Sulfur diffusion in rhyolite melts

 Diffusion rates for sulfur in rhyolite melt have been measured at temperatures of 800–1100° C, water contents of 0–7.3 wt%, and oxygen fugacities from the quartz-fayalite-magnetite buffer to air. Experiments involved dissolution of anhydrite or pyrrhotite into rhyolite melt over time scales of hours to days. Electron microprobe analysis was used to measure sulfur concentration profiles in the quenched glasses. Regression of the diffusion data in dry rhyolite melt gives D_sulfur=0.05·exp{−221±80RT}, which is one to two orders of magnitude slower than diffusion of other common magmatic volatiles such as H₂O, CO₂ and Cl^-. Diffusion of sulfur in melt with 7 wt% dissolved water is 1.5 to 2 orders of magnitude faster than diffusion in the anhydrous melt, depending on temperature. Sulfur is known to dissolve in silicate melts as at least two different species, S²⁻ and S⁶⁺, the proportions of which vary with oxygen fugacity; despite this, oxygen fugacity does not appear to affect sulfur diffusivity except under extremely oxidizing conditions. This result suggests that diffusion of sulfur is controlled by one species over a large range in oxygen fugacity. The most likely candidate for the diffusing species is the sulfide ion, S²⁻. Re-equilibration between S²⁻ and S⁶⁺ in oxidized melts must generally be slow compared to S²⁻ diffusion in order to explain the observed results. In a silicic melt undergoing degassing, sulfur will tend to be fractionated from other volatile species which diffuse more rapidly. This is consistent with analyses of tephra from the 1991 eruption of Mount Pinatubo, Philippines, and from other high-silica volcanic eruptions. Received: 26 April 1995 / Accepted: 1 November 1995     

Water diffusion in basalt and andesite melts under high pressures

Water diffusion is one of the most important characteristics of many processes dealt with in magmatic geochemistry, petrology, and volcanology. We have experimentally examined water diffusion in Fe-free andesite and basalt melts (stoichiometric mixtures of the minerals albite + diopside + wollastonite) at 3 and 100 MPa, 1300×C, up to approximately 4 wt % water in the melts, and a total (lithostatic) pressure of 100 MPa on a high gas pressure apparatus equipped with a unique internal device. The experiments were conducted simultaneously with the use of two different methods: diffusion hydration and couples. Water solubility in the melts and water concentrations along the diffusion profiles (C _{H 2 O}) were determined by quantitative IR microspectroscopy, using the Beer-Lambert law. A structural chemical model is proposed for calculating and predicting the concentration dependence of the molar absorption coefficient of the hydroxyl group and water molecules in andesite and basalt glasses. The diffusion coefficients of water (D _{H 2 O}) are derived by the mathematical analysis of concentration profiles and the analytical solution of the second Fick diffusion law. Preliminary results indicated D _{H 2 O} is roughly one order of magnitude higher in basaltic melts than in andesitic ones (at the same temperatures and P _{H 2 O}) and significantly (exponentially) increases with increasing water concentrations in andesitic and basaltic melts. The newly obtained experimental data are proved to be fully consistent with the results obtained on the D _{H 2 O} dependence on C _{H 2 O} in melts of acid rocks (rhyolite and obsidian). The derived quantitative dependence between D _{H 2 O} and melt viscosity is used to develope principles of a new method for predicting and calculating the temperature, concentration, and pressure dependences of D _{H 2 O} in magmatic melts of the of acid-basic series (up to 3 wt % C _{H 2 O}) at crustal T, P parameters.     

An experimental investigation of high-temperature interactions between seawater and rhyolite,andesite, basalt and peridotite

