Elasticity,crystal structure and phase transitions

It is demonstrated that in many cases the ratio of elastic velocities of polymorphs of a material depends primarily on the crystal structures involved, and only secondarily on the composition. Crucial to this demonstration is the use of estimates, from the Hashin-Shtrikman bounds, of the elastic properties of mixtures of simple oxides isochemical to particular compounds. Normalization to the oxide mixture properties displays the interrelationships between the densities and velocities of different crystal structures. A wide range of velocity-density trends through possible phase transitions is found. Transitions involving increases of Si coordination from 4 to 6 tend to have lower slopes. Velocity-density correlations are reasonably consistent with the average trends through phase transitions.Comparison of models of the transition zone with the characteristics of the olivine-spinel-oxides transitions indicates that in some studies the lower mantle density may have been underestimated or the mean atomic weight of the lower mantle overestimated. The transition zone of Model B1 of Jordan and Anderson, which was derived entirely from seismic data, is consistent, overall, with the olivine-oxides transition and uniform composition, but the individual discontinuities are not consistent with the olivine-spinel and spinel-oxides transitions.     

Elasticity of the ilmenite - perovskite phase transformation in CdTiO3

Ultrasonic data for the velocities of the ilmenite and perovskite polymorphs of CdTiO₃ have been determined as a function of pressure to 7.5 kbar at room temperature for polycrystalline specimens hot-pressed at pressures up to 25 kbar. This transition is characterized by the following velocity (ν)-density (?) relationships: (1) the changes in compressional (ν_p) and bulk sound (ν_?) velocities are comparable in percentage magnitude to the density jump, while the shear (ν_s) velocity jump is three times greater than that for ?; (2) (ν_p/ν_s) decreases across the transition from the low- to high-pressure phase; and (3) low slopes (linear or logarithmic) on ν-? diagrams. The (ν_p/ν_s) behaviour for the ilmenite-perovskite transformation is unusual for the transitions studied in our laboratory. The observed relationships (1) and (2) are typical of the elasticity behaviour across phase transformations which involve increases in cation-anion co-ordination and in nearest-neighbour interatomic distances, such as those exhibited by CdTiO₃ in transforming from the ilmenite to the perovskite phase. Elasticity systematics for isostructural sequences are used to estimate the bulk moduli of the perovskite polymorphs of CaSiO₃ (2.7 Mbar) and MgSiO₃ (2.8 Mbar).     

Elasticity of antigorite,seismic detection of serpentinites,and anisotropy in subduction zones

Serpentinization of the mantle wedge is an important process that influences the seismic and mechanical properties in subduction zones. Seismic detection of serpentines relies on the knowledge of elastic properties of serpentinites, which thus far has not been possible in the absence of single-crystal elastic properties of antigorite. The elastic constants of antigorite, the dominant serpentine at high-pressure in subduction zones, were measured using Brillouin spectroscopy under ambient conditions. In addition, antigorite lattice preferred orientations (LPO) were determined using an electron back-scattering diffraction (EBSD) technique. Isotropic aggregate velocities are significantly lower than those of peridotites to allow seismic detection of serpentinites from tomography. The isotropic V_P/V_S ratio is 1.76 in the Voigt–Reuss–Hill average, not very different from that of 1.73 in peridotite, but may vary between 1.70 and 1.86 between the Voigt and Reuss bonds. Antigorite and deformed serpentinites have a very high seismic anisotropy and remarkably low velocities along particular directions. V_P varies between 8.9 km s^? 1 and 5.6 km s^? 1 (46% anisotropy), and 8.3 km s^? 1 and 5.8 km s^? 1 (37%), and V_S between 5.1 km s^? 1 and 2.5 km s^? 1 (66%), and 4.7 km s^? 1 and 2.9 km s^? 1 (50%) for the single-crystal and aggregate, respectively. The V_P/V_S ratio and shear wave splitting also vary with orientation between 1.2 and 3.4, and 1.3 and 2.8 for the single-crystal and aggregate, respectively. Thus deformed serpentinites can present seismic velocities similar to peridotites for wave propagation parallel to the foliation or lower than crustal rocks for wave propagation perpendicular to the foliation. These properties can be used to detect serpentinite, quantify the amount of serpentinization, and to discuss relationships between seismic anisotropy and deformation in the mantle wedge. Regions of high V_P/V_S ratios and extremely low velocities in the mantle wedge of subduction zones (down to about 6 and 3 km.s^?1 for V_P and V_S, respectively) are difficult to explain without strong preferred orientation of serpentine. Local variations of anisotropy may result from kilometer-scale folding of serpentinites. Shear wave splittings up to 1–1.5 s can be explained with moderately thick (10–20 km) serpentinite bodies.     

