Water in coesite: Incorporation mechanism and operation condition,solubility and P-T dependence,and contribution to water transport and coesite preservation

A series of coesite,coexisting with or without a liquid phase,was synthesized in the nominal system SiO2-H2O at800-1450℃and 5 GPa.Micro-Raman spectroscopy was used to identity the crystalline phase,electron microprobe and LA-ICP-MS were employed to quantity some major and trace elements,and unpolarized FTIR spectroscopy was applied to probe the different types of hydrogen defects,explore water-incorporation mechanisms and quantify water contents.Trace amounts of A1 and B were detected in the coesite.Combining our results with the results in the literatures,we have found no positive correlation between the Al contents and the"Al"-based hydrogen concentrations,suggesting that previously proposed hydrogen-incorporation mechanism H^++Al^3+■Si^4+does not function in coesite.In contrast,we have confirmed the positive correlation between the B contents and the B-based hydrogen concentrations.The hydrogen-incorporation mechanism H^++B3^+■Si^4+readily takes place in coesite at different P-T conditions,and significantly increases the water content at both liquid-saturated and liquid-undersaturated conditions.For the SiO2-H2O system,we have found that type-Ⅰhydrogarnet substitution plays a dictating role in incorporating water into coesite at liquid-saturated condition,type-II hydrogarnet substitution contributes significantly at nearly dry condition,and both operate at conditions in between.The water solubility of coesite,as dictated by the type-Ⅰhydrogarnet substitution,positively correlates with both P and T,cH2O=-105(30)+5.2(32)×P+0.112(26)×T,with cH2O in wt ppm,P in GPa and T in℃.Due to its low water solubility and small fraction in subducted slabs,coesite may contribute insignificantly to the vertical water transport in subduction zones.Furthermore,the water solubility of any coesite in exhuming ultra-high pressure metamorphic rocks should be virtually zero as coesite becomes metastable.With an adequately fast waterdiffusion rate,this metastable coesite should be completely dry,which may have been the key factor to the partial preservation of most natural Coe.As a byproduct,a new IR experimental protocol for accurate water determination in optically anisotropic nominally anhydrous minerals has been found.Aided with the empirical method of Paterson(1982)it employs multiple unpolarized IR spectra,collected from randomly-orientated mineral grains,to approximate both total integrated absorbance and total integrated molar absorption coefficient.Its success relies on a high-level orientation randomness in the IR analyses.     

Application of soft computing techniques for shallow foundation reliability in geotechnical engineering

This research focuses on the application of three soft computing techniques including Minimax Probability Machine Regression(MPMR),Particle Swarm Optimization based Artificial Neural Network(ANN-PSO)and Particle Swarm Optimization based Adaptive Network Fuzzy Inference System(ANFIS-PSO)to study the shallow foundation reliability based on settlement criteria.Soil is a heterogeneous medium and the involvement of its attributes for geotechnical behaviour in soil-foundation system makes the prediction of settlement of shallow a complex engineering problem.This study explores the feasibility of soft computing techniques against the deterministic approach.The settlement of shallow foundation depends on the parametersγ(unit weight),e0(void ratio)and CC(compression index).These soil parameters are taken as input variables while the settlement of shallow foundation as output.To assess the performance of models,different performance indices i.e.RMSE,VAF,R^2,Bias Factor,MAPE,LMI,U(95),RSR,NS,RPD,etc.were used.From the analysis of results,it was found that MPMR model outperformed PSO-ANFIS and PSO-ANN.Therefore,MPMR can be used as a reliable soft computing technique for non-linear problems for settlement of shallow foundations on soils.     

Petrological geodynamics of mantle melting III. AlphaMELTS + multiphase flow: The effect of water

The influence of water is evaluated in this last contribution of a series aiming to study the petrological and dynamic evolution of mantle melting. Water is considered to be either a chemical component in the melt or solid assemblage but it can also be present as a pure water phase in a oversaturated environment. A three-phase-flow model was developed for this purpose.Only a limited set of conditions has been applied to the 1-D upwelling mantle column. A range of fixed temperatures (1150–1450 °C) and water contents in the solid mantle (0, 0.02 wt.%, 0.2 ​wt.%) have been imposed at the entry point (120 ​km deep) for the two melting models introduced in the previous installments, dynamic equilibrium melting (DEM) and dynamic fractional melting (DFM) model.As expected, for a given temperature at the base of the mantle column, the depth of the first melt formation increases with higher water content in the mantle. After the first melt is created, very negligible amount of melt is formed over a certain depth interval which approximately ends at the depth where the first melting of the dry mantle would take place. However melt is present as a dynamic phase thorough the entire region regardless whether the DEM or DFM model has been applied.Under a quasi-steady state regime, the melt and residual mantle compositions vary significantly over depth, depending on the conditions imposed to the model (DEM, DFM, bottom temperature and water content). Several distinctions can be made at the extraction point (top of the mantle column ​= ​15 ​km deep). For DEM and DFM models at this lowest depth, the most influential factor affecting the melt composition after the quasi-steady state condition has been reached is the temperature at the base of the column. In general, for a high temperature model, the input water in the mantle does not seem to play a significant role on the bulk composition of the melt (except for the water content in melt). But at low temperature water does have some noticeable influence on the variation of some chemical components in melt ($Si{O}_2$, $F{e}_2{O}_3$, $CaO$, $N{a}_{2}O$ at T ​= ​1250 °C or lower). A similar conclusion can be made also for the residual mantle composition. The presence of a dynamic free water phase is detected only in absence of melt or in coexistence with a melt phase when the mantle is relatively cold (bottom temperature $\le$1250 °C) and the input water content at the base of the model is relatively high (0.2 ​wt.%).Complete output data for several numerical simulations and six animations illustrating various melting models are available following the instructions in the supplementary material.     

