The Mg2GeO4 olivine-spinel phase transition

Enthalpies and entropies of transition for the Mg₂GeO₄ olivine-spinel transformation have been determined from self-consistency analyses of Dachille and Roy's (1960), Hensen's (1977) and Shiota et al.'s (1981) phase boundary studies. When all three data sets are analyzed simultaneously,ΔH ₉₇₃ andΔS ₉₇₃ are constrained between ?14000 to ?15300 J mol^?1 and ?13.0 to ?14.1·J mol^?1 K^?1, respectively. High-temperature solution calorimetric experiments completed on both polymorpha yield a value of ?14046±1366 J mol^?1 forΔH ₉₇₃. Kieffer-type lattice vibrational models of Mg₂GeO₄ olivine and spinel based on newly-measured infrared and Raman spectra predict a value of ?13.3±0.6 J mol^?1 K^?1 forΔS ₁₀₀₀. The excellent agreement between these three independent determinations ofΔH andΔS suggests that the synthesis runs of Shiota et al. (1981) at high pressures and temperatures bracket equilibrium conditions. In addition, no configurational disorder of Mg and Ge was needed to obtain the consistent parameters quoted. The Raman spectrum and X-ray diffractogram show that little disorder, if any, is present in Mg₂GeO₄ spinel synthesized at 0.2 GPa and 973–1048 K.     

Magnetic measurements in electrical prospecting by resistivity methods

The electrical resistivity and induced polarization (IP) methods are widely used in geological mapping, prospecting and exploration of mineral deposits, engineering geology, hydrogeology, archaeology, and geotechnical and environmental applications. Historically, these methods have formed the basis of the electrical prospecting technique. In these methods, a DC or low-frequency AC electrical current is introduced into the earth through a grounded transmitter line. The measured quantity is the electric field. However, if the earth’s resistivity or chargeability changes horizontally, this change gives rise to an anomalous magnetic field, which is studied by the magnetometric resistivity (MMR) and magnetic induced polarization (MIP) methods, respectively. Along with advantages, some shortcomings are inherent in the MMR and MIP techniques. Apparently, the main drawback of these methods is that the magnetic fields of both the transmitter line wire and ground electrodes on the surface are several orders of magnitude greater than the anomalous magnetic field response. This introduces a significant “noise” to magnetic-resistivity data. We investigate the potential of using a circular electric dipole (CED) in magnetometric resistivity techniques. It has been found that the application of a CED, instead of a conventional transmitter line, dramatically enhances the signal-to-noise ratio.     

A computer simulation study of OH defects in Mg2SiO4 and Mg2GeO4 spinels

Classical atomistic simulation techniques have been used to investigate the energies of hydrogen defects in Mg₂SiO₄ and Mg₂GeO₄ spinels. Ringwoodite (γ-Mg₂SiO₄) is considered to be the most abundant mineral in the lower part of the transition zone and can incorporate large amounts of water in the form of hydroxyls, whereas the germanate spinel (γ-Mg₂GeO₄) corresponds to a low-pressure structural analogue for ringwoodite. The calculated defect energies indicate that the most favourable mechanisms for hydrogen incorporation are coupled either with the reduction of ferric iron or with the creation of tetrahedral vacancies. Hydrogen will go preferentially into tetrahedral vacancies, eventually leading to the formation of the hydrogarnet defect, before associating with other negatively charged point defects. The presence of isolated hydroxyls is not expected. The same trend is observed for germanate, and thus γ-Mg₂GeO₄ could be used as a low-pressure analogue for ringwoodite in studies of water-related defects and their effect on physical properties.     

The phase boundary between wadsleyite and ringwoodite in Mg2SiO4 determined by in situ X-ray diffraction

