Interdiffusion of Na,K,and Ca Between Granitic Melts and NaCl Liquid

This study is aimed at determining the diffusion coefficient of net-work modifiers (mainly Na, K, and Ca) in a two-phase melt-NaCl system, in which the melts are granitic and the system is NaCl-rich in composition. The diffusion coefficients of Na, K, and Ca were measured at the temperatures of 750 – 1400°C, pressures of 0.001 × 10⁸ – 2 × 10⁸ Pa, and initial H₂O contents of 0 wt% –6.9 wt% in the granitic melts. The diffusion coefficients of Fe and Mg were difficult to resolve. In all experiments a NaCl melt was present as well. In the absence of H₂O, the diffusion of net-work modifiers follows an Arrhanious equation at 1 × 10⁵ Pa: lgD_ca=−3. 88−5140/T, lgD_k =−3. 79−4040/T, and lgD_Na, =−4.99−3350/T, where D is in cm² /s andT is in K. The diffusion coefficients of Ca, Na, K, and Fe increase non-linearly with increasing H₂O content in the melt. The presence of about 2 wt% H₂O m the melt will lead to a dramatical increase in diffusivity, but higher H₂O content has only a minor effect. This change is probably the result of a change in the melt structure when H₂O is present. The diffusion coefficients measured in this study are significantly different from those in previous works. This may be understood in terms of the “transient two-liquid equilibrium” theory. Element interdiffusion depends not only on its concentration, but also on its activity co-efficient gradient, which is reflected by the distribution coefficient, of the two contacting melts.     

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     

Determination of sulfur speciation and oxidation state of olivine hosted melt inclusions

In order to better understand what controls sulfur speciation in melt inclusions, and how that pertains to the original basalt composition, we have conducted a series of heating experiments on naturally quenched and crystalline olivine-hosted melt inclusions. Sulfur speciation was determined from S Kα peak shift measurements by electron microprobe on the experimentally heated inclusions as well as a series of naturally quenched inclusions, and matrix glasses.Naturally quenched olivine-hosted melt inclusions record a similar but more variable sulfur speciation relative to matrix glasses, (up to 45–50% variation in S⁶⁺/S_total). Much of this range can be attributed to the effect of degassing which may either increase or decrease the S⁶⁺/S_total. In addition, olivine melt re equilibration and H diffusion out of the inclusion both potentially result in the oxidation of melt inclusions. Heating of melt inclusions can have different effects on the sulfur speciation under different conditions. A slight decrease in S⁶⁺/S_total and oxygen fugacity (∼0.1 log units) can occur from overheating of inclusions (above the temperature of entrapment), resulting from excess ferrous iron in the melt. An increase in heating times should result in an oxidation of the inclusion generated by increased H diffusion out of the inclusion. However, results of heating experiments on melt inclusions from an Izu backarc basalt for less than 30  min do not show a significant increase in sulfur oxidation. In addition, experiments conducted at both IW and FMQ have measured sulfur speciation consistent with naturally quenched inclusions suggesting that at experimental temperatures near that of olivine crystallization the furnace atmosphere does not exert significant control on the melt fO₂. By taking these parameters into account, sulfur speciation and oxidation state of basaltic melt trapped within inclusions can be accurately determined from both naturally quenched and heated olivine hosted melt inclusions.     

Solubility of platinum and palladium in silicate melts under high water pressure as a function of redox conditions

