Local structure of calcium silicate melts from classical molecular dynamics simulation and a newly constructed thermodynamic model

The distributions of local structural units of calcium silicate melts were quantified by means of classical molecular dynamics simulation and a newly constructed structural thermodynamic model. The distribution of five kinds of Si-O tetrahedra Qi from these two methods was compared with each other and also with the experimental Raman spectra, an excellent agreement was achieved. These not only displayed the panorama distribution of microstructural units in the whole composition range, but also proved that the thermodynamic model is suitable for the utilization as the subsequent application model of spectral experiments for the thermodynamic calculation. Meanwhile, the five refined regions mastered by different disproportionating reactions were obtained. Finally, the distributions of two kinds of connections between Qi were obtained, denoted as Qi-Ca-Qj and Qi-[Ob]-Qj, from the thermodynamic model, and a theoretical verification was given that the dominant connections for any composition are equivalent connections.

Zircon saturation model in silicate melts:a review and update

Zircon stability in silicate melts-which can be quantitatively constrained by laboratory measurements of zircon saturation-is important for understanding the evolution of magma.Although the original zircon saturation model proposed by Watson and Harrison(Earth Planet Sci Lett 64(2):295-304,1983) is widely cited and has been updated recently,the three main models currently in use may generate large uncertainties due to extrapolation beyond their respective calibrated ranges.This paper reviews and updates zircon saturation models developed with temperature and compositional parameters.All available data on zircon saturation ranging in composition from mafic to silicic(and/or peralkaline to peraluminous)at temperatures from 750 to 1400℃ were collected to develop two refined models(1 and 2) that may be applied to the wider range of compositions.Model 1 is given by lnCZr(melt)=(14.297±0.308)+(0.964 ± 0.066).M-(11113±374)/r,and model 2 given by lnCZr(melt)=(18.99±0.423)-(1.069±0.102)·lnG-(12288±593)/T,where CZr(melt) is the Zr concentration of the melt in ppm and parameters M [=(Na+K+2 Ca)/(Al·Si)](cation ratios) and G [=(3·Al2 O3+SiO2)/(Na2-O+K2 O+CaO+MgO+FeO)](molar proportions)represent the melt composition.The errors are at one sigma,and T is the temperature in Kelvin.Before applying these models to natural rocks,it is necessary to ensure that the zircon used to date is crystallized from the host magmatic rock.Assessment of the application of both new and old models to natural rocks suggests that model 1 may be the best for magmatic temperature estimates of metaluminous to peraluminous rocks and that model 2 may be the best for estimating magmatic temperatures of alkaline to peralkaline rocks.

Mathematical Viscosity Models for Ternary Metallic and Silicate Melts

The mathematical viscosity models for metallic melts were discussed. The experimental data of Ag-Au-Cu systems were used to verify the models based on Chou′s general geometric thermodynamic model and the calculated results are consistent with the reported experimental data. A new model predicting the viscosity of multi-component silicate melts was established. The CaO-MnO-SiO 2,CaO-FeO-SiO 2 and FeO-MnO-SiO 2 silicate slag systems were used to verify the model.

Surface roughness affects metastable non-wetting behavior of silicate melts on thermal barrier coatings

Airborne silicate pollutants in flight corridors pose a serious threat to aviation safety whose severity is directly linked to the wettability of molten silicates on thermal barrier coatings(TBCs)at high temperatures(1200–2000℃).Despite its importance,the wettability of silicate melt on TBCs has not been well investigated.In particular,the surface morphology characteristics of TBCs can be expected to have a first-order effect on the wettability of silicate melt on such TBCs.Here,a series of atmospheric plasma spray(APS)yttria-stabilized zirconia(YSZ)TBCs with varying surface roughness were generated through the application of mechanical polishing.The metastable nonwetting behavior of three representative types of airborne silicate ash(volcanic ash,fly ash and a synthetic calcium–magnesium–aluminum–silicates(CMAS)powder)on these TBCs with varying surface roughness was investigated.It was observed that the smoother the surface of TBCs was,the larger the contact angle was with the molten silicate melts,and consequently,the smaller the area of damage was on the TBCs.Thus,the reduction in TBCs surface roughness(here via mechanical polishing)led to an improvement in the wetting and spreading resistance of TBCs to silicate melts at high temperature.In support of these observations and conclusions,the surface morphology of the TBC(both before and after polishing)had been characterized,and the mechanism of the surface roughness-dependence of wettability had been discussed.These results should contribute to reducing the deposition rate of silicate melt on TBCs,thus extending the lifetime of turbine blades and reducing maintenance costs.

