Influence of stacking faults on the spiral growth of polytype structures in mica

A systematic theoretical deduction of polytype structures of mica that can result by the spiral growth mechanism operating in faulted 1M, 2M ₁ and 3T basic matrices is reported. As a prerequisite, all possible intrinsic and extrinsic stacking fault configurations in each of the basic matrices have been worked out and their stacking fault energy (SFE) estimated. The deduction of polytype structures on the basis of the “faulted-matrix model” takes into account (i) the introduction of each of the low energy fault configurations in the exposed ledge of the screw dislocations, (ii) the change in the layer-position of the fault within the exposed ledge and (iii) the variation of the strength of the generating screw dislocation. At each stage, the spirally-grown polytypes are deduced for each basic structure. The most probable structures are predicted on the basis of the lowest SFE for the same strength of the screw dislocation and are then compared with the polytype structures reported in the literature. It was found that the faulted matrix model accounts successfully for the origin of all the polytype structures in mica. Furthermore, it may provide a basis for limiting the number of trial structures for determining the structures of long period polytypes.     

The mass of the compact object in the low-mass X-ray binary 2S 0921-630

We interpret the observed radial-velocity curve of the optical star in the low-mass X-ray binary 2S 0921-630 using a Roche model, taking into account the X-ray heating of the optical star and screening of X-rays coming from the relativistic object by the accretion disk. Consequences of possible anisotropy of the X-ray radiation are considered. We obtain relations between the masses of the optical and compact (X-ray) components, m _v and m _x , for orbital inclinations i = 60°, 75°, and 90°. Including X-ray heating enabled us to reduce the compact object’s mass by ～0.5–1 M _⊙, compared to the case with no heating. Based on the K0III spectral type of the optical component (with a probable mass of m _v ? 2.9 M _⊙), we concluded that m _x ? 2.45?2.55 M _⊙ (for i = 75°?90°). If the K0III star has lost a substantial part of its mass as a result of mass exchange, as in the V404 Cyg and GRS 1905+105 systems, and its mass is m _v ? 0.65?0.75 M _⊙, the compact object’s mass is close to the standard mass of a neutron star, m _x ? 1.4 M _⊙ (for i = 75°?90°). Thus, it is probable that the X-ray source in the 2S 0921-630 binary is an accreting neutron star.     

Magnetic properties of the clinopyroxenes aegirine and hedenbergite: a magnetic susceptibility study on single crystals

Two natural clinopyroxene single crystals were investigated, an aegirine-augite (AEG) and a magnesian hedenbergite (HED). Both samples were carefully characterized by electron microprobe, X-ray diffraction, and Mössbauer spectroscopy. Magnetic susceptibility measurements of powdered samples reveal low temperature antiferromagnetic coupling and Curie-Weiss behaviour with T _N =7.5(5)?K, Θ _P =?19(1)?K for AEG, and T _N =31(1)?K, Θ _P =+21(1)?K for HED, respectively. Low temperature Mössbauer spectra exhibit relaxation phenomena. Magnetic susceptibility measurements of the single crystals show the direction of the magnetic moments to be lying within the a/c plane for both samples: 50(±2)° from a and 57(±2)° from c in AEG, and 45(±2)° from a and 60(±2)° from c in HED, respectively. The antiferromagnetic interchain interaction competes with the ferromagnetic intrachain interaction in both pyroxenes. In the magnesian hedenbergite a field induced magnetic transition is found. Its dependence on temperature, magnetic field and crystallographic direction is investigated and described.     