The phase boundary between wadsleyite and ringwoodite in Mg₂SiO₄ has been determined in situ using a multi-anvil apparatus and synchrotron X-rays radiation at SPring-8. In spite of the similar X-ray diffraction profiles of these high-pressure phases with closely related structures, we were able to identify the occurrence of the mutual phase transformations based on the change in the difference profile by utilizing a newly introduced press-oscillation system. The boundary was located at ~18.9 GPa and 1,400°C when we used Shim’s gold pressure scale (Shim et al. in Earth Planet Sci Lett 203:729–739, 2002), which was slightly (~0.8 GPa) lower than the pressure as determined from the quench experiments of Katsura and Ito (J Geophys Res 94:15663–15670, 1989). Although it was difficult to constrain the Clapeyron slope based solely on the present data due to the kinetic problem, the phase boundary [P (GPa)=13.1+4.11×10⁻³×T (K)] calculated by a combination of a P–T position well constrained by the present experiment and the calorimetric data of Akaogi et al. (J Geophys Res 94:15671–15685, 1989) reasonably explains all the present data within the experimental error. When we used Anderson’s gold pressure scale (Anderson et al. in J Appl Phys 65:1535–1543, 1989), our phase boundary was located in ~18.1 GPa and 1,400°C, and the extrapolation boundary was consistent with that of Kuroda et al. (Phys Chem Miner 27:523–532, 2000), which was determined at high temperature (1,800–2,000°C) using a calibration based on the same pressure scale. Our new phase boundary is marginally consistent with that of Suzuki et al. (Geophys Res Lett 27:803–806, 2000) based on in situ X-ray experiments at lower temperatures (<1,000°C) using Brown’s and Decker’s NaCl pressure scales.     

Pressure-induced structural modifications in Mg2GeO4-olivine: A Raman spectroscopic study

Raman spectra of Mg₂GeO₄-olivine were obtained from ambient pressure up to 34 GPa at ambient temperature. Under quasi-hydrostatic pressure conditions, the following modifications in the Raman spectra occur as pressure increases: 1) near 11 GPa, two sharp extra bands appear in the 600–700 cm^?1 frequency range, and increase in intensity with respect to the olivine bands; 2) above 22 GPa, these two bands become very intense, and the number, position and relative intensity of the other vibrational bands drastically change; 3) the intensity of sharp bands progressively decreases above 25 GPa. The transformation occurs at lower pressures under non-hydrostatic conditions. During decompression to atmospheric pressure, the high-pressure phase partially reverts to olivine. These observations can be interpreted as the progressive metastable transformation from the olivine structure to a crystalline phase with four-fold coordinated Ge, in which the GeO₄ tetrahedra are polymerized. We propose that the metastable high-pressure phase is a structurally disordered spinelloid close to the hypothethical ω- or ?^*-phase, and forms by a shear mechanism assisted by the development of a dynamical instability in the olivine structure. Implications for the transformations undergone by olivines under far-from-equilibrium conditions (e.g. in subducting lithospheric slabs and in shocks) are discussed.     

Thermodynamics of the xanthoconite-proustite and pyrostilpnite-pyrargyrite phase transition as determined by abrasive stripping voltammetry

The electrochemical reduction of xanthoconite, proustite, pyrostilpnite, and pyrargyrite was studied by abrasive stripping voltammetry, a technique which is based upon a preliminary mechanical transfer of trace amounts of the mineral onto the surface of a paraffin impregnated graphite electrode. Because the electrochemical reduction proceeds near to reversibility and is very similar for each pair of minerals, the peak potentials in differential pulse voltammetry can be used to calculate the standard enthalpy of phase transformation of xanthoconite to proustite and of pyrostilpnite to pyrargyrite: _T H _{(xanth proust)} ^O = 35.46 ± 14.15 kJ/mol and _T H _{(pyrostilp pyrarg)} ^O = 38.85 ± 6.60 kJ/mol. These values are not accessible otherwise until now.     

The cubic-tetragonal phase transition in the system majorite (Mg4Si4O12) – pyrope (Mg3Al2Si3O12), and garnet symmetry in the Earth's transition zone