Natural seawater was allowed to react with rhyolite, andesite, basalt, and peridotite at 200°–500° C, and 1,000 bars at water/rock mass ratios of 5 and 50 in order to investigate the effects of rock type, water/rock ratio, and temperature on solution chemistry and alteration mineralogy. The results indicate that interactions of seawater with various igneous rocks are similar in the production of a hydrous Mg-silicate and anhydrite as major alteration products. Fluids involved in the interactions lose Mg to alteration phases while leaching Fe, Mn, and Si from the rocks. The pH of the solutions is primarily controlled by Mg-OH-silicate formation and therefore varies with Mg and Si concentration of the system. Other reactions which involve Mg (such as Mg-Ca exchange) or which produce free H⁺, cause major differences in fluid chemistry between different seawater/ rock systems. High water/rock ratio systems (50/1) are generally more acidic and more efficient in leaching than low ratio systems (5/1), due to relatively more seawater Mg available for Mgsilicate production. The experiments show that large-scale seawater/rock interaction could exert considerable control on the chemistry of seawater, as well as producing large bodies of altered rock with associated ore-deposits.Active plate margins of convergence or divergence are suitable environments for hydrothermal systems due to the concurrence of igneous activity, tectonism, and a nearby water reservoir (seawater or connate water). The experimental data indicate that seawater interactions with igneous host rocks could generate many of the features of ore-deposits such as the Kuroko deposits of Japan, the Raul Mine of Peru, the Bleida deposit of Morocco, and deposits associated with ophiolites. Serpentinization of peridotite and alteration of igneous complexes associated with plate margins can also be explained by seawater interaction with the cooling rock. Geothermal energy production could benefit from experimental investigations of hot water/rock systems by development of chemical, temperature, and pressure control systems to maximize the lifetime of hydrothermal flow.     

Interaction of rhyolite melts with monazite,xenotime, and zircon surfaces

The interfacial contact region between a rhyolite melt and the accessory minerals monazite, xenotime, and zircon is investigated using molecular dynamics simulations. On all surfaces, major structural rearrangement extends about 1 nm into the melt from the interface. As evidenced by the structural perturbations in the ion distribution profiles, the affinity of the melt for the surface increases in going from monazite to xenotime to zircon. Alkali ions are enriched in the melt in contact with an inert wall, as well as at the mineral surfaces. Melt in contact with zircon has a particularly strong level of aluminum enrichment. In xenotime, the enrichment of aluminum is less than that in zircon, but still notable. In monazite, the aluminum enrichment in the contact layer is much less. It is expected that the relative surface energies of these accessory minerals will be a strong function of the aluminum content of the melt and that nucleation of zircon, in particular, would be easier for melts with higher aluminum concentration. The crystal growth rate for zircon is expected to be slower at a higher aluminum concentration because of the effectiveness of aluminum in solvating the zircon surface. The variable interfacial concentration profiles across the series of accessory minerals will likely affect the kinetics of trace element incorporation, as the trace elements must compete with the major elements for surface sites on the growing accessory minerals.     

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.     

Interdiffusion of hydrous dacitic and rhyolitic melts and the efficacy of rhyolite contamination of dacitic enclaves

Effective binary diffusion coefficients of Si during the interdiffusion of hydrous, 3 and 6% H₂O, dacitic and rhyolitic melts have been determined at 1.0 GPa, 1100°–1400°C. Water is shown to enhance diffusivities by one to two orders of magnitude above dry Si diffusivities in the same compositional system for SiO₂ compositions 65–75wt%. The effect of silica content on diffusion is small and typically within experimental error. With 3% H₂O in the melts the Arrhenius equation for Si diffusion at 70% SiO₂ is: $${\text{D = }}2.583\operatorname{x} 10^{ - {\text{ }}8} {\text{ }}\exp ( - 126.5/R{\text{T}})$$ where D is the diffusivity in m²/s, the activation energy (126.5) is in kJ/mol, R is in J/mol and T in Kelvin. Although less-well constrained, the Si diffusivity at 70% SiO₂ with 6% H₂O in the melts can be described by: $${\text{D = }}2.692\operatorname{x} 10^{ - {\text{ }}7} {\text{ }}\exp ( - 131.4/R{\text{T}})$$ The activation energies for diffusion are substantially below the activation energy of 236.4kJ/mol measured during anhydrous interdiffusion in the same system (Baker 1990). The decrease in activation energy with the initial addition of 3% water and the relative insensitivity of the activation energy to the additional water is related to the abundance of OH species in the melt, and the reduction of (Si,Al)-O bond strengths due to the interaction of hydroxyls with the (Si,Al)-O network. Changes in the pre-exponential factor of Arrhenius equations are attributed to the abundance of H₂O species in the melts. No decoupling of non-alkalies from SiO₂ during interdiffusion of the two melts was observed, although alkalies diffuse much more rapidly than non-alkalies (but were not measured quantitatively in this study) and can become decoupled. Interdiffusion of Si and all non-alkalies is demonstrated to be predictable, at least to within a factor of ten, by the Eyring equation. Using the diffusion data of this study for nonalkalies and of other studies for alkalies and Sr isotopes the contamination of a host rhyolitic magma by dacitic enclaves, 5 and 50 cm radius, has been modeled for temperatures of 1000°, 900°, and 800° C with water contents of 3 and 6%. Even when the effects of phenocrysts on diffusion in the dacitic enclaves are estimated the results of the modeling demonstrate that significant contamination is possible in the case of small enclaves, and even large enclaves have the potential to affect the composition of their host magma in geologically short times.     