Lithospheric stress in Mongolia,from earthquake source data

Lithospheric stress in Mongolia has been studied using mechanisms of 84 M_(LH)≥ 4 earthquakes that occurred in the 20 th century and instrumental seismic moments of 17,375 M_(LH)≥2.5 events recorded between 1970 and 2000.The M_(LH)≥ 3.5 earthquakes mostly have strike-slip mechanisms in southern and central Mongolia,with frequent reverse-slip motions in the west and normal slip in the north,especially,in the area of Lake Hovsgol.The principal stresses are,respectively,S_HS_vS_h in the center and in the south;high horizontal compression with S_HS_hS_v in the west;and a heterogeneous stress pattern with S_vS_HS_h in the north.According to seismic moments of M_(LH)=2.5 events,oblique slip generally predominates over the territory,at S_v≈S_HS_h,while frequent strike slip motions in the west record high horizontal compression(S_HS_vS_h).Earthquake mechanisms show the principal horizontal compression S_H to be directed W-E in the east,NE-SW in the central and Gobi-Altay regions,and approximately N-S in the west of Mongolia.The patterns of principal lithospheric stresses in the territory of Mongolia have undergone three events of dramatic change for a few recent decades,and these events were synchronous with three similar events in the Baikal rift system(BRS):in the latest 1960 s,latest 1970 s to earliest 1980 s,and in the latest 1980 s to earliest 1990 s.The seismicity of Mongolia has been controlled by superposition of variable stresses associated with rifting activity pulses in the neighbor BRS on the background of quasi-stationary super-regional compression.     

The measurement of D/H ratio in alkenones and their isotopic heterogeneity

Previous paleoenvironmental studies reported the δD values of a mixture of coeluting alkenones. Here, we present a semi-preparative normal-phase high-performance liquid chromatography–mass spectrometry (NP-HPLC–MS) method for purifying long chain (C₃₇ and C₃₈) unsaturated methyl and ethyl ketones (alkenones) on the basis of chain length and degree of unsaturation.The method was applied to purify alkenones in suspended particles and surface sediments from a site in Chesapeake Bay, eastern USA. The hydrogen isotopic composition of di- and triunsaturated C₃₇ and C₃₈ alkenones differed significantly on the basis of chain length and the degree of unsaturation, demonstrating the importance of gas chromatography–isotope ratio-mass spectrometry (GC–irMS) analysis of individual alkenones for accurate paleoenvironmental reconstruction. Constant fractionation factors between alkenones with different chain length but the same degree of unsaturation (${\alpha }_{{\text{C}}_{37:2}''–''{\text{C}}_{38:2}}\text{and}{\alpha }_{{\text{C}}_{37:3}''–''{\text{C}}_{38:3}}=1.01$) and those with the same chain length but different degree of unsaturation (${\alpha }_{{\text{C}}_{37:2}''–''{\text{C}}_{37:3}}\text{and}{\alpha }_{{\text{C}}_{38:2}''–''{\text{C}}_{38:3}}=0.97$) in all samples suggest that the values may represent hydrogen isotope fractionation associated with elongation and desaturation during alkenone biosynthesis.     