 Garnets along the join Mg₄Si₄O₁₂ (majorite end member) – Mg₃Al₂Si₃O₁₂ (pyrope) synthesized at 2000 °C, 19 GPa are, after quench, tetragonal in the compositional range up to 20 mol% pyrope, but cubic at higher Al contents. Lattice constants a _tet and a _tet in the tetragonal compositional range converge with increasing pyrope contents towards the lattice constant of the cubic garnets. The elastic strain and the intensity of the (222) reflection as a function of composition indicate a second-order phase transition near 20 mol% pyrope. From the wedge-like shape of pseudomerohedral twins and their interaction near 90° twin-boundary corners, as well as from the absence of growth-induced dislocations, it is concluded that the Al-poor garnets are also cubic at synthesis conditions but invert by (Mg,Si) ordering on the octahedral sites into tetragonal phases of space group I4₁/a upon quench. This implies that the cubic-to-tetragonal phase transition in Mg₄Si₄O₁₂ garnet occurs below 2000 °C at 19 GPa and at even lower temperatures in more aluminous compositions. A composition-dependent Landau model is consistent with a direct transformation from Ia3d to I4₁/a. Comparison of the T-X stability field of majorite-pyrope garnets with the chemistry of majorite-rich garnets expected to occur in the Earth's transition zone shows that the latter will be cubic under all conditions. Softening of elastic constants, which commonly accompanies ferroelastic phase transitions, may affect the seismic velocities of garnets in the deeper transition zone where majorite contents are highest. Received July 5, 1996 / Revised, accepted September 24, 1996     

Delineation of shallow resistivity structure in the city of Burdur,SW Turkey by vertical electrical sounding measurements

The city of Burdur, which is built on an alluvium aquifer, is located in one of the most seismically active zones in southwestern Turkey. The soil properties in the study site are characterized by unconsolidated and water-saturated sediments including silty, clayey and sandy units, and shallow groundwater level is the other characteristic of the site. Thus, the city is under soil liquefaction risk during a large earthquake. A resistivity survey including 189 vertical electrical sounding (VES) measurements was carried out in 2000 as part of a multi-disciplinary project aiming to investigate settlement properties in Burdur city and its vicinity. In the present study, the VES data acquired by using a Schlumberger array were re-processed with 1D and 2D inversion techniques to determine liquefaction potential in the study site. The results of some 1D interpretations were compared to the data from several wells drilled during the project. Also, the groundwater level map that was previously obtained by hydrological studies was extended toward north by using the resistivity data. 2D least-squares inversions were performed along nine VES profiles. This provided very useful information on vertical and horizontal extends of geologic units and water content in the subsurface. The study area is characterized by low resistivity distribution (<150 Ωm) originating from high fluid content in the subsurface. Lower resistivity (3–30 Ωm) is associated with the Quaternary and the Tertiary lacustrine sediments while relatively high resistivity (40–150 Ωm) is related to the Quaternary alluvial cone deposits. This study has also shown that the resistivity measurements are useful in the estimation of liquefaction risk in a site by providing information on the groundwater level and the fluid content in the subsurface. Based on this, we obtained a liquefaction hazard map for the study area. The liquefaction potential was classified by considering the resistivity distributions from 2D inversion of the VES profiles, the types of the sediments and the extended groundwater level map. According to this map, the study area was characterized by high liquefaction hazard risk.     

High pressure phase transformations in the joins Mg2SiO4-Ca2SiO4 and MgO-CaSiO3

High pressure phase transformations for all the mineral phases along the joins Mg₂SiO₄-Ca₂-SiO₄ and MgO-CaSiO₃ in the system MgO-CaO-SiO₂ were investigated in the pressure range between 100 and 300 kbar at about 1,000 °C, by means of the technique involving a diamond-anvil press coupled with laser heating. In addition to the four end-members, there are three stable intermediate mineral components in these two joins. Phase behaviour of all the end-member components at high pressure have been reported earlier and are reviewed here. Results of this study reveal that the three intermediate components are all unstable relative to the end-members at pressures greater than 200 kbar. Ultimately, monticellite (CaMgSiO₄) decomposes into CaSiO₃ (perovskite-type)+MgO; merwinite (Ca₃MgSi₂O₈) decomposes into Ca₂SiO₄(K₂NiF₄-type)+CaSiO₃ (perovskite-type)+MgO; and akermanite (Ca₂MgSi₂O₇) decomposes into CaSiO₃ (perovskite-type)+MgO. Note that the decomposition reactions of all phases studied here result in the formation of MgO. Intermediate Ca-Mg silicates transform to pure Ca-silicates plus MgO, while pure Mg₂SiO₄ transforms to MgSiO₃+MgO.     