Elastic and thermal properties of fluoride and oxide analogues in the rocksalt,fluorite, rutile and perovskite structures

Fluorides are considered as models for the physical properties of oxides on the basis of Goldschmidt's crystal chemical arguments. The well-established bulk modulus (K)-volume (V) relationship KV = constant is sddddhown to hold for fluorides and oxides belonging to the four isostructural series. The bulk moduli of equivolume oxides and fluorides are scaled as 4S², where S = Z^O/2Z^F is the ratio of the effective unit charges and is approximately 77% for all of the crystal structures. The fluorides have distinctly lower melting and Debye temperatures which offers the possibility of using these compounds as models for the high-temperature elastic behaviour of their oxide analogues.     

A comparison of garnet-ilmenite-perovskite phase equilibria in germanate and silicate systems at high pressures

Phase equilibria have been investigated in the system CaGeO₃MgGeO₂Al₂O₃ and on germanium analogues of basalt and a pyrolite-related system at pressures between 2 and 11 GPa and at temperatures between 850 and 1200°C. Solid solubility relationships between garnet, ilmenite and perovskite-type phases were determined and compared with those in the corresponding silicate systems. There are some interesting similarities where the germanate equilibria are able to provide insight into the phase chemistry of corresponding silicate systems. However, there are also some significant differences that limit the ability of germanate models to predict the probable behaviour of corresponding silicate systems at higher pressures.     

Elasticity of pyroxene-garnet and pyroxene-ilmenite phase transformations in germanates

Ultrasonic data for the velocities of the low- and high-pressure polymorphs of germanate compounds undergoing the pyroxene-garnet (CaGeO₃, CdGeO₃) and pyroxene-ilmenite (MgGeO₃, MnGeO₃) phase transformations have been determined as a function of pressure to 7.5 kbar at room temperature for polycrystalline specimens hot-pressed at pressures up to 60 kbar. These transitions are characterized by the following velocity (υ)-density (ρ) relationships: (1) the velocity jumps are comparable in percentage magnitude to the density jumps, with the exception of shear velocity for the pyroxene-ilmenite transition; (2) the ratio (υ_p/υ_s) of the compressional to shear velocity is constant or increases slightly across the transitions; and (3) low slopes (linear or logarithmic) on υ-ρ diagrams. The observed relationships (1) and (2) are similar to those for the coesite-stishovite transition, but are in marked contrast with those from the olivine-spinel and olivine-beta phase transformations. Coordination changes are thus important factors to be considered in establishing velocity-density systematics governing polymorphic transitions. The υ-ρ changes across the pyroxene-garnet and pyroxene-ilmenite transitions are also distinctly smaller than those produced by compression or thermal expansion of a homogeneous material or by varying composition at constant mean atomic weight. Systematic trends in the elastic properties for isostructural sequences support the concept of germanates as models for the elasticity of their silicate analogues; this scheme is applied to estimate the bulk moduli of the garnet (1.80 Mbar) and ilmenite (2.11 Mbar) polymorphs of MgSiO₃.     

