Anomalous elasticity of talc at high pressures: Implications for subduction systems

Talc is a layered hydrous silicate mineral that plays a vital role in transporting water into Earth’s interior and is crucial for explaining geophysical observations in subduction zone settings. In this study, we explored the structure, equation of state, and elasticity of both triclinic and monoclinic talc under high pressures up to 18 GPa using first principles simulations based on density functional theory corrected for dispersive forces. Our results indicate that principal components of the full elastic constant tensor C₁₁ and C₂₂, shear components C₆₆, and several off-diagonal components show anomalous pressure dependence. This non-monotonic pressure dependence of elastic constant components is likely related to the structural changes and is often manifested in a polytypic transition from a low-pressure polytype talc-I to a high-pressure polytype talc-II. The polytypic transition of talc occurs at pressures within its thermodynamic stability. However, the bulk and shear elastic moduli show no anomalous softening. Our study also shows that talc has low velocity, extremely high anisotropy, and anomalously high V_P/V_S ratio, thus making it a potential candidate mineral phase that could readily explain unusually high V_P/V_S ratio and large shear wave splitting delays as observed from seismological studies in many subduction systems.     

The thermodynamics of substances at very high pressures and temperatures and some mineral reactions in the earth's mantle

The thermodynamic properties of 25 substances (elements, compounds, modifications) are calculated on the basis of an extrapolation of their caloric values and compressibilities into the region of pressures up to 2mbar and temperatures up to 4,000K. The extrapolation methods are described. The ratio of molar volumes is used to predict the thermodynamic properties of the high pressure modifications. It is inferred that water vapour and oxides of Mg, Fe, and Si ought to be stable in the entire mantle. In the lower mantle garnet should be more stable than the perovskite-type phase of MgSiO₃ (in presence of Al₂O₃ or Fe₂O₃). ‘Perovskite’ phase plus MgO are more stable here than forsterite, Mg₂SiO₄. Pyrrhotite, FeS, reveals astonishing stability in the entire mantle and in the outer core as well. Carbon dioxide, CO₂, may exist only in the upper mantle, whereas methane, CH₄, remains stable in the entire mantle.     

Metal-silicate partitioning of cesium: Implications for core formation

Here we present the first set of metal-silicate partitioning data for Cs, which we use to examine whether the primitive mantle depletion of Cs can be attributed to core segregation. Our experiments independently varied pressure from 5 to 15 GPa, temperature from 1900 to 2400 °C, metallic sulfur content from pure Fe to pure FeS, silicate melt polymerization, expressed as a ratio of non-bridging oxygens to tetrahedrally coordinated cations (nbo/t) from 1.26 to 3.1, and fO₂ from two to four log units below the iron-wüstite buffer. The most important controls on the partitioning behavior of alkalis were the metallic sulfur content, expressed as X_S, and the nbo/t of the silicate liquid. Normalization of X_S to 0.5 yielded the following expressions for D-values as a function of nbo/t: log D_Na = −2.0 + 0.44 × (nbo/t), log D_K = −2.4 + 0.67 × ( nbo/t), and log D_Cs = −3.2 + 1.17 × (nbo/t). Normalization of nbo/t to 2.7 resulted in the following equations for D-values as a function of S content: log D_Na = −4.1 + 6.4 × X_S, log D_K = −7.7 + 13.9 × X_S, and log D_Cs = −12.1 + 23.3 × X_S.There appears to be a negative pressure effect up to 15 GPa, but it should be noted that this trend was not present before normalization, and is based on only two measurements. There is a positive trend in cesium’s metal-silicate partition coefficient with increasing temperature. D_Cs exhibits the largest change and increased by a factor of three over 500 °C. The effect of oxygen fugacity has not been precisely determined but in general, lowering fO₂ by two log units resulted in a rise in all D-values of approximately an order of magnitude. In general, the sensitivity of partition coefficients to changing parameters increased with atomic number.The highest D-value for Cs observed in this study is 0.345, which was obtained at nbo/t of 2.7 and a metal phase of pure FeS. This metallic composition has far more S than has been suggested for any credible core-forming metal. We therefore conclude that the depletion of Cs in Earth’s mantle is either caused by radically different behavior of Cs at pressures higher than 15 GPa or is not related to core formation. Even so, we have shown that a planet with a sufficient S inventory may incorporate significant amounts of alkali elements into its core.     