The effect of crystal field stabilization on the olivine→spinel transition in the system Mg2SiO4 - Fe2SiO4

Crystal field stabilization (CFS) plays a significant role in determining equilibrium phase boundaries in olivine→spinel transformations involving transition-metal cations, including Fe²⁺ which is a major constituent of the upper mantle. Previous calculations for Fe₂SiO₄ ignored pressure and temperature dependencies of crystal field stabilization enthalpies (CFSE) and the electronic configurational entropy (S _CFS). We have calculated free energy changes (ΔG _CFS) due to differences of crystal field splittings between Fe₂SiO₄ spinel and fayalite from: ΔG _CFS=?ΔCFSE?TΔS _CFS, as functions of P and T, for different energy splittings of t _2g orbital levels of Fe²⁺ in spinel. The results indicate that ΔG _CFS is always negative, suggesting that CFS always promotes the olivine→spinel transition in Fe₂SiO₄, and expands the stability field of spinel at the expense of olivine. Because of crystal field effects, transition pressures for olivine→spinel transformations in compositions (Mg_1?x Fe _x )₂SiO₄ are lowered by approximately 50x kbar, which is equivalent to having raised the olivine→spinel boundary in the upper mantle by about 15 km.     

Heat capacity studies of phase transitions in langbeinites II. K2Mg2(SO4)3

Heat capacity measurements have been made on a synthetic sample of langbeinite, K₂Mg₂(SO₄)₃, from 13 to 342 K in an adiabatic calorimeter. Three phase transitions, at 51.0, 54.9 and 63.8 K, have been observed in this material. Our study is the first to report the existence of such phase transitions in K₂Mg₂(S0₄)₃ and disputes predictions that none would take place below 77 K. Two models which have been proposed to explain the transition in potassium langbeinites are discussed in light of these results.     

Twinning induced by the rhombohedral to orthorhombic phase transition in lanthanum gallate (LaGaO3)

Phase-transformation-induced twins in pressureless-sintered lanthanum gallate (LaGaO₃) ceramics have been analysed using the transmission electron microscopy (TEM). Twins are induced by solid state phase transformation upon cooling from the rhombohedral to orthorhombic (o, Pnma) symmetry at ∼145°C. Three types of transformation twins {101} _o , {121} _o , and {123} _o were found in grains containing multiple domains that represent orientation variants. Three orthorhombic orientation variants were distinguished from the transformation domains converged into a triple junction. These twins are the reflection type as confirmed by tilting experiment in the microscope. Although not related by group–subgroup relation, the transformation twins generated by phase transition from rhombohedral to orthorhombic are consistent with those derived from taking cubic aristotype of the lowest common supergroup symmetry as an intermediate metastable structure. The r→ o phase transition of first order in nature may have occurred by a diffusionless, martensitic-type or discontinuous nucleation and growth mechanism.     

High temperature single crystal X-ray diffraction studies of the ortho-proto phase transition in enstatite,Mg2Si2O6 at 1360 K

A high temperature single-crystal X-ray diffraction study of enstatite, Mg₂Si₂O₆ was undertaken at 296, 900, 1200, 1360 and 1400 K. During the X-ray data collection at 1360 K (T₀), orthoenstatite (Pbca) transformed to protoenstatite (Pbcn). The unit cell parameters measured at T₀ are a=18.456(4), b=8.960(2) and c=5.270(1) Å for ortho and a=9.306(1), b=8.886(1) and c=5.360(1) Å for proto. The discontinuous increase in c and decrease in b due to the ortho to proto transformation are associated with the drastic unkinking of the silicate chains, whereas the abrupt increase in a results from the large expansion of the M2 — O distances along a coupled with the increase in the out-of-plane tilting of the silicate tetrahedra. Stacking faults form in ortho prior to the phase transition, as well as in proto between 1360 and 1400 K. With increasing temperature, the silicate B chain in ortho straightens faster than the A chain as the configurations of the SiA and SiB tetrahedra tend to become similar. At T₀, the A and B chains with the O3-O3-O3 angles (O3 being the bridging oxygen atom) of 163.0° and 149.5° in ortho, respectively, attain an identical angle of 168.4° in proto. The configuration of the silicate chain in proto resembles that of the A chain in ortho. Rigid-body thermal vibration analysis suggests that between 1200 and 1400 K the largest, the second largest and the smallest thermal librational motions of the [SiO₄] tetrahedra in both ortho and proto are approximately around a, c and b, respectively. Below 1200 K, the largest thermal librational amplitudes of the SiA and SiB tetrahedra in ortho are quite different, but become nearly equivalent at T₀. In contrast to the results reported for all iron-bearing orthopyroxenes at high temperature, switching of the O3B atoms coordinated with the M2 cation occurs during the ortho to proto transformation, but not in ortho below T₀. The ortho-proto transition does not affect the configuration of the M1 octahedron significantly, but results in a decrease of the mean M2 — O bond distance by 0.043 Å and a highly distorted M2 octahedron in proto.     