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.     

Solubility of carbon dioxide in melts of andesite,tholeiite, and olivine nephelinite composition to 30 kbar pressure

Carbon dioxide solubilities in H₂O-free hydrous silicate melts of natural andesite (CA), tholeiite (K 1921), and olivine nephelinite (OM1) compositions have been determined employing carbon-14 beta-track mapping techniques. The CO₂ solubility increases with increasing pressure, temperature, and degree of silica-undersaturation of the silicate melt. At 1650° C, CO₂ solubility in CA increases from 1.48±0.05 wt % at 15 kbar to 1.95±0.03 wt % at 30 kbar. The respective solubilities in OM1 are 3.41±0.08 wt % and 7.11±0.10 wt %. The CO₂ solubility in K1921 is intermediate between those of CA and OM1 compositions. At lower temperatures, the CO₂ contents of these silicate melts are lower, and the pressure dependence of the solubility is less pronounced. The presence of H₂O also affects the CO₂ solubility (20–30% more CO₂ dissolves in hydrous than in H₂O-free silicate melts); the solubility curves pass through an isothermal, isobaric maximum at an intermediate CO₂/(CO₂+H₂O) composition of the volatile phase. Under conditions within the upper mantle where carbonate minerals are not stable and CO₂ and H₂O are present a vapor phase must exist. Because the solubility of CO₂ in silicate melts is lower than that of H₂O, volatiles must fractionate between the melt and vapor during partial melting of peridotite. Initial low-temperature melts will be more H₂O-rich than later high-temperature melts, provided vapor is present during the melting. Published phase equilibrium data indicate that the compositional sequence of melts from peridotite +H₂O+CO₂ parent will be andesite-tholeiite-nephelinite with increasing temperature at a pressure of about 20 kbar. Examples of this sequence may be found in the Lesser Antilles and in the Indonesian Island Arcs.     

Q_2黄土流变特性及其统计损伤流变模型

通过对西安地区不同湿度原状Q2黄土的单轴蠕变试验和三轴蠕变试验,得到了Q2黄土的单轴、三轴蠕变曲线和应力-应变等时曲线。试验曲线分析表明,Q2黄土具有明显的非线性流变特性。Q2黄土的粘弹性特性可采用五元件广义的Kelvin模型来描述,其线性粘塑性特性可用与一滑块并联的Maxwell模型来描述,而非线性粘塑性特性可通过损伤与塑性应变的耦合作用来反映。在考虑损伤门槛值的统计损伤及黄土粘弹塑性组合模型的基础上,应用应变等效原理,建立了考虑瞬时损伤的统计损伤流变模型,并通过拟牛顿法确定了相应的模型参数。该模型能够很好地模拟黄土流变非线性特征,该模型不仅参数较少,而且适用性较广。     