Change of structure,phase composition and magnetic properties with the oxidation of titanomagnetites

Summary Phase, structural and magnetic changes, occurring under oxidation and at increased temperatures, are studied on four samples of magnetic fractions. The samples of magnetic fractions, containing titanomagnetites at different oxidation levels, were oxidized at a temperature of 400°C for 1, 60 and 300 mins. With the aid of X-rays and Mössbauer's spectrometry it has been proved that under oxidation non-stoichiometric titanomagnetites and titanomagnetites plus ilmenite and pseudobrookite are formed.     

Orthorhombic perovskite phases observed in olivine,pyroxene and garnet at high pressures and temperatures

Ferromagnesian silicate olivines, pyroxenes and garnets with Mg/(Mg + Fe)?0.3 (molar) have been found to transform to high-pressure phases characterized by the orthorhombic perovskite structure when compressed to pressures above 250 kbar in a diamond-anvil press and heated to temperatures above 1,000°C with a YAG laser. The zero-pressure density of the perovskite phase of (Mg,Fe)SiO₃ is about 3–4% greater than that of the close-packed oxides, rocksalt plus stishovite. For (Mg,Fe)₂SiO₄ compounds, the perovskite plus rocksalt phase assemblage is 2–3% denser than the mixed oxides. The experimental synthesis of such high-density perovskite phases in olivine, pyroxene and garnet compounds suggests that (Mg,Fe)SiO₃-perovskite is the dominant mineral phase in the earth's lower mantle.     

Serpentinization,abiogenic organic compounds,and deep life

The hydrocarbons and other organic compounds generated through abiogenic or inorganic processes are closely related to two science subjects,i.e.,energy resources and life’s origin and evolution."The earth’s primordial abiogenic hydrocarbon theory"and"the serpentinization of abiogenic hydrocarbon theory"are the two mainstream theories in the field of related studies.Serpentinization generally occurs in slow expanding mid-ocean ridges and continental ophiolites tectonic environment,etc.The abiogenic hydrocarbons and other organic compounds formed through the serpentinization of ultramafic rocks provide energy and raw materials to support chemosynthetic microbial communities,which probably was the most important hydration reaction for the origin and early evolution of life.The superposition of biological and abiological processes creates big challenge to the identification of the abiogenic organic materials in serpentinite-hosted ecosystem.Whether abiotic(inorganic)process can form oil and gas resource is a difficult question that has been explored continuously by scientific community for more than a century but has not yet been solved.However,some important progress has been made.The prospecting practice of abiogenic hydrocarbons in commercial gases from the Songliao Basin,China,provides an important example for exploring abiogenic natural gas resources.     

Elasticity of MgSiO3 in the ilmenite phase

The single-crystal elastic moduli of the ilmenite phase of MgSiO₃ have been determined from Brillouin spectroscopy. They are: C₁₁ = 472, C₁₂ = 168, C₃₃ = 382, C₁₃ = 70, C₄₄ = 106, C₁₄ = ?27, C₆₆ = 152 and C₂₅ = ?24 in GPa. These elastic properties are consistent with a structural mechanical model where the silicon octahedra are very stiff under compression and shear. This latter property yields an unexpectedly high shear modulus for the magnesium silicate ilmenite as compared with analogue compounds. The further transformation to perovskite will probably be associated with a significant increase in elastic properties since the strong silicon polyhedra form a structural network in this phase. The transformation of spinel and stishovite to ilmenite is associated with a slight density increase and a slight decrease in acoustic velocities. This transformation will probably not produce a seismic discontinuity even if it does occur in the Earth's mantle.     

Elasticity of pyrope and majorite-pyrope solid solutions to high temperatures

Majorite-garnet solid solutions are major mineral phases in the Earth’s upper mantle and transition zone. Here we present the first Brillouin scattering measurements of the elasticity of majorite (Mj, Mg₄Si₄O₁₂)-pyrope (Py, Mg₃Al₂Si₃O₁₂) solid solutions (Mj₅₀Py₅₀ and Mj₈₀Py₂₀) and single-crystal elasticity of pure synthetic pyrope at temperatures up to 800°C. The temperature derivatives of the adiabatic bulk (K_S) and shear (μ) moduli for all compositions along the Mj-Py join are the same within the experimental uncertainties (−∂K_S/∂T=14.0-14.5(20) MPa/K, −∂μ/∂T=8.3-9.2(10) MPa/K). The temperature dependence of the acoustic velocities for Mj-Py solid solutions is about half that of other major transition zone minerals. This implies that temperature variations in the transition zone, inferred from lateral velocity heterogeneity, can be significantly underestimated if the properties of majoritic garnet are not taken into account.     