In situ observation of a phase transition in Fe2SiO4 at high pressure and high temperature

We used an in situ measurement method to investigate the phase transition of Fe₂SiO₄ polymorphs under high pressures and temperatures. A multi-anvil high-pressure apparatus combined with synchrotron X-ray radiation was used. The stability of each polymorph was identified by observing the X-ray diffraction data from the sample. In most experiments, the diffraction patterns were collected 10–30 min after reaching the desired pressure and temperature conditions. The transition boundary between the olivine and spinel phase at T = 1,000–1,500 K and P = 2–8 GPa was determined to occur at P (GPa) = 0.5 + 0.0034 × T (K). The transition pressure determined in this study was in general agreement with that observed in previous high-pressure experiments. However, the slope of the transition, dP/dT, determined in our study was significantly higher than that estimated by the previous study combined with the in situ X-ray method.     

High-pressure phase transition and behavior of protons in brucite Mg(OH)2: a high-pressure–temperature study using IR synchrotron radiation

 Infrared absorption spectra of brucite Mg (OH)₂ were measured under high pressure and high temperature from 0.1 MPa 25 °C to 16 GPa 360 °C using infrared synchrotron radiation at BL43IR of Spring-8 and a high-temperature diamond-anvil cell. Brucite originally has an absorption peak at 3700 cm⁻¹, which is due to the OH dipole at ambient pressure. Over 3 GPa, brucite shows a pressure-induced absorption peak at 3650 cm⁻¹. The pressure-induced peak can be assigned to a new OH dipole under pressure. The new peak indicates that brucite has a new proton site under pressure and undergoes a high-pressure phase transition. From observations of the pressure-induced peak under various P–T condition, a stable region of the high-pressure phase was determined. The original peak shifts to lower wavenumber at −0.25 cm⁻¹ GPa⁻¹, while the pressure-induced peak shifts at −5.1 cm⁻¹ GPa⁻¹. These negative dependences of original and pressure-induced peak shifts against pressure result from enhanced hydrogen bond by shortened O–H···O distance, and the two dependences must result from the differences of hydrogen bond types of the original and pressure-induced peaks, most likely from trifurcated and bent types, respectively. Under high pressure and high temperature, the pressure-induced peak disappears, but a broad absorption band between 3300 and 3500 cm⁻¹ was observed. The broad absorption band may suggest free proton, and the possibility of proton conduction in brucite under high pressure and temperature. Received: 16 July 2001 / Accepted: 25 December 2001     

Mapping lithology and assessing recharge characteristics in a granitic hard rock aquifer: Inference from 2D resistivity,induced polarization,tracer and moisture measurements

Two dimensional Electrical Resistivity Tomography (ERT) investigation along with Time Domain Induced Polarization (TDIP) investigation covering 1.6 km line were carried out at 3 natural recharge sites in a overexploited groundwater granite watershed, situated in a semi arid region in the state of Telangana, India. At these sites, shallow and/ or deep moisture influx measurements were also carried out using injected tritium tracer and neutron moisture probe. The watershed is covered by sandy loam to silt loam soil, receives an average annual rainfall of 620 mm with the pre monsoon groundwater level ranging from 8m to 29m bgl. The spot investigations were done to assess and understand the recharge process and groundwater potential in terms of resistivity/conductivity and moisture characteristics of the subsurface rock formation.     