The solubility of platinum and palladium in a silicate melt of the composition Di ₅₅ An ₃₅ Ab ₁₀ was determined at 1200°C and 2 kbar pressure in the presence of H₂O-H₂ fluid at an oxygen fugacity ranging from the HM to WI buffer equilibria. The influence of sulfur on the solubility of platinum in fluid-bearing silicate melt was investigated at a sulfur fugacity controlled by the Pt-PtS equilibrium at 1200°C and a pressure defined in such a way that the \(f_{H_2 O} \) and \(f_{O_2 } \) values were identical to those of the experiments without sulfur. The experiments were conducted in a high pressure gas vessel with controlled hydrogen content in the fluid. Oxygen fugacity values above the NNO buffer were controlled by solid-phase buffer mixtures using the two-capsule technique. Under more reducing conditions, the contents of H₂O and H₂ were directly controlled by the argon to hydrogen ratio in a special chamber. The hydrogen fugacity varied from 5.2 × 10^?2 bar (HM buffer) to 1230 bar (\(X_{H_2 } \) = 0.5). Pt and Pd contents were measured in quenched glass samples by neutron activation analysis. The results of these investigations showed that the solubility of Pt and Pd increases significantly in the presence of water compared with experiments in dry systems. The content of Pd within the whole range of redox conditions and that of Pt at an oxygen fugacity between the HM to MW buffer reactions are weakly dependent on \(f_{O_2 } \) and controlled mainly by water fugacity. This suggests that, in addition to oxide Pt and Pd species soluble at the ppb level in haplobasaltic melts, much more soluble (ppm level) hydroxide complexes of these metals are formed under fluid-excess conditions. Despite a decrease in water fugacity under reducing conditions, Pt solubility increases sharply near the MW buffer. It was shown by electron paramagnetic resonance spectrometry that, in contrast to dry melts, fluid-saturated silicate melts do not contain a pure metal phase (micronuggets). Therefore, the increase in Pt solubility under reducing conditions can be explained by the formation of Pt hydride complexes or Pt-fluid-silicate clusters. At a sulfur fugacity controlled by the Pt-PtS equilibrium, the solubility of Pt in iron-free silicate melts as a function of redox conditions is almost identical to that obtained in the experiments without sulfur at the same water and oxygen fugacity values. These observations also support Pt dissolution in iron-free silicate melts as hydroxide species.     

Experimental data on the speciation of sulfur as a function of oxygen fugacity in basaltic melts

The speciation of sulfur as a function of oxygen fugacity was calculated in glasses of basaltic composition saturated experimentally with either sulfide or sulfate phases. The experiments were conducted on mixtures of synthetic and natural materials equilibrated at 1300 °C and 1 GPa in a piston-cylinder apparatus. Sulfur speciation was calculated by measuring the peak shift of the sulfur Kα radiation relative to a sulfide standard, whereas oxygen fugacity was calculated from the composition of olivine and spinel present in the assemblages. The results are consistent with sulfur being present as sulfite (S⁴⁺) in addition to sulfate (S⁶⁺) in oxidized melts. Therefore, sulfur speciation derived from SKα peak shifts should be seen as ”sulfate mole fraction equivalents“ (X(S⁶⁺)_eq.). Using the data available, an empiric function:

X(S6+)_eq.=0.86/(1+exp(2.89−2.23ΔFMQ))     

Sulfur speciation and network structural changes in sodium silicate glasses: Constraints from NMR and Raman spectroscopy

Information about the state of sulfur in silicate melts and glasses is important in both earth sciences and materials sciences. Because of its variety of valence states from S²⁻ (sulfide) to S⁶⁺ (sulfate), the speciation of sulfur dissolved in silicate melts and glasses is expected to be highly dependent on the oxygen fugacity. To place new constraint on this issue, we have synthesized sulfur-bearing sodium silicate glasses (quenched melts) from starting materials containing sulfur of different valence states (Na₂SO₄, Na₂SO₃, Na₂S₂O₃ and native S) using an internally heated gas pressure vessel, and have applied electron-induced SKα X-ray fluorescence, micro-Raman and NMR spectroscopic techniques to probe their structure. The wavelength shift of SKα X-rays revealed that the differences in the valence state of sulfur in the starting compounds are largely retained in the synthesized sulfur-bearing glasses, with a small reduction for more oxidized samples. The ²⁹Si MAS NMR spectra of all the glasses contain no peaks attributable to the SiO_4-nS_n (with n > 0) linkages. The Raman spectra are consistent with the coexistence of sodium sulfate (Na₂SO₄) species and one or more types of more reduced sulfur species containing S-S linkages in all the sulfur-bearing silicate glasses, with the former dominant in glasses produced from Na₂SO₄-doped starting materials, and the latter more abundant in more reduced glasses. The ²⁹Si MAS NMR and Raman spectra also revealed changes in the silicate network structure of the sulfur-bearing glasses, which can be interpreted in terms of changes in the chemical composition and sulfur speciation.     

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.     