Thermodynamic properties of Fe-rich smectite-nontronite

The results of thermochemical studies are reported for nontronite samples from the Pinares-de-Majari (Eastern Cuba) (Sample I) and Kempirsai serpentine massif (South Urals, Kazakhstan) (Sample II). The enthalpies of formation of dehydrated hydroxyl-bearing nontronites from elements were determined by melt dissolution calorimetry using high-temperature heat-flux Tiana-Calvet microcalorimeter: Δ _f H _el ^o (298.15 K): ?4958 ± 13 kJ/mol for Mg_0.4(Fe _1.5 ³⁺ Mg_0.4Ni_0.1)[Si_3.7Al_0.3O₁₀](OH)₂ (I) and ?5003.6 ± 8.0 kJ/mol for Mg_0.3Na_0.1Ca_0.1(Fe _1.4 ³⁺ Mg_0.5Ni_0.1)[Si_3.7Al_0.3O₁₀](OH)₂ (II). It was determined experimentally that the enthalpy of dehydration (removal of molecular adsorption and interlayer water) of the studied nontronites is 6 ± 2 kJ per 1 mole H₂O. The enthalpy of formation of nontronite of theoretical composition Mg_0.15Fe ₂ ³⁺ [Si_3.7Al_0.3]O₁₀(OH)₂ was estimated at ?4750 kJ/mol. The Gibbs free energies of formation of the nontronites were calculated.     

Effect of weathering on the geomechanical properties of andesite, Ankara – Turkey

Andesite exposed in different parts of Ankara has different weathering categories varying from fresh to residual soil. The geomechanical properties of the andesite are significantly affected by weathering. Buildings constructed especially in completely weathered and residual soil levels of the andesite have some geotechnical problems. In this study, the variation of the geomechanical properties of the andesite due to weathering is investigated in three selected sites of Ankara, through optical microscope, X-ray diffraction analyses, major element analyses, pressuremeter tests, physicomechanical tests, and seismic refraction method. The data gathered from the field and laboratory studies were used to assess the characteristics of the weathering zones. Based on the data obtained from this study, an idealized weathering profile is assessed. No bearing capacity and consolidation settlement problems exist in the area. However, care should be taken for immediate settlement of the buildings. Slopes with heights less than 8 m are not expected to cause any significant problems for buildings. There exists a ground amplification problem in the study area. The natural period of the building should not match that of the weathered rock. The ground response analyses reveal that the buildings with four to seven stories may be adversely affected from earthquakes due to resonance phenomenon. Therefore, this has to be taken into account when designing new buildings.     

Thermodynamic properties of organic iodine compounds

A critical evaluation has been made of the thermodynamic properties reported in the literature for 43 organic iodine compounds in the solid, liquid, or ideal gas state. These compounds include aliphatic, cyclic and aromatic iodides, iodophenols, iodocarboxylic acids, and acetyl and benzoyl iodides. The evaluation has been made on the basis of carbon number systematics and group additivity relations, which also allowed to provide estimates of the thermodynamic properties of those compounds for which no experimental data were available. Standard molal thermodynamic properties at 25 °C and 1 bar and heat capacity coefficients are reported for 13 crystalline, 29 liquid, and 39 ideal gas organic iodine compounds, which can be used to calculate the corresponding properties as a function of temperature and pressure. Values derived for the standard molal Gibbs energy of formation at 25 °C and 1 bar of these crystalline, liquid, and ideal gas organic iodine compounds have subsequently been combined with either solubility measurements or gas/water partition coefficients to obtain values for the standard partial molal Gibbs energies of formation at 25 °C and 1 bar of 32 aqueous organic iodine compounds. The thermodynamic properties of organic iodine compounds calculated in the present study can be used together with those for aqueous inorganic iodine species to predict the organic/inorganic speciation of iodine in marine sediments and petroleum systems, or in the near- and far-field of nuclear waste repositories.     

Thermodynamic properties and phase stability of wadsleyite II

The thermodynamical stability of a newly observed wadsleyite II phase in the Mg₂SiO₄ system is studied by the density functional theory. The wadsleyite II equation of state has been derived. The phase boundaries of Mg₂SiO₄ polymorphs: wadsleyite, wadsleyite II and ringwoodite are studied using the quasi-harmonic approximation at high external pressures. Clapeyron slopes determined for wadsleyite II–ringwoodite and wadsleyite–wadsleyite II boundaries are 0.0047 and 0.0058 GPa/K, respectively. It is shown that the wadsleyite II phase is not thermodynamically preferred in the pure Mg₂SiO₄ system and will probably not occur between wadsleyite and ringwoodite phases.