Pressure induced phase transition in Pb<Subscript>6</Subscript>Bi<Subscript>2</Subscript>S<Subscript>9</Subscript>

The crystal structure of Pb₆Bi₂S₉ is investigated at pressures between 0 and 5.6 GPa with X-ray diffraction on single-crystals. The pressure is applied using diamond anvil cells. Heyrovskyite (Bbmm, a = 13.719(4) Å, b = 31.393(9) Å, c = 4.1319(10) Å, Z = 4) is the stable phase of Pb₆Bi₂S₉ at ambient conditions and is built from distorted moduli of PbS-archetype structure with a low stereochemical activity of the Pb²⁺ and Bi³⁺ lone electron pairs. Heyrovskyite is stable until at least 3.9 GPa and a first-order phase transition occurs between 3.9 and 4.8 GPa. A single-crystal is retained after the reversible phase transition despite an anisotropic contraction of the unit cell and a volume decrease of 4.2%. The crystal structure of the high pressure phase, β-Pb₆Bi₂S₉, is solved in Pna2 ₁ (a = 25.302(7) Å, b = 30.819(9) Å, c = 4.0640(13) Å, Z = 8) from synchrotron data at 5.06 GPa. This structure consists of two types of moduli with SnS/TlI-archetype structure in which the Pb and Bi lone pairs are strongly expressed. The mechanism of the phase transition is described in detail and the results are compared to the closely related phase transition in Pb₃Bi₂S₆ (lillianite).     

Crystal field transitions in Co2[Al4Si5]O18 cordierite and CoAl2O4 spinel determined by neutron spectroscopy

Inelastic magnetic neutron scattering has been used to determine the energy of the ⁴ A ₂→⁴ T ₂ transition in CoAl₂O₄ spinel and the δ₁ transition in Co₂[Al₄Si₅]O₁₈ cordierite. The observed crystal field splitting in Co-spinel is 485 meV (3900 cm⁻¹), which corresponds to a crystal field stabilization energy of 56.2 kJmol⁻¹. The transition energy of the δ₁ transition in Co-cordierite has been determined to be 21 meV (170 cm⁻¹). The present data demonstrate that magnetic neutron scattering can be used to measure crystal field transitions at energies of interest in the study of 3d-containing silicates. It may be used to measure transition energies when the use of optical spectroscopy is inappropriate. Received: 30 January 1997 / Accepted: 5 July 1997     

The incommensurate-commensurate phase transition in akermanite,Ca2MgSi2O7, observed by in-situ 29Si MAS NMR spectroscopy

²⁹Si MAS NMR spectra of synthetic akermanite, Ca₂MgSi₂O₇, exhibit a splitting into three or more lines in the stability feld of the low-temperature incommensurate phase. With increasing temperature, these lines continuously merge into a single line which is then characteristic of the high-temperature, melilite-type structure. The data point to the non-equivalence of Si sites in the low-temperature phase and the gradual structural changes as the phase transition temperature is approached.     

PM_(2.5)降尘诱导A549细胞G2/M期阻滞的机制研究

PM_(2.5)降尘作用于A549细胞后,MTT法检测细胞存活率,扫描电镜观察细胞形态,流式细胞术检测细胞周期改变,RT-PCR检测周期阻滞相关基因p53、p21、CDK1、c-myc和lncRNA H19的表达水平,Western-blot检测周期蛋白cyclin B1表达。通过转染H19 siRNA干扰H19的表达,RT-PCR检测其对p53、c-myc及CDK1表达的影响,以探讨PM2.5降尘诱导A549细胞周期阻滞的作用机制。结果显示,PM2.5降尘暴露可降低A549细胞存活率,随作用浓度及时间增加呈递减趋势,并可观察到细胞形态破坏,细胞膜表面吸附聚集大量粉尘颗粒。PM2.5作用于细胞24 h后,A549细胞增殖阻滞在G2/M期,周期阻滞相关基因p53、p21及H19表达增加,CDK1及cyclin B1表达降低。此外,转染H19 siRNA后成功干扰H19的表达,并调控CDK1表达进一步降低。综合以上结果,PM2.5降尘处理A549细胞后可通过激活p53及p21活性,抑制CDK1和cyclin B1表达水平,诱导G2/M期阻滞从而抑制细胞增殖。短期暴露于PM2.5后,lncRNA H19在染毒细胞中可能发挥特异性癌基因的作用,通过与p53及c-myc结合参与调控细胞周期,干扰H19低表达使细胞G2/M期阻滞更加明显。