The fidelity of melt inclusions as records of melt composition

A series of experiments created melt inclusions in plagioclase and pyroxene crystals grown from a basaltic melt at 1,150°C, 1.0 GPa to investigate diffusive fractionation during melt inclusion formation; additionally, P diffusion in a basaltic melt was measured at 1.0 GPa. Melt inclusions and melts within a few 100 microns of plagioclase–melt interfaces were analyzed for comparison with melt compositions far from the crystals. Melt inclusions and melt compositions in the boundary layer close to the crystal–melt interface were similar, but both differ significantly in incompatible element concentrations from melt found greater than approximately 200 microns away from the crystals. The compositional profiles of S, Cl, P, Fe, and Al in the boundary layers were successfully reproduced by a two-step model of rapid crystal growth followed by diffusive relaxation toward equilibrium after termination of crystal growth. Applying this model to investigate possible incompatible element enrichment in natural melt inclusions demonstrated that at growth rates high enough to create the conditions for melt inclusion formation, ∼10⁻⁹–10⁻⁸ m s⁻¹, the concentration of water in the boundary layer near the crystal was similar to that of the bulk melt because of its high diffusion coefficient, but sulfur, with a diffusivity similar to major elements and CO₂, was somewhat enriched in the boundary layer melt, and phosphorus, with its low diffusion coefficient similar to other high-field strength elements and rare earth elements, was significantly enriched. Thus, the concentrations of sulfur and phosphorus in melt inclusions may over-estimate their values in the bulk melt, and other elements with similar diffusion coefficients may also be enriched in melt inclusions relative to the bulk melt. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Influence of oxygen fugacity on the solubility of carbon and hydrogen in FeO-Na<Subscript>2</Subscript>O-SiO<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> melts in equilibrium with liquid iron at 1.5 GPa and 1400°C

Equilibria in the model melt (NaAlSi₃O₈(80) + FeO(20))-C-H₂ system were experimentally studied at ΔlogfO₂(IW) from −2.2 to −5.6, a pressure of 1.5 GPa, and a temperature of 1400°C. The experiments were conducted in a piston-cylinder apparatus using Pt capsules. The low fO₂ values were imposed during the experiments by adding 2, 5, and 7 wt % of finely dispersed SiC to NaAlSi₃O₈(80) + FeO(20) powder. The experimental products were investigated by electron microprobe analysis and Raman spectroscopy. The investigations showed that melting at 1.5 GPa and 1400°C in the stability field of a metallic iron phase produces silicate liquids containing both oxidized and reduced H and C species. Carbon and hydrogen are dissolved in the melt as C-H (CH₄) complexes. In addition, OH⁻ groups, molecular hydrogen H₂, and molecular water H₂O were observed in the melts. The proportions of dissolved C and H species strongly depend on oxygen fugacity. With decreasing fO₂, the content of O-H species decreases and that of H-C species increases. The obtained data and previous results (Kadik et al., 2004, 2006) allow us to suppose a fundamental change in the character of magmatic transfer of C-O-H components during the evolution of the redox state of the Earth’s mantle in geologic time toward higher fO₂ in its interiors.     

Magmatic processes that generated the rhyolite of Glass Mountain, Medicine Lake volcano, N. California

Glass Mountain consists of a 1 km³, compositionally zoned rhyolite to dacite glass flow containing magmatic inclusions and xenoliths of underlying shallow crust. Mixing of magmas produced by fractional crystallization of andesite and crustal melting generated the rhyolite of Glass Mountain. Melting experiments were carried out on basaltic andesite and andesite magmatic inclusions at 100, 150 and 200 MPa, H₂O-saturated with oxygen fugacity controlled at the nickel-nickel oxide buffer to provide evidence of the role of fractional crystallization in the origin of the rhyolite of Glass Mountain. Isotopic evidence indicates that the crustal component assimilated at Glass Mountain constitutes at least 55 to 60% of the mass of erupted rhyolite. A large volume of mafic andesite (2 to 2.5 km³) periodically replenished the magma reservoir(s) beneath Glass Mountain, underwent extensive fractional crystallization and provided the heat necessary to melt the crust. The crystalline residues of fractionation as well as residual liquids expelled from the cumulate residues are preserved as magmatic inclusions and indicate that this fractionation process occurred at two distinct depths. The presence and composition of amphibole in magmatic inclusions preserve evidence for crystallization of the andesite at pressures of at least 200 MPa (6 km depth) under near H₂O-saturated conditions. Mineralogical evidence preserved in olivine-plagioclase and olivine-plagioclase-high-Ca clinopyroxene-bearing magmatic inclusions indicates that crystallization under near H₂O-saturated conditions also occurred at pressures of 100 MPa (3 km depth) or less. Petrologic, isotopic and geochemical evidence indicate that the andesite underwent fractional crystallization to form the differentiated melts but had no chemical interaction with the melted crustal component. Heat released by the fractionation process was responsible for heating and melting the crust. Received: 26 March 1996 / Accepted: 14 November 1996     

