygen isotope difference between melt and internal standard by values from–0.85 to +1.29‰. The obtained data are described by the model based on mass-balance equations and the inferred existence of O⁰, O^–, and O^2– (bridging, non-bridging, and free oxygen) ions in the melts. An application of the model requires the intra-structure isotope fractionation between bridging and non-bridging oxygens. Calculations show that the intra-structure isotope fractionation in our experiments is equal to 4.2 ± 1.0‰. To describe the obtained oxygen isotope effects at the melts relatively to temperature and fraction of non-bridging oxygen a general equation was proposed.     

The experimental calibration of the iron isotope fractionation factor between pyrrhotite and peralkaline rhyolitic melt

A first experimental study was conducted to determine the equilibrium iron isotope fractionation between pyrrhotite and silicate melt at magmatic conditions. Experiments were performed in an internally heated gas pressure vessel at 500 MPa and temperatures between 840 and 1000 °C for 120-168 h. Three different types of experiments were conducted and after phase separation the iron isotope composition of the run products was measured by MC-ICP-MS. (i) Kinetic experiments using ⁵⁷Fe-enriched glass and natural pyrrhotite revealed that a close approach to equilibrium is attained already after 48 h. (ii) Isotope exchange experiments—using mixtures of hydrous peralkaline rhyolitic glass powder (∼4 wt% H₂O) and natural pyrrhotites (Fe_1 − xS) as starting materials— and (iii) crystallisation experiments, in which pyrrhotite was formed by reaction between elemental sulphur and rhyolitic melt, consistently showed that pyrrhotite preferentially incorporates light iron. No temperature dependence of the fractionation factor was found between 840 and 1000 °C, within experimental and analytical precision. An average fractionation factor of Δ ⁵⁶Fe/⁵⁴Fe_{pyrrhotite-melt} = −0. 35 ± 0.04‰ (2SE, n = 13) was determined for this temperature range. Predictions of Fe isotope fractionation between FeS and ferric iron-dominated silicate minerals are consistent with our experimental results, indicating that the marked contrast in both ligand and redox state of iron control the isotope fractionation between pyrrhotite and silicate melt. Consequently, the fractionation factor determined in this study is representative for the specific Fe²⁺/ΣFe ratio of our peralkaline rhyolitic melt of 0.38 ± 0.02. At higher Fe²⁺/ΣFe ratios a smaller fractionation factor is expected. Further investigation on Fe isotope fractionation between other mineral phases and silicate melts is needed, but the presented experimental results already suggest that even at high temperatures resolvable variations in the Fe isotope composition can be generated by equilibrium isotope fractionation in natural magmatic systems.