The partitioning of Pt-Re-Os between solid and liquid metal in the Fe-Ni-S system at high pressure: Implications for inner core fractionation

Coupled ¹⁸⁶Os/¹⁸⁸Os and ¹⁸⁷Os/¹⁸⁸Os enrichments of plume-derived lavas have been suggested to reflect contributions of materials from the outer core (Brandon et al., 1998). This hypothesis is based on the assumption that the Earth’s liquid outer core has high Pt/Os and slightly high Re/Os ratios as a result of the crystallization of the solid inner core, and shows coupled enrichments in the ¹⁸⁶Os/¹⁸⁸Os and ¹⁸⁷Os/¹⁸⁸Os ratios, reflecting the decay of ¹⁹⁰Pt and ¹⁸⁷Re to ¹⁸⁶Os and ¹⁸⁷Os, respectively. Partitioning experiments of Pt-Re-Os between solid and liquid metal were performed at 5-20 GPa and 1250-1400 °C, to examine the effects of pressure in the Fe-Ni-S system. The ratios (D_Os/D_Pt, D_Os/D_Re) of measured partition coefficients of Pt, Re and Os are almost constant with increasing pressure. D_Os/D_Pt increases significantly, whereas D_Os/D_Re decreases, with increasing sulphur content in the liquid metal. On the basis of the present experimental results, it is unlikely that the required Pt-Re-Os fractionation is generated during inner core crystallization, assuming that the light element in the Earth’s core is sulphur.     

Solubility of CO2 in olivine melilitite at high pressures and role of CO2 in the earth's upper mantle

The positions of the liquidi and the near-liquidus phases of olivine-melilitite+CO₂ have been determined under MH-buffered and furnace-buffered conditions up to 40 kb. It is found that CO₂ alone lowers the liquidus compared to dry conditions, yet its influence is minor compared to H₂O. The major role of CO₂ is to favour the growth of orthopyroxene and garnet over that of olivine at least at high pressures. CO₂-contents of glasses from experiments just above the liquidus (MH-buffered) were determined as 5.1 % at 10kb; 7.5 % at 20kb, 9.3 % at 30kb and 10–11 % (estimated) at 40 kb. Experiments on (pyrolite –40 % olivine)+H₂O+CO₂ show that CO₂ occurs under mantle conditions as carbonate under subsolidus conditions and dissolved in a melt above the solidus. At 30kb, the solidus lies between 1,000 ° C and 1,050 ° C for vapour-saturated conditions, at and at .     

动态高压下斜长石的熔融和玻璃化研究

斜长石在冲击波产生的动态高温高压作用下较易熔融和淬火为非晶态物质,其矿物学名为熔长石。在随州陨石冲击变质特征的研究中,发现橄榄石、辉石等矿物除出现微裂隙外均保存完好,而多数斜长石颗粒则已熔融和玻璃化。可区分出两种形态的熔长石,一种是保持了原有矿物颗粒外形的‘继形熔长石’,另一种则以熔池状和脉状体形式产出的‘改形熔长石’。两种熔长石的光学和物理性质相似,它们的化学成分与晶质斜长石也基本相同,说明斜长石在高压下熔融时没有与周围物质发生明显的组分交换。在吉林陨石的人工冲击实验产物中,斜长石是最先熔融的硅酸盐矿物,也多以填隙的他形颗粒或脉状体和熔池的形式产出。经与其它陨石的静态高压淬火实验研究结果的比较,推定继形和改形熔长石的形成条件为≈20GPa和≤1100℃。本研究结果对了解地幔橄榄岩和俯冲的大洋板片部分熔融作用,以及地球火山岩玻璃和超基性岩中铬尖晶石的玻璃相岩浆包襄体物理化学性质有一定参考价值。     

Experimental study of the bcc-fcc phase transformations in the Fe-rich system Fe-Si at high pressures