Electrical conductivity of hydrous silicate melts and aqueous fluids: Measurement and applications

The combination of magnetotelluric survey and laboratory measurements of electrical conductivity is a powerful approach for exploring the conditions of Earth's deep interior. Electrical conductivity of hydrous silicate melts and aqueous fluids is sensitive to composition, temperature, and pressure, making it useful for understanding partial melting and fluid activity at great depths. This study presents a review on the experimental studies of electrical conductivity of silicate melts and aqueous fluids, and introduces some important applications of experimental results. For silicate melts, electrical conductivity increases with increasing temperature but decreases with pressure. With a similar Na^+ concentration, along the calc-alkaline series electrical conductivity generally increases from basaltic to rhyolitic melt, accompanied by a decreasing activation enthalpy. Electrical conductivity of silicate melts is strongly enhanced with the incorporation of water due to promoted cation mobility. For aqueous fluids, research is focused on dilute electrolyte solutions. Electrical conductivity typically first increases and then decreases with increasing temperature, and increases with pressure before approaching a plateau value. The dissociation constant of electrolyte can be derived from conductivity data. To develop generally applicable quantitative models of electrical conductivity of melt/fluid addressing the dependences on temperature, pressure, and composition, it requires more electrical conductivity measurements of representative systems to be implemented in an extensive P-T range using up-to-date methods.

Application of Hydrothermal Diamond Anvil Cell to Homogenization Experiments of Silicate Melt Inclusions

The homogenization of silicate melt inclusions （SMIs）,small droplets of silicate melt trapped in magmatic minerals,is an important component of petrogenetic and magmatic research.Conventional homogenization experiments on SMIs use microscope-mounted heating stages capable of producing high temperatures at 1 atm and cold-seal high-pressure vessels.Heating stages are generally used for SMIs with low internal pressures and allow in situ observations of the homogenization processes.In contrast,cold-seal high-pressure vessels are generally used to heat SMIs that have high internal pressures,although the homogenized SMIs can only be observed after quenching in this approach.Here we outline an alternative approach that uses a hydrothermal diamond anvil cell （HDAC） apparatus to homogenize SMIs.This is the only current method wherein phase changes in high-internal-pressure SMIs can be observed in situ during homogenization experiments,which represents an advantage over other conventional methods.Using an HDAC apparatus prevents high-internal-pressure SMIs from decrepitating during heating by elevating their external pressure,in addition to allowing in situ observations of SMIs.The type-V HDAC that is currently being used has a shorter distance between the sample chamber and the observation window than earlier types,potentially enabling continuous observation of the processes involved in heating and SMI homogenization through an objective lens with a long working distance.Homogenization experiments using HDAC require that a number of steps,including HDAC preparation,sample preparation,sample loading,preheating,and formal heating,be carefully followed.Homogenization experiments on SMIs within granite samples from the Jiajika pegmatite deposit （Sichuan,China） are best performed using an HDAC-based approach,because the elevated proper external pressure of these SMIs,combined with a short heating duration,helps to suppress material leakage and any reactions within the SMIs,in addition to allowing in situ observations during homogenization experiments.Furthermore,using the HDAC approach has other benefits：heating rates can be precisely controlled,wafer oxidization can be prevented,and samples can be subjected to in situ microbeam analysis.In summary,homogenization using HDAC provides more reliable results than those obtained using conventional heating equipment.Future developments will include improvements to the quenching method and temperature controls for the HDAC apparatus,thereby improving the utility of this approach for SMI homogenization experiments.

Copper partitioning between granitic silicate melt and coexisting aqueous fluid at 850°C and 100 MPa

Experiments on the partitioning of Cu between different granitic silicate melts and the respective coexisting aqueous fluids have been performed under conditions of 850 ℃, 100 MPa and oxygen fugacity （fO2） buffered at approaching Ni-NiO （NNO）. Partition coefficients of Cu （Dcu = Cfluid/Cmelt） were varied with different alumina/alkali mole ratios [Al2O3/（Na2O ＋ K2O）, abbreviated as Al/ Alk], Na/K mole ratios, and SiO2 mole contents. The DCu increased from 1.28 ± 0.01 to 22.18 ±0.22 with the increase of Al/Alk mole ratios （ranging from 0.64 to 1.20） and Na/K mole ratios （ranging from 0.58 to 2.56）. The experimental results also showed that Dcu was positively correlated with the HCl concentration of the starting fluid. The Dcu was independent of the SiO2 mole content in the range of SiO2 content considered. No Dcu value was less than 1 in our experiments at 850 ℃ and 100 MPa, indicating that Cu preferred to enter the fluid phase rather than the coexisting melt phase under most conditions in the melt-fluid system, and thus a significant amount of Cu could be transported in the fluid phase in the magmatichydrothermal environment. The results indicated that Cu favored partitioning into the aqueous fluid rather than the melt phase if there was a high Na/K ratio, Na-rich, peraluminous granitic melt coexisting with the high Cl^- fluid.

Intermediate-acidic silicate melt found in continental mantle of East China

CO2-RICH fluid inclusions have been found in 6 anhydrous peridotite xenolith minerals in Ceno-zoic basalts of 5 areas in East China.Electron probe backscattering electron image reveals thatseveral inclusions appear in all the rock sections,completely filled with glass or with cavities attheir center part（CO2 has escaped）.Some inclusions show devitrification and daughter miner-als appear.We have carried out the analysis on the non-devitrification glass in the inclusions.