Petrology and P–T history of the Wutai amphibolites: implications for tectonic evolution of the Wutai Complex,China

The Wutai Complex represents the best preserved granite-greenstone terrane in the North China Craton. The complex comprises a sequence of metamorphosed ultramafic to felsic volcanic rocks, variably deformed granitoid rocks, along with lesser amounts of siliciclastic and carbonate rocks and banded iron formations. Petrological evidence from the Wutai amphibolites indicates four metamorphic evolutionary stages. The M₁ assemblage is composed of plagioclase+quartz+actinolite+chlorite+epidote+biotite+rutile, preserved as mineral inclusions in garnet porphyroblasts. The metamorphic conditions for this assemblage cannot be quantitatively estimated. The M₂ stage is represented by garnet porphyroblasts in a matrix of quartz, plagioclase, amphibole, biotite, rutile and ilmenite. P–T conditions for this assemblage have been estimated using the program Tweequ at 10–12 kbar and 600–650°C. The M₃ assemblage is shown by amphibole+plagioclase±ilmenite symplectic coronas around embayed garnets and yields P–T conditions of 6.0–7.0 kbar and 600–650°C. M₄ is represented by chlorite and epidote rimming garnet, chlorite rimming amphibole and epidote replacing plagioclase under greenschist-facies conditions of 400–500°C and relatively lower pressures. Taken together, the qualitative P–T estimates from M₁ and M₄ and the quantitative P–T estimates from M₂ and M₃ define a clockwise P–T path for the Wutai amphibolites.The estimated P–T path from the four stages suggests that the Wutai Complex underwent initial burial and crustal thickening (M₁+M₂), subsequent isothermal exhumation (M₃), and finally cooling and retrogression (M₄). This tectonothermal path, along with those of the Fuping and Hengshan complexes, which bound the southeast and northwest margins, respectively, of the Wutai Complex, is considered to record the early Paleoproterozoic collision between the eastern and western segments of the North China craton.     

Thermal expansion and high-temperature P21/c–C2/c phase transition in clinopyroxene-type LiFeGe2O6 and comparison to NaFe(Si,Ge)2O6

A synthetic clinopyroxene with composition LiFe³⁺Ge₂O₆, monoclinic s.g. P2₁/c, a = 9.8792(7), b = 8.8095(5), c = 5.3754(3) Å, β = 108.844(6)°, V = 442.75(16) ų, has been studied by in situ low- and high-temperature single-crystal X-ray diffraction. The variation of lattice parameters and the intensity of the b-type reflections (h + k = 2n + 1, only present in the P-symmetry) with increasing temperature showed a displacive phase transition from space group P2₁/c to C2/c at a transition temperature T _tr = 789 K, first order in character, with a sudden volume increase of 1.6% and a decrease of β by 1° at the transition. This spontaneous dilatation is reversible, shows a limited hysteresis of ±10°C, and corresponds to the vanishing of the b-type reflections, thus indicating a symmetry increase to space group C2/c. Below T _tr an expansion is observed for all the cell parameters, while the β angle remained almost constant; at T > T _tr the thermal volume expansion is due to dilatation of the structure in the $(\bar{1}\,0\,1) A synthetic clinopyroxene with composition LiFe³⁺Ge₂O₆, monoclinic s.g. P2₁/c, a = 9.8792(7), b = 8.8095(5), c = 5.3754(3) ?, β = 108.844(6)°, V = 442.75(16) ?³, has been studied by in situ low- and high-temperature single-crystal X-ray diffraction. The variation of lattice parameters and the intensity of the b-type reflections (h + k = 2n + 1, only present in the P-symmetry) with increasing temperature showed a displacive phase transition from space group P2₁/c to C2/c at a transition temperature T _tr = 789 K, first order in character, with a sudden volume increase of 1.6% and a decrease of β by 1° at the transition. This spontaneous dilatation is reversible, shows a limited hysteresis of ±10°C, and corresponds to the vanishing of the b-type reflections, thus indicating a symmetry increase to space group C2/c. Below T _tr an expansion is observed for all the cell parameters, while the β angle remained almost constant; at T > T _tr the thermal volume expansion is due to dilatation of the structure in the ([`1] 0 1)(\bar{1}\,0\,1) plane, mostly along [0 1 0], and pure shear in the (0 1 0) plane due to the decrease of β. From comparison with silicate analogues, the germanate clinopyroxenes are more expansible, while the P2₁/c expands more than the C2/c phase. The evolution of Q ² (calculated as the normalized intensity of b-type reflections) with T in the framework of the Landau theory has been done using a standard expression for a first order phase transition. We observe a jump of Q ₀² = 0.538(2) at T _tr, with T _c of 481(7) K, b/a = −2,290 K, and c/a = 3,192 K, and thus far from being tri-critical point. A closely related composition (LiFe³⁺Si₂O₆) shows an equivalent phase transition at 228 K, which is very close to the tri-critical point and 561 K cooler. This result indicates that a change in the composition of tetrahedral sites can have dramatic effects on the P2₁/c ↔ C2/c displacive phase transition in clinopyroxenes. The major changes observed in the evolution of the crystal structure with T are observed in the M2 polyhedron, with a volume decrease by ca. 13.3%, compared to ca. 1.3% observed in the M1 polyhedron. The tetrahedra behave as rigid units with neither a significant change of volume at T > T _tr (<1‰), nor a change of tilting of the basal plane. No change in coordination is observed at T > T _tr in the M2 polyhedron, which remains sixfold coordinated although a strong deformation of this polyhedron is observed. This deformation is related to a strong change by 51.4° at T _tr of the kinking angle (O3–O3–O3 angle) of the B-chain of tetrahedra, which switches from O-rotated to S-rotated [from 143.3(5)° to 194.7(6)°]. The A-chain is S-rotated at T < T _tr [206.8(5)° at 703 K] and extends by 12° at the transition.     