In situ X-ray diffraction experiments at high pressure were carried out up to 8.9 GPa and 1100 °C to study phase transformations of iron and two iron-silicon alloys Fe_0.91Si_0.09 and Fe_0.83Si_0.17. For iron, the transformation from the bcc phase to the fcc phase was observed at pressures 3.8–8.2 GPa and temperatures that are consistent with previous in situ X-ray diffraction studies. Reversal of the transformation of iron was found to be sensitive to temperature; hysteresis of the transformation increased from 25 °C at 3.8 GPa to 100 °C at 7.0 GPa, primarily because the bcc-fcc phase boundary has a negative Clayperon slope. In the binary system Fe-Si, the observations of the present study indicate that the ferrite (bcc phase)-stabilizing behavior of silicon persists at high pressures and that the maximum solubility of silicon in the fcc phase increases with increasing pressure: (1) the transformation from the bcc phase to the fcc phase was observed in Fe_0.91Si_0.09 at 6.0, 7.4 and 8.9 GPa and the temperatures measured at the onset of the transformations were 300 °C higher than those in iron at similar pressures, (2) the transformation rate in Fe_0.91Si_0.09 was extremely sluggish compared to that of iron, and (3) the bcc-fcc phase transformation was not observed in Fe_0.91Si_0.09 at 4.7 GPa up to 1000 °C and in Fe_0.83Si_0.17 at 8.2 GPa and 1100 °C. Received: 1 June 1998 / Revised, accepted: 9 October 1998     

Thermodynamic modeling of non-ideal mineral-fluid equilibria in the system Si-Al-Fe-Mg-Ca-Na-K-H-O-Cl at elevated temperatures and pressures: Implications for hydrothermal mass transfer in granitic rocks

We present the results of thermodynamic modeling of fluid-rock interaction in the system Si-Al-Fe-Mg-Ca-Na-H-O-Cl using the GEM-Selektor Gibbs free energy minimization code. Combination of non-ideal mixing properties in solids with multicomponent aqueous fluids represents a substantial improvement and it provides increased accuracy over existing modeling strategies. Application to the 10-component system allows us to link fluid composition and speciation with whole-rock mineralogy, mass and volume changes. We have simulated granite-fluid interaction over a wide range of conditions (200-600 °C, 100 MPa, 0-5 m Cl and fluid/rock ratios of 10⁻²-10⁴) in order to explore composition of magmatic fluids of variable salinity, temperature effects on fluid composition and speciation and to simulate several paths of alteration zoning. At low fluid/rock ratios (f/r) the fluid composition is buffered by the silicate-oxide assemblage and remains close to invariant. This behavior extends to a f/r of 0.1 which exceeds the amount of exsolved magmatic fluids controlled by water solubility in silicate melts. With increasing peraluminosity of the parental granite, the Na-, K- and Fe-bearing fluids become more acidic and the oxidation state increases as a consequence of hydrogen and ferrous iron transfer to the fluid. With decreasing temperature, saline fluids become more Ca- and Na-rich, change from weakly acidic to alkaline, and become significantly more oxidizing. Large variations in Ca/Fe and Ca/Mg ratios in the fluid are a potential geothermometer. The mineral assemblage changes from cordierite-biotite granites through two-mica granites to chlorite-, epidote- and zeolite-bearing rocks. We have carried out three rock-titration simulations: (1) reaction with the 2 m NaCl fluid leads to albitization, chloritization and desilication, reproducing essential features observed in episyenites, (2) infiltration of a high-temperature fluid into the granite at 400 °C leads to hydrolytic alteration commencing with alkali-feldspar breakdown and leading to potassic, phyllic and argillic assemblages; this is associated with reduction and iron metasomatism as observed in nature and (3) interaction with a multicomponent fluid at 600 °C produces sodic-calcic metasomatism. Na, Ca and Fe are the most mobile elements whereas immobility of Al is limited by f/r ∼ 400. All simulations predict a volume decrease by 3.4-5.4%, i.e., porosity formation at f/r < 30. At higher fluid/rock ratios simulation (2) produces a substantial volume increase (59%) due to mineral precipitation, whereas simulation (3) predicts a volume decrease by 49% at the advanced albitization-desilication stage. Volume changes closely correlate with mass changes of SiO₂ and are related to silica solubility in fluids. The combined effects of oxygen fugacity, fluid acidity and pH for breakdown of aqueous metal complexes and precipitation of ore minerals were evaluated by means of reduced activity products. Sharp increases in saturation indexes for oxidative breakdown occur at each alteration zone whereas reductive breakdown or involvement of other chloride complexes favor precipitation at high fluid/rock ratios only. Calculations of multicomponent aqueous-solid equilibria at high temperatures and pressures are able to accurately predict rock mineralogy and fluid chemistry and are applicable to diverse reactive flow processes in the Earth’s crust.     