Solubility of FeO in (Mg,Fe)SiO3 perovskite and the post-perovskite phase transition

Phase relations in Mg_0.5Fe_0.5SiO₃ and Mg_0.25Fe_0.75SiO₃ were investigated in a pressure range from 72 to 123 GPa on the basis of synchrotron X-ray diffraction measurements in situ at high-pressure and -temperature in a laser-heated diamond-anvil cell (LHDAC). Results demonstrate that Mg_0.5Fe_0.5SiO₃ perovskite is formed as a single phase at 85–108 GPa and 1800–2330 K, indicating a high solubility of FeO in (Mg,Fe)SiO₃ perovskite at high pressures. Post-perovskite appears coexisting with perovskite in Mg_0.5Fe_0.5SiO₃ above 106 GPa at 1410 K, the condition very close to the post-perovskite phase transition boundary in pure MgSiO₃. The coexistence of perovskite and post-perovskite was observed to 123 GPa. In addition, post-perovskite was formed coexisting with perovskite also in Mg_0.25Fe_0.75SiO₃ bulk composition at 106–123 GPa. In contrast to earlier experimental and theoretical studies, these results show that incorporation of FeO stabilizes perovskite at higher pressures. This could be due to a larger ionic radius of Fe²⁺ ion, which is incompatible with a small Mg²⁺ site in the post-perovskite phase.     

合肥塘西河异味物质及异味影响因子研究

以合肥市塘西河为研究对象,2014-2015年逐月对其水体水质和异味物质进行监测,同时结合塘西河浮游植物群落结构调查,综合分析塘西河异味物质变化规律及其影响因素.研究发现,塘西河异味暴发集中发生在夏季,夏季二甲基异莰醇浓度可达4909 ng/L,土腥素浓度可达197 ng/L.浮游植物群落结构调查表明,秋、冬季塘西河优势种类为蓝藻,春、夏季为硅藻、绿藻或隐藻.主成分分析得到5种主成分分别解释了光照、有机质、微生物活动、氮、磷等对水质的影响.相关性分析结果表明,氮是塘西河异味的限制因素,水体中氮浓度较高是异味产生的重要原因.     

Synthesis and crystal-chemical characterization of MgSiO3 perovskite

The orthorhombic MgSiO₃ perovskite has been synthesized with the aid of a double-stage split-sphere-type high-pressure apparatus at about 280 kbar and 1000°C. The unit cell dimensions are: a = 4.7754(3)Å, b = 4.9292(4)Å and c = 6.8969(5)Å with the probable space group Pbnm. Calculated density is 4.108 g cm^?3. Crystal structure determination has been carried out by means of both the geometrical simulation (DLS) technique and the ordinary powder X-ray analysis. The results indicate that the MgSiO₃ perovskite is closer to the ideal perovskite than ScAlO₃ perovskite.     

Organochlorine compounds in bottom sediments,benthos, and fish in the volga pool of the Rybinsk Reservoir

The concentrations of three groups of organochlorine compounds (HCCH, DDT, and PCB) in bottom sediments, zebra mussel, and two fish species—zope and roach—in the Volga Pool of the Rybinsk Reservoir. The concentrations of the examined toxicants can be ranked in the ascending order as follows: HCCH<DDT<PCB. The total concentration of organochlorine compounds (OCC) and their metabolites are very low, thus allowing the Volga Pool to be regarded as a background region for the Upper and Middle Volga Basin. A congener-specific determination of PCB was carried out, and priority congeners were identified for monitoring the ecosystem pollution by dioxin-like compounds.     