Immiscible separation of metalliferous Fe/ Ti-oxide melts from fractionating alkali basalt: P-T-f O2 conditions and two-liquid elemental partitioning

Globules of iron-dominated (59–69 wt% FeO_tot) and titanium-dominated (43.5 wt% TiO₂) oxide melts have been detected in igneous xenoliths from Pliocene-to-Pleistocene alkali basalts of the Western Carpathians. Fluid inclusion and mineral composition data indicate immiscible separation of the high-iron-oxide melt (HIM) at magmatic temperatures. The HIM separation occurred during clinopyroxene (augite) accumulation in an alkali trachybasalt and continued during crystallization of amphibole (kaersutite) and K-feldspar (anorthoclase), the latter coexisting with trachyte and alkalic rhyolite residual melts. Some HIM was also expelled from sub-alkalic rhyolite (70–77% SiO₂), coexisting with An_27–45 plagioclase and quartz in granitic (tonalite-trondhjemite) xenoliths. Oxygen fugacities during HIM separation range from −1.4 to +0.6 log units around the QFM buffer. A close genetic relationship between HIM-hosted xenoliths and mantle-derived basaltic magma is documented by mineral ¹⁸O values ranging from 4.9 to 5.9‰ V-SMOW. δD values of gabbroic kaersutite between −61 and −86‰ V-SMOW are in agreement with a presumed primary magmatic water source. Most trace elements, except Li, Rb and Cs, have preferentially partitioned into the HIM. The HIM/Si-melt partition coefficients for transition elements (Sc, V, Cr, Co, Ni) and base metals (Zn, Cu, Mo) are between 2–160, resulting in extreme enrichment in the HIM. La and Ce also concentrate in the silicic melt, whereas Tb-Tm in the HIM. Hence, the immiscible separation causes REE fractionation and produces residual silicic melt enriched in LREE and depleted in HREE. The weak fractionation among Tb-Tm and Yb, Lu can be attributed to recurrent extraction of the HIM from the magmatic system, while flat HREE chondrite-normalized patterns are interpreted to indicate no or little loss of the HIM. Received: 30 September 1997 / Accepted: 23 March 1998     

Sulfur Isotope Fractionation in Magmatic Systems：Models of Rayleigh Distillation and Selective Flux

The effect of Rayleigh distillation by outgassing of SO2 and H2S on the isotopic composition of sulfur remaining in silicate melts is quantitatively modelled.A threshold mole fraction of sulfur in sulfide component of the melts is reckoned to be of critical importance in shifting the δ^34S of the melts mith respect to the original magmas.The partial equilibrium fractionation in a magmatic system is evaluated by assuming that a non-equilibrium flux of sulfur occurs between magmatic volatiles and the melts,while an equilibrium fractionation is approached between sulfate and sulfide within the melts.The results show that under high fo2 conditions,the sulfate/sulfide ratio in a melt entds to increase,and the δ^34S value of sulfur in a solidified rock might then be shifted in the positive direction.This may either be due to Rayleigh outgassing in case the mole fraction of sulfide is less than the threshold,or due to a unidirectional increase in δ^34S value of the sulfate with decreaing temperature,Conversely,at low fo2,the sulfate/sulfide ratio tends to decrease and the δ^34S value of total sulfur could be driven in the negative direction,either because of the Rayleigh outgassing in case the mole fraction of sulfide is greater than the threshold,or because of a unidirectional decrease inδ^34S value of the sulfide.To establish isotopic equilibrium between sulfate and sulfide,the HM,QFM or WM buffers in the magmatic system are suggested to provide the redox couple that could simultaneously reduce the sulfate and oxidize the sulfide.CaO present in the silicatte Melts is also called upon to participate in the chemical equilibrium between sulfate and sulfide,Consequently,the δ^34S value of an igneous rock could considerably deviate from that of its original magma due to the influence of oxygen fugacity and temperature at the time of magma solidification.     