Phonon density of states in iron at high pressures and high temperatures

The phonon density of states (DOS) in iron has been measured in situ by nuclear resonance inelastic X-ray scattering (NRIXS) at high pressures and high temperatures in a resistively heated diamond anvil cell. The DOS data provide a variety of thermodynamic and elastic parameters essential for characterizing iron at depth in the Earth interior, such as average sound velocity, Debye temperature, atomic mean square displacement, average kinetic energy, vibrational entropy and specific heat. The NRIXS data were collected at 6, 20, and 29 GPa and at temperatures up to 920 K. Temperatures were directly determined from the measured spectra by the ratio of intensities of the phonon creation/annihilation side bands that are determined only by the Boltzmann factor. The change of the DOS caused by the structural transition from -Fe to -Fe is small and not resolvable within the experimental precision. However, the phonon energies in -Fe are clearly shifted to lower values with respect to - and -Fe. The temperature dependence of derived thermodynamic parameters is presented and compared with those obtained by Debyes model. The Debye temperatures that best describe the data decrease slightly with increasing temperature.     

The system: Two alkali feldspars-KCl-NaCl-H2O at moderate to high temperatures and low pressures

Because of frequent discrepancies between the available experimental data and the measured composition of alkali chloride aqueous solutions coexisting with two alkali feldspars in high temperatures-low pressures natural systems, a systematic investigation of the system KAlSi₃O₈-NaAlSi₃O₈-KCl-NaCl-H₂O has been undertaken.Experiments have been carried out at temperatures from 300 °C to 660 °C, pressures from 0.2 to 2 kbar and total chloride concentrations ranging from 0.05 to 14 moles/kg H₂O.No effect of pressure on the feldspars solvus could be detected. Smoothing the experimental data on the basis of the regular assymetric solid solution model yields a critical temperature of 661°C and a critical composition of Or_0.36Ab_0.64.The equilibrium constant C = m _KCl/m _NaCl does not depend on total chloride molality, as long as the aqueous solution is homogeneous. But, in the miscibility gap (liquid+vapour) of the fluid, C is always lower in the vapour than in the liquid. The higher the temperature and the lower the pressure, the more striking this effect. For instance, at 500 ° C C _vaqour/C _liquid = 1 above 1 kb, 0.9 at 600 bars, 0.8 at 500 bars, 0.7 at 400–450 bars.The effect of pressure can be neglected in homogeneous fluids and in the liquid phase of unmixed fluids, but it is very important in the vapour phase (dilute solutions at low pressure).The selected values of C _max are (±0.01) 300 ° C0.083; 400 ° C0.139; 500 ° C0.200; 600 ° C0.264; 650 ° C0.298Such a behaviour of the fluid at low pressures explains the abnormally low values of m _KCl/m _NaCl measured in many natural hydrothermal systems. A new mechanism of alkali metasomatism (especially potassic alterations) is also proposed, taking into account the unmixing of alkali chloride aqueous solutions. This model seems particularly interesting in late magmatic hydrothermal processes, such as those occuring in porphyry type deposits.     

Silicon isotopes in the inner Solar System: Implications for core formation, solar nebular processes and partial melting

We report Si isotopic data on a suite of terrestrial mantle-derived samples, meteorites and a lunar sample. Our data on co-existing mantle minerals, peridotites and basalts demonstrate lack of any resolvable high temperature fractionation during igneous processes. We show that the δ³⁰Si of the bulk silicate Earth (BSE) is identical, within analytical uncertainties, to carbonaceous and ordinary chondrites (CHUR). Based on our data the difference between δ³⁰Si_BSE and δ³⁰Si_CHUR is 0.035 ± 0.035. Whole-rock differentiated meteorites from different parent bodies (Mars, Vesta) and a lunar breccia sample also show similar δ³⁰Si suggesting broad-scale Si isotope homogeneity in the inner Solar System with an average δ²⁹Si = −0.20 ± 0.01 and δ³⁰Si = −0.39 ± 0.02 relative to the NBS28 Si isotope standard.A difference between δ³⁰Si_BSE and δ³⁰Si_CHUR of 0.035, as observed in our study, translates to less than 1.67 wt.% Si in the core considering a continuous accretion model whereas estimates using a batch model are even lower. Within uncertainties (±0.035‰) in the δ³⁰Si difference between the BSE and CHUR, a maximum of 3.84 wt.% Si could be present in the Earth’s core whereas at δ³⁰Si_BSE-δ³⁰Si_CHUR = 0, there is no requirement of Si in the Earth’s core. Such low Si in the core necessitates the presence of other light elements in the core to explain its density deficit. Our data also places constraints on the oxidation state of the Earth’s mantle during core segregation. The uncertainties in estimating the concentration of oxidized Fe in the mantle during the first 90% of accretion arise from uncertainties in the estimates of the equilibrium partition coefficient of silicon between metal and silicate at conditions relevant to core formation. For δ³⁰Si_BSE-δ³⁰Si_CHUR = 0.035 ± 0.035, the concentration of oxidized Fe in the mantle during the first 90% of accretion could be as low as ∼1%. However, at δ³⁰Si_BSE-δ³⁰Si_CHUR = 0, the Si isotope data do not require any change in the mantle concentration of oxidized Fe during accretion from the present day value of 6.26%.     

Constraints on core formation from Pt partitioning in mafic silicate liquids at high temperatures

A new high temperature piston cylinder design has enabled the measurement of platinum solubility in mafic melts at temperatures up to 2500 °C, 2.2 GPa pressure, and under reducing conditions for 1-10 h. These high temperature and low f_O2 conditions may mimic a magma ocean during planetary core formation. Under these conditions, we measured tens to hundreds of ppm Pt in the quenched silicate glass corresponding to , 4-12 orders of magnitude lower than extrapolations from high f_O2 experiments at 1 bar and at temperatures no higher than 1550 °C. Moreover, the new experiments provide coupled textural and compositional evidence that noble metal micro-nuggets, ubiquitous in experimental studies of the highly siderophile elements, can be produced on quench: we measure equally high Pt concentrations in the rapidly quenched nugget-free peripheral margin of the silicate as we do in the more slowly quenched nugget-bearing interior region. We find that both temperature and melt composition exercise strong control on and that Pt⁰ and Pt¹⁺ may contribute significantly to the total dissolved Pt such that low f_O2 does not imply low Pt solubility. Equilibration of metal alloy with liquid silicate in a hot primitive magma might not have depleted platinum to the extent previously believed.     

Dehydration Melting of Metabasalt at 8-32 kbar: Implications for Continental Growth and Crust-Mantle Recycling