Thermal structure and energy of the Hakone volcano,Japan

The thermal energy balance and the temperature profile of the Hakone volcano are considered quantitatively. Across the Hakone volcano and its surroundings the heat flow values vary from 10^–1 to 10³ mW/m², due to thermal conduction and mass flow involving volcanic steam and hot spring discharge. An area with extremely low heat flow is observed in the western side of the caldera showing the presence of percolating meteoric water. The hydrothermal activity is intense in the eastern half of the caldera.The total heat discharge from the high temperature zone (discharge area) of the Hakone volcano amounts to 11.0×10⁷ W. The magmatic steam energy discharge is 95.0×10⁶ W. The thermal energy by redistribution of the terrestrial heat flow by the lateral deep ground water flow is calculated to be 9.00×10⁶ W. For the model having the vertical vent in the volcano's central part up to 1 km depth below the ground surface from a magma reservoir the computed temperature distribution is consistent with the observed values. The depth of the magma reservoir is 7 km below the ground surface and the diameter is 5 km.     

Elasticity of (Mg, Fe)(Si, Al)O3-perovskite at high pressure

The most abundant mineral on Earth has a perovskite crystal structure and a chemistry that is dominated by MgSiO₃ with the next most abundant cations probably being aluminum and ferric iron. The dearth of experimental elasticity data for this chemically complex mineral limits our ability to calculate model seismic velocities for the lower mantle. We have calculated the single crystal elastic moduli (c_ij) for (Mg, Fe^3 +)(Si, Al)O₃ perovskite using density functional theory in order to investigate the effect of chemical variations and spin state transitions of the Fe³⁺ ions. Considering the favored coupled substitution of Mg²⁺-Si^4 + by Fe³⁺-Al³⁺, we find that the effect of ferric iron on seismic properties is comparable with the same amount of ferrous iron. Ferric iron lowers the elastic moduli relative to the Al charge-coupled substitution. Substitution of Fe³⁺ for Al³⁺, giving rise to an Fe/Mg ratio of 6%, causes 1.8% lower longitudinal velocity and 2.5% lower shear velocity at ambient pressure and 1.1% lower longitudinal velocity and 1.8% lower shear velocity at 142 GPa. The spin state of the iron for this composition has a relatively small effect (< 0.5% variation) on both bulk modulus and shear modulus.     

Mechanical behavior of magma reservoir envelopes: Elasticity of the olivine tholeiite solidus

A study of the elasticity of the solidus of igneous rocks provides a means of evaluating several high temperature mechanical characteristics of the zone that forms the transition region between solid rock and rock with a small fraction of partial melt — that is, the magma reservoirenvelope. This type of study has been performed for Hawaiian olivine tholeiite, by employing the theoretical treatment ofWalsh (1969). The effective aggregate bulk modulus (K*), aggregate rigidity (μ*), aggregate Young’s modulus (E*) and the aggregate Poisson’s ratio (n*) have been used to characterize the range in elastic behavior expected for this partially molten envelope. The details of mineralogy, mineral crystal chemistry and microstructure for a tholeiitic basalt from a deep-ponded flow unit (the Boiling Pots), as well as the geometry of melt pocket aspect ratios have been used to provide a basis for computing the elasticity for a shallow reservoir solidus. For a broad range in modal mineralogy, the internal 0–1% melt represents a transition region from an aggregate elasticity controlled by mineral composition, to an elastic behavior dominated by the melt phase (evaluated at a melt pocket aspect ratio ofε=0.001). For vesicular rocks in a low pressure environment, the internal 0–1% melt represents a transition from porosity-controlled elasticity to melt-controlled elasticity, evaluated at a prevalent aspect ratio ofε=0.001, and over the porosity range Φ=0.0?0.20 (20%). Thin melt films found to separate plagioclase microlites (0.0001=ε) are capable of effecting a 94.7% reduction in Young’s modulus, E*, over the 0–1% melt range, and suggest that the reservoir envelope may be critically weakened by rather small volume fractions of liquid, if dispersed in such narrow packets.