Fe–Mg diffusion in olivine I: experimental determination between 700 and 1,200<Emphasis Type="Bold">°</Emphasis>C as a function of composition,crystal orientation and oxygen fugacity

We have determined Fe–Mg diffusion coefficients in olivines from different sources (Nanga Parbat, Pakistan and San Carlos, Arizona, USA) at atmospheric pressure as a function of composition, oxygen fugacity (10⁻⁵–10⁻¹² Pa) and temperature (700–1200°C) using thin films produced by pulsed laser deposition and RBS to analyze the concentration profiles. We have characterized the nano-scale structure and composition of the thin films annealed at various conditions and shown that the nature of the film (e.g. crystallinity, wetting behavior) depends strongly on the annealing conditions. If these variations are not taken into account in the form of boundary conditions for modeling the diffusion profiles, artifacts would result in the diffusion data. The diffusion coefficients obtained from 75 experiments reveal that (i) between fO₂ of 10⁻⁵ and 10⁻¹⁰ Pa, diffusion along all three principal crystallographic directions in olivine, [100], [010] and [001], are described by a constant activation energy of ∼200 kJ/mol, precluding any temperature dependence of diffusion anisotropy and change of mechanism of diffusion at temperatures between 950 and 1200°C, (ii) diffusion coefficients increase with oxygen fugacity at fO₂ > 10⁻¹⁰ Pa, with an fO₂ exponent that lies between 1/4 and 1/7, and (iii) at fO₂ below 10⁻¹⁰ Pa, and consequently at temperatures below ∼900°C, diffusion becomes weakly dependent/independent of fO₂, indicating a change of diffusion mechanism. Activation energy of diffusion at these conditions is slightly higher, ∼220 kJ/mol. The data, including the change of mechanism, are analyzed in terms of point defect chemistry in Part II of this work to derive an equation that allows calculation of diffusivities in olivine over its entire field of stability. Availability of directly measured data at temperatures down to 700°C imply that for the first time diffusion coefficients can be interpolated, rather than extrapolated, for modeling most natural systems.     

The partitioning of sulfur between multicomponent aqueous fluids and felsic melts

Sulfur partitioning between melt and fluid phase largely controls the environmental impact of volcanic eruptions. Fluid/melt partitioning data also provide the physical basis for interpreting changes in volcanic gas compositions that are used in eruption forecasts. To better constrain some variables that control the behavior of sulfur in felsic systems, in particular the interaction between different volatiles, we studied the partitioning of sulfur between aqueous fluids and haplogranitic melts at 200 MPa and 750–850 °C as a function of oxygen fugacity (Ni–NiO or Re–ReO₂ buffer), melt composition (Al/(Na?+?K) ratio), and fluid composition (NaCl and CO₂ content). The data confirm a first-order influence of oxygen fugacity on the partitioning of sulfur. Under “reducing conditions” (Ni–NiO buffer), D^fluid/melt is nearly one order of magnitude larger (323?±?14 for a metaluminous melt) than under “oxidizing conditions” (Re–ReO₂ buffer; 74?±?5 for a metaluminous melt). This effect is likely related to a major change in sulfur speciation in both melt and fluid. Raman spectra of the quenched fluids show the presence of H₂S and HS^? under reducing conditions and of SO₄^2? and HSO₄^? under oxidizing conditions, while SO₂ is undetectable. The latter observation suggests that already at the Re–ReO₂ buffer, sulfur in the fluid is almost completely in the S⁶⁺ state and, therefore, more oxidized than expected according to current models. CO₂ in the fluid (up to x_CO2?=?0.3) has no effect on the fluid/melt partitioning of sulfur, neither under oxidizing nor under reducing conditions. However, the effect of NaCl depends on redox state. While at oxidizing conditions, D^fluid/melt is independent of x_NaCl, the fluid/melt partition coefficient strongly decreases with NaCl content under reducing conditions, probably due to a change from H₂S to NaSH as dominant sulfur species in the fluid. A decrease of D^fluid/melt with alkali content in the melt is observed over the entire compositional range under reducing conditions, while it is prominent only between the peraluminous and metaluminous composition in oxidizing experiments. Overall, the experimental results suggest that for typical oxidized, silicic to intermediate subduction zone magmas, the degassing of sulfur is not influenced by the presence of other volatiles, while under reducing conditions, strong interactions with chlorine are observed. If the sulfur oxidation state is preserved during an explosive eruption, a large fraction of the sulfur released from oxidized magmas may be in the S⁶⁺ state and may remain undetected by conventional methods that only measure SO₂. Accordingly, the sulfur yield and the possible climatic impact of some eruptions may be severely underestimated.     