Experiments on the Saturation of Fluorite in Magmatic Systems: Implications for Maximum F Concentration and Fluorine-Cation Bonding in Silicate Melt

The effects of melt composition,temperature and pressure on the solubility of fluorite(CaF2),i.e.,fluorine concentration in silicate melts in equilibrium with fluorite,are summarized in this paper.The authors present a statistic study based on experimental data in literature and propose a predictive model to estimate F concentration in melt at the saturation of fluorite(CFin melt^Fl-sat).The modeling indicates that the compositional effect of melt cations on the variation in can be expressed quantitatively as one parameter FSI(fluorite saturation index):FSI=(3Al^NM+Fe^2++6Mg+Ca+1.5Na-K)/(Si+Ti+Al^NF+Fe^3+),in which all cations are in mole,and Al^NF and Al^NM are A1 as network-forming and network-modifying cations,respectively.The dependence of CFin melt^Fl-sat on FSI is regressed as:CFin melt^Fl-sat=1.130-2.014·exp(1000/T)+2.747·exp(P/T)+0.111·CmeltH2O+17.641·FSI,in which T is temperature in Kelvin,P is pressure in MPa,CmeltH2O is melt H2O content in wt.%,and CFin melt^Fl-sat is in wt.%(normalized to anhydrous basis).The reference dataset used to establish the expression for conditions within 540-1010℃,50-500 MPa,0-7 wt.%melt H2O content,0.4 to 1.7 for A/CNK,0.3 wt.%-7.0 wt.%for CFin melt^Fl-sat.The discrepancy of CFin melt^Fl-sat between calculated and measured values is less than±0.62 wt.%with a confidence interval of 95%.The expression of FSI and its effect on CFin melt^Fl-sat indicate that fluorine incorporation in silicate melts is largely controlled by bonding with network-modifying cations,favorably with Mg,Al^NM,Na,Ca and Fe^2+in a decreasing order.The proposed model for predicting CFin melt^Fl-sat is also supported by our new experiments saturated with magmatic fluorite performed at 100-200 MPa and 800-900℃.The modeling of magma fractional crystallization emphasizes that the saturation of fluorite is dependent on both the compositions of primary magmas and their initial F contents.

Experimental constraints on trace element partitioning between coesite and hydrous silicate melt at 5 GPa and 1500-1750℃

Trace element partitioning between coesite and hydrous silicate melt has been investigated at 5 GPa and 1500-1750℃.High-P experiments successfully produced large coesite crystals in equilibrium with large silicate melt pools(plus kyanite and corundum crystals in some cases).Scanning electron microscopy and micro-Raman spectroscopy were employed to characterize the phases and the textures.Wavelength-dispersive electron microprobe analyses were performed to quantify conventional major elements,and laser ablation-inductively coupled plasma-mass spectrometry analyses were successfully conducted to quantify trace elements.Eventually,high-P partition coefficients were obtained for 33 elements.In general coesite is a very pure phase.With a few possible exceptions like Sc,Ti,and V,nearly all other trace elements are incompatible in coesite.Moreover,the partitioning behaviors of nearly all trace elements except some 4+cations cannot be readily described by the lattice strain model,presumably implying a minor role for the cation size in the trace-element partitioning.Combining our experimental results with the results in the literature,some T and P effects on the element partitioning behavior have been observed:T seemingly has different effects on different trace elements,but P might negatively correlate with the partition coefficients in all cases.Due to its large modal fraction in some subducted materials such as the continental crustal material,coesite might play an important role in the distributions of some trace elements,Ti for example.

Water and partial melting of Earth's mantle

Water plays a crucial role in the melting of Earth's mantle. Mantle magmatisms mostly occur at plate boundaries(including subduction zones and mid-ocean ridges) and in some intraplate regions with thermal anomaly. At oceanic subduction zones, water released by the subducted slab may induce melting of the overlying mantle wedge or even the slab itself, giving rise to arc magmatism, or may evolve into a supercritical fluid. The physicochemical conditions for the formation of slab melt and supercritical fluid are still under debate. At mid-ocean ridges and intraplate hot zones, water and CO_2 cause melting of the upwelling mantle to occur at greater depths and in greater extents. Low degree melting of the mantle may occur at boundaries between Earth's internal spheres, including the lithosphere-asthenosphere boundary(LAB), the upper mantletransition zone boundary, and the transition zone-lower mantle boundary, usually attributed to contrasting water storage capacity across the boundary. The origin for the stimulating effect of water on melting lies in that water as an incompatible component has a strong tendency to be enriched in the melt(i.e., with a mineral-melt partition coefficient much smaller than unity), thereby lowering the Gibbs free energy of the melt. The partitioning of water between melt and mantle minerals such as olivine, pyroxenes and garnet has been investigated extensively, but the effects of hydration on the density and transport properties of silicate melts require further assessments by experimental and computational approaches.