Long-term earthquake prediction in western Anatolia with the time- and magnitude-predictable model

Instrumental and historical data on mainshocks for 13 seismogenic sources in western Anatolia have been used to apply a regional time- and magnitude-predictable model. Considering the interevent time between successive mainshocks, the following two predictive relations were computed: log T _t = 0.13 M _min + 0.21 M _p ? 0.15 log M ₀ + 2.93 and M _f = 0.87 M _min ? 0.06 M _p + 0.33 log M ₀ ? 6.54. Multiple correlation coefficient and standard deviation have been computed as 0.50 and 0.29, respectively, for the first relation, and 0.65 and 0.47, respectively, for the second relation. The positive dependence of T _t on M _p and the negative dependence of M _f on M _p indicate the validity of time- and magnitude-predictable model on the area considered in this study. On the basis of these relations and using the occurrence time and magnitude of the last main shocks in each seismogenic source, the probabilities of occurrence P(Δt) of the next main shocks during the next 50 years with decade interval as well as the magnitude of the expected main shocks were determined. The highest probabilities P ₁₀ = 80 % (M _f = 6.8 and T _t = 13 years) and P ₁₀ = 32 % (M _f = 7.6 and T _t = 29 years) were estimated for the seismogenic source 11 (Golhisar-Dalaman-Rhodes) for the occurrence of a strong and a large earthquake during the future decade, respectively.     

Precursory seismicity rate changes prior to the large and major earthquakes along the Sagaing fault zone,Central Myanmar

In this study, the seismicity rate changes that can represent an earthquake precursor were investigated along the Sagaing Fault Zone (SFZ), Central Myanmar, using the Z value technique. After statistical improvement of the existing seismicity data (the instrumental earthquake records) by removal of the foreshocks and aftershocks and man-made seismicity changes and standardization of the reported magnitude scales, 3574 earthquake events with a M _w ≥ 4.2 reported during 1977–2015 were found to directly represent the seismotectonic activities of the SFZ. To find the characteristic parameters specifically suitable for the SFZ, seven known events of M _w ≥ 6.0 earthquakes were recognized and used for retrospective tests. As a result, utilizing the conditions of 25 fixed earthquake events considered (N) and a 2-year time window (T _w), a significantly high Z value was found to precede most of the M _w ≥ 6.0 earthquakes. Therefore, to evaluate the prospective areas of upcoming earthquakes, these conditions (N = 25 and T _w = 2) were applied with the most up-to-date seismicity data of 2010–2015. The results illustrate that the vicinity of Myitkyina and Naypyidaw (Z = 4.2–5.1) cities might be subject to strong or major earthquakes in the future.     