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.     

Gold solubility in oxidized and reduced, water-saturated mafic melt

We have performed experiments to evaluate Au solubility in natural, water-saturated basaltic melts as a function of oxygen fugacity. Experiments were carried out at 1000 °C and 200 MPa, and oxygen fugacity was controlled at the fayalite-magnetite-quartz (FMQ) oxygen fugacity buffer and FMQ + 4. All experiments were saturated with a metal-chloride aqueous solution loaded initially as a 10 wt% NaCl eq. fluid. The stable phase assemblage at FMQ consists of basalt melt, olivine, clinopyroxene, a single-phase aqueous fluid, and metallic Au. The stable phase assemblage at FMQ + 4 consists of basalt melt, clinopyroxene, magnetite-spinel solid solution, a single-phase aqueous fluid, and metallic Au. Silicate glasses (i.e., quenched melt) and their contained crystalline material were analyzed by using both electron probe microanalysis (EPMA) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Measured Au concentrations in the quenched melt range from 4.8 μg g⁻¹ to 0.64 μg g⁻¹ at FMQ + 4, and 0.54 μg g⁻¹ to 0.1 μg g⁻¹ at FMQ. The measured solubility of Au in olivine and clinopyroxene was consistently below the LA-ICP-MS limit of detection (i.e., 0.1 μg g⁻¹). These melt solubility data place important limitations on the dissolved Au content of water-saturated, Cl- and S-bearing basaltic liquids at geologically relevant fO₂ values. The new data are compared to published, experimentally-determined values for Au solubility in dry and hydrous silicate liquids spanning the compositional range from basalt to rhyolite, and the effects of melt composition, oxygen fugacity, pressure and temperature are discussed.     

Interaction of model F-bearing silicic melt with chloride fluid,uraninite, and columbite at 750°C and 1000–2000 bar and its implications for estimation of the ore-forming capability of the upper crustal magma chamber beneath the Strel’tsovka caldera,eastern Transbaikalia

The experimental study of an F-bearing silicic melt—U, Nb, Ta minerals—chloride-fluoride fluid system is focused on ascertaining the origin of uranium deposits spatially related to intraplate silicic volcanism. The first series of experiments on uranium solubility in silicic melts close in composition to ore-bearing rhyolite of the unique Strel’tsovka Mo-U ore field has been performed in order to determine more precisely the ore genesis. As starting solid phases, model homogeneous glass of the chemical composition (wt %) 72.18 SiO₂, 12.19 Al₂O₃, 1.02 FeO, 0.20 MgO, 0.33 CaO, 4.78 Na₂O, 3.82 K₂O, 1.44 Li₂O, and 2.4 F (LiF, NaF, KF, CaF₂, MgF₂); synthetic UO₂ and UO₃·0.33H₂O; and natural columbite were used. The starting solutions contained 1.0 m Cl and 10⁻² m F. The runs were conducted in a gas vessel at a pressure of 1000 bar and in a high-pressure hydrothermal vessel at 2000 bar. The O₂ (H₂) fugacity was set by Ni-NiO, Co-CoO, Fe₃O₄-Fe₂O₃, and Cu-Cu₂O buffers. The equilibrium between melt and solution for major elements is reached during the first day, whereas 5–7 days are required for ore elements (U, Nb, Ta) to come into equilibrium. The solubility of Nb and especially Ta in Cl-F solutions equilibrated with F-bearing melt is extremely low. The solubility of U is much higher (10⁻⁴−10⁻⁵ mol/kg H₂O). The energy dispersive spectroscopy of run products allowed us to establish that columbite dissolved incongruently with formation of U- and F-bearing pyrochlores. The performed experiments have shown that a silicic melt close to the rhyolitic magma of the Strel’tsovka caldera in composition is not able to generate postmagmatic ore-forming solutions containing more than 10⁻⁶−10⁻⁵ mol U/kg H₂O under the relatively low pressure necessary for the existence of the first type of fluid. The amount of uranium that could have precipitated from this fluid in the zone of ore deposition is estimated at 216–9000 t. This estimate is two orders of magnitude lower than the total uranium resources of the deposits localized in the Strel’tsovka caldera. Thus, the upper crustal silicic magma chamber hardly was a source of uranium for Mo-U deposits of the Strel’tsovka ore field.     

Oxygen diffusion in basalt and andesite melts: experimental results and discussion of chemical versus tracer diffusion

Chemical diffusion coefficients for oxygen in melts of Columbia River basalt (Ice Harbor Dam flow) and Mt. Hood andesite have been determined at 1 atm. The diffusion model is that of sorption or desorption of oxygen into a sphere of uniform initial concentration from a constant and semi-infinite atmosphere. The experimental design utilizes a thermogravimetric balance to monitor the rate of weight change arising from the response of the sample redox state to an imposed fO₂. Oxygen diffusion coefficients are approximately an order-ofmagnitude greater for basaltic melt than for andesitic melt. At 1260° C, the oxygen diffusion coefficients are: D=1.65×10^–6cm²/s and D=1.43×10^–7cm²/s for the basalt and andesite melts, respectively. The high oxygen diffusivity in basaltic melt correlates with a high ratio of nonbridging oxygen/tetrahedrally coordinated cations, low melt viscosity, and high contents of network-modifying cations. The dependence of the oxygen diffusion coefficient on temperature is: D=36.4exp(–51,600±3200/RT)cm²/s for the basalt and D=52.5exp(–60,060±4900/RT)cm²/s for the andesite (R in cal/deg-mol; T in Kelvin). Diffusion coefficients are independent of the direction of oxygen diffusion (equilibrium can be approached from extremely oxidizing or reducing conditions) and thus, melt redox state. Characteristic diffusion distances for oxygen at 1260° C vary from 10^-2 to 10² m over the time interval of 1 to 10⁶ years. A compensation diagram shows two distinct trends for oxygen chemical diffusion and oxygen tracer diffusion. These different linear relationships are interpreted as supporting distinct oxygen transport mechanisms. Because oxygen chemical diffusivities are generally greater than tracer diffusivities and their Arrhenius activation energies are less, transport mechanisms involving either molecular oxygen or vacancy diffusion are favored.     

Sulphur solubility in andesitic to basaltic melts: implications for Hekla volcano

The solubility of sulphur in sulphide-saturated, H₂O-bearing basaltic–andesitic and basaltic melts from Hekla volcano (Iceland) has been determined experimentally at 1,050°C, 300 and 200 MPa, and redox conditions with oxygen fugacity (logfO₂) between QFM−1.2 and QFM+1.1 (QFM is a quartz–fayalite–magnetite oxygen buffer) in the systems containing various amounts of S and H₂O. The S content of the H₂O-rich glasses saturated with pyrrhotite decreases from 2,500 ppm in basalt to 1,500 ppm in basaltic andesite at the investigated conditions. Furthermore, the reduction of water content in the melt at pyrrhotite saturation and fixed T, P and redox conditions leads to a decrease in S concentration from 2,500 to 1,400 ppm for basaltic experiments (for H₂O decrease from 7.8 to 1.4 wt%) and from 1,500 to 900 ppm (for H₂O decrease from 6.7 to 1.7 wt%) for basaltic andesitic experiments. Our experimental data, combined with silicate melt inclusion investigations and the available models on sulphide saturation in mafic magmas, indicate that the parental basaltic melts of Hekla were not saturated with respect to sulphide. During magmatic differentiation, the S content in the residual melts increased and might have reached sulphide saturation with 2,500 ppm dissolved S. With further magma crystallization, the S concentration in the melt was controlled by the sulphide saturation of the magma, decreasing from ~2,500 to 900 ppm S.     

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.