Bulk modulus of Fe-rich olivines corrected for non-hydrostaticity

In situ X-ray diffraction was used to measure the isothermal bulk modulus at room conditions (K_T0) of synthetic olivines with different iron contents. The chemical formulae of the olivine samples were ${({\mathrm{Fe}}_x,{\mathrm{Mg}}_{1?x})}_2\mathrm{Si}{\mathrm{O}}_4$ with x = 0.45; 0.64; 0.82; 1, with 1% standard deviation (referenced as Fa45, Fa64, Fa82 and Fa100, respectively). All experiments were performed in the multi-anvil apparatus installed at NSLS beamline X17B2, to pressures up to about 7 GPa. Unit-cell volumes under hydrostatic conditions and differential stresses present in the samples were calculated using the method developed by Singh et al. (1998), and pressures measured using NaCl as a standard were then corrected for these stresses. Using a second-order Birch–Murnaghan equation of state, we obtained the isothermal bulk modulus of each composition: $K_{T0}^{\mathrm{Fa45}}=131.4\pm 2.6$ GPa, $K_{T0}^{\mathrm{Fa64}}=132.1\pm 3.1$ GPa, $K_{T0}^{\mathrm{Fa82}}=136.3\pm 1.7$ GPa and $K_{T0}^{\mathrm{Fa100}}=134.8\pm 1.4$ GPa. These values combined with data available in the literature show that the K_T0 of Fe-rich olivines increases very slowly with the Fe content, but possibly not in a simple linear trend.     

Petrogenesis of the late Cretaceous Turnagoel intrusion in the eastern Pontides： Implications for magma genesis in the arc setting

A series of Cretaceous plutons is present in the eastern Pontides of northeastern Turkey.The Turnagl intrusion is the least studied and,thus,the least understood plutons in the orogen.This intrusion consists of hornblende-biotite granodiorites emplaced at 78 Ma based on LA-ICP-MS U-Pb zircon dating.It is of sub- alkaline affinity,belongs to the medium- to high-K calc-alkaline series,and displays features typical of Itype granites.The rocks of the intrusion are enriched in large-ion lithophile elements and light rare earthelements with negative Eu anomalies（Eu/Eu^*= 0.69-0.82）,but are deficient in high-field-strength elements.They have a small range of (⁸⁷Sr/⁸⁶Sr)_i（0.7060-0.7063）,ε_Ndi（-2.6 to -3.1）,and δ¹⁸O（+8.1 to +9.1） values.Their Pb isotopic ratios are ²⁰⁶Pb/²⁰⁴Pb = 18.63-18.65,²⁰⁷Pb/²⁰⁴Pb = 15.62-15.63,and ²⁰⁸Pb/²⁰⁴Pb = 38.53-38.55.The fractionation of plagioclase,hornblende,and Fe-Ti oxides had key functions in the evolution of the Tumagl intrusion.The crystallization temperatures of the melts ranged from 758 to 885℃ as determined by zircon and apatite saturation thermometry.All these characteristics,combined with the low values of K₂O/Na₂O and（Na₂O + K₂O）/（FeO^t+MgO + TiO₂）,as well as the high values of （CaO + FeO^t + MgO + TiO₂）.suggest an origin by dehydration melting from a metabasaltic lowercrustal source.     

Thermodynamic modeling of binary CH4–CO2 fluid inclusions

An equation of state (EOS) explicit in Helmholtz free energy has been improved to calculate the PVTx and vapor–liquid phase equilibrium properties of CH₄–CO₂ fluid mixture. This EOS, where four mixing parameters are used, is based on highly accurate EOSs recommended by NIST for pure components (CH₄ and CO₂) and contains a simple generalized departure function presented by Lemmon and Jacobsen (1999). Comparison with experimental data available indicates that the EOS can calculate both vapor–liquid phase equilibrium and volumetric properties of this binary fluid system with accuracy close to that of experimental data up to high temperature and pressure within full range of composition. The EOS of CH₄–CO₂ fluid, together with the updated Gibbs free energy model of solid CO₂ (dry ice), is applied to calculate the CH₄ content (x_CH4) and molar volume (V_m) of the CH₄–CO₂ fluid inclusion based on the assumption that the volume of an inclusion keeps constant during heating and cooling. $V_{\text{m}}-x_{{\text{CH}}_4}$ diagrams are presented, which describe phase transitions involving vapor, liquid and CO₂ solid phases of CH₄–CO₂ fluid inclusions. Isochores of CH₄–CO₂ inclusions at given $x_{{\text{CH}}_4}$ and V_m can be easily calculated from the improved EOS.     

Single planet formation regime in the high-ionization environment:Possible origin of hot Jupiters and super-Earths

We studied the particle growth in a protoplanetary disk in a high-ionization environment and found that icy planet formation is inactive for a disk with an ionization rate 100 times higher than that of the present Solar System. In particular, in the case of M 10~(-7.4)M_☉yr~(-1), only rocky planet formation occurs. In such a case, all the solid materials in the disk drift inward, eventually reach the inner MRI front,and accumulate there. They form a dense, thin sub-disk of solid particles, which undergoes gravitational instability to form rocky planetesimals. The planetesimals rapidly grow into a planet through pebble accretion. Consequently, rocky planets tend to be much larger than planets formed through other regimes(tandem planet formation regime and dispersed planet formation regime), in which icy planet formation actively takes place. These rocky planets may evolve into hot Jupiters if they grow fast enough to the critical core mass of the runaway gas accretion before the dispersal of the disk gas, or they may evolve into super-Earths if the gas dispersed sufficiently early.