We report the results of partial melting experiments between8 and 32 kbar, on four natural amphibolites representative ofmetamorphosed Archean tholeiite (greenstone), high-alumina basalt,low-potassium tholeiite and alkali-rich basalt. For each rock,we monitor changes in the relative proportions and compositionof partial melt and coexisting residual (crystalline) phasesfrom 1000 to 1150C, within and beyond the amphibole dehydrationreaction interval. Low percentage melts coexisting with an amphiboliteor garnet amphibolite residue at 1000–1025C and 8–16kbar are highly silicic (high-K₂O granitic at 5%; melting, low-Al₂O₃trondhjemitic at 5–10%). Greater than 20% melting is onlyachieved beyond the amphibole-out phase boundary. Silicic tointermediate composition liquids (high-Al₂O₃ trondhjemitic-tonalitic,granodioritic, quartz dioritic, dioritic) result from 20–40%melting between 1050 and 1100C, leaving a granulite (plagioclase+ clinopyroxene orthopyroxene olivine) residue at 8 kbarand garnet granulite to eclogite (garnet + clinopyroxene) residuesat 12–32 kbar. Still higher degrees of melting ( 40–60%)result in mafic liquids corresponding to low-MgO, high-Al₂O₃basaltic and basaltic andesite compositions, which coexist withgranulitic residues at 8 kbar and edogitic or garnet granulitic(garnet + clinopyroxene + plagioclase orthopyroxene) residuesat higher pressures (12–28 kbar). As much as 40% by volumehigh-Al₂O₃ trondhjemitic-tonalitic liquid coexists with an eclogiticresidue at 1100–1150C and 32 kbar. The experimental datasuggest that the Archean tonalite-trondhjemite-granodiorite(TTG) suite of rocks, and their Phanerozoic equivalents, thetonalite-trondhjemite-dacite suite (including ‘adakites’and other Na-rich granitoids), can be generated by 10–40%melting of partially hydrated metabasalt at pressures abovethe garnet-in phase boundary (12 kbar) and temperatures between1000 and 1100C. Anomalously hot and/or thick metabasaltic crustis implied. Although a rare occurrence along modern convergentplate margins, subductionrelated melting of young, hot oceaniccrust (e.g. ocean ridges) may have been an important (essential)element in the growth of the continental crust in the Archean,if plate tectonic processes were operative. Coupled silicicmelt generation-segregation and mafic restite disposal may alsooccur at the base of continental or primitive (sub-arc?) crust,where crustal overthickening is a consequence of underplatingand overaccretion of mafic magmas. In either setting, net growthof continental crust and crustmantle recycling may be facilitatedby relatively high degrees of melting and extreme density contrastsbetween trondhjemitictonalitic liquids and garnet-rich residues.Continuous chemical trends are apparent between the experimentalcrystalline residues, and mafic migmatites and garnet granulitexenoliths from the lower crust, although lower-crustal xenolithsin general record lower temperatures (600–900C) and pressures(5–13 kbar) than corresponding residual assemblages fromthe experiments. However, geo-thermobarometry on eclogite xenolithsin kimberlites from the subcontinental mantle indicates conditionsappropriate for melting through and beyond the amphibole reactioninterval and the granulite-eclogite transition. If these samplesrepresent ancient (eclogitized) remnants of subducted or otherwisefoundered basaltic crust, then the intervening history of theirprotoliths may in some cases include partial melting. KEY WORDS: dehydration melting; metabasalt; continental growth; crust–mantle recycling ^*Corresponding author. Present address: Mineral Physics Institute and Center for High Pressure Research, Department of Earth and Space Sciences, State University of New York at Stony Brook, Stony Brook, NY 11794, USA     

The solubility and speciation of molybdenum in water vapour at elevated temperatures and pressures: Implications for ore genesis

The solubility of molybdenum trioxide in liquid-undersaturated water vapour has been investigated experimentally at 300, 320, and 360 °C and 39-154 bars. Results of these experiments show that the solubility of MoO₃ in water vapour is between 1 and 29 ppm, which is 19-20 orders of magnitude higher than the vapour pressure of MoO₃(g). Molybdenum solubility increases exponentially with f_H2O, suggesting the formation of a gaseous hydrated complex of the type MoO₃·nH₂O by the reaction:

(A.1)     

The stability of hercynite at high pressures and temperatures

The stability of hercynite (FeAl₂O₄) has been investigated experimentally between 7 and 24 GPa and 900 and 1,700°C. Hercynite breaks down to its constituent oxides at 7–8.5 GPa and temperatures >1,000°C. The incorporation of a small magnetite component in the hercynite necessitated a small correction to fix the location of the endmember reaction: FeAl₂O₄  = Al₂O₃ + FeO in P–T space. After making this correction, the position of the phase boundary was used to evaluate thermodynamic data for hercynite. Our results support a relatively large S ₂₉₈^° for hercynite, on the order of 115 J mol⁻¹ K⁻¹. Experiments up to 24 GPa and 1,400°C failed to detect any high-pressure polymorph of FeAl₂O₄; only corundum + wüstite were detected. This behaviour contrasts with that observed for the analogous MgAl₂O₄ system where the constituent oxides recombine at high pressure to produce “post-spinel” phases with CaFe₂O₄-type and CaTi₂O₄-type structures.