Analysis of factors controlling soil N2O emission by principal component and path analysis method

Nitrous oxide (N₂O) is a potent greenhouse gas. Mitigating N₂O emission is critical for combating global climate change and improving the ecological environment. Many studies have focused on factors affecting N₂O emission from agricultural soils, but rarely on the relationship among these factors. In the present study, continuous measurement on N₂O emission was conducted in a maize system in Griffith, Australia and the relationships between N₂O emission, soil properties and weather conditions were examined. Principal component analysis and path analysis were used to analyze these data in correlation coefficient and the direct and indirect effects to N₂O emission. Results indicated that (1) the major factors affecting N₂O emission were WFPS, mineralized nitrogen (Mineral N), daily mean temperature (T _mean) and CO₂ concentration. The factors of direct influence N₂O emission were following Mineral N, CO₂, WFPS, and T _mean. The indirect influence N₂O emission was following T _mean, WFPS, Mineral N, and CO₂ concentration. (2) The standard multiple regression describing the relationship between N₂O emission and its major factors were Y = ?37.162 + 0.5267 X ₁ + 0.4331 X ₂ + 0.3014 X ₃ + 0.2392 X ₄ (r = 0.924, p < 0.01, n = 151), where Y is N₂O emission, X ₁ is Mineral N, X ₂ is CO₂, X ₃ is WFPS and X ₄ is T _mean. (3) N₂O emission from agricultural soils can be monitored and mitigated through improved management practices such as irrigation, straw retention and fertilizer application.     

X-ray and HRTEM study of sursassite: Crystal structure,stacking disorder,and sursassite-pumpellyite intergrowth

Sursassite is monoclinic, space group P2 ₁/m, a=8.70, b=5.79, c=9.78 Å, β=108.9°. The crystal structure was determined with X-rays and refined to R=0.065, obtaining Mn₂Al₃[(OH)₃(SiO₄)(Si₂O₇)] as ideal crystal chemical formula. Sursassite, isostructural with macfallite Ca₂Mn₃[(OH)₃(SiO₄)(Si₂O₇)], is closely related to pumpellyite Ca₂Al₃[(OH)₃(SiO₄)(Si₂O₇)]. In fact both sursassite and pumpellyite, apart from the different chemical composition, are built up by common structural layers, which are repeated by different stacking vectors. As a result, faulted stacking sequences are energetically possible. Examination by high resolution transmission electron microscopy (HRTEM) shows that frequent (001) pumpellyite-like lamellae are intergrown with thicker (001) sursassite lamellae. Usually, the guest lamellae are a few unit cells thick along [001] and continuous along the (001) plane, although also rare interrupted lamellae are found.     

Synthesis and thermal stability of 2 \frac{1}{2}-octahedral sodium mica,NaMg2.5 (OH)2∫i4O10]

A new 2 \(\frac{1}{2}\) -octahedral sheet silicate, NaMg_2.5 Si₄O₁₀ (OH)₂, has been synthesized from oxide mixtures in the temperature range 500–600°C at pressures between 1 and 5 kb. The lattice parameters are a ₀ = 5.298 Å, b ₀ = 9.047 Å, c ₀ = 9.479 Å and ß=99.55°. X-ray data are given in the text. At temperatures above 605° C/1 kb and 630° C/5 kb, it decomposes to magnesiorichterite plus quartz.     

How stacking disorder can conceal the actual structure of micas: the case of phengites

The present study deals with how stochastic stackings of tetrahedral/octahedral phengitic sheets bearing diverse cation distributions affect diffraction signals and the structural inferences therefrom derived. The interest for such minerals is dictated by that the stability of phengite polytypes, their cation distributions and P/T conditions of crystallization are related to each other. We focus our attention on layers’ probabilistic sequences that preserve the topology of the polytypes 2M ₁(SG: C2/c) and 3T(SG: P3₁12). Neutron diffraction intensities are modelled by a Monte Carlo approach and then used as artificial experimental data for conventional structure refinements that yield the occupancy factors in the fourfold (Si, Al) and sixfold (Al, Mg) coordination sites of 2M ₁ and 3T. The cation ordering from structure refinement tallies with the one of the “average structure” of a stochastic stacking, but it can significantly differ from those of the individual tetrahedral/octahedral sheets. For instance, sheets having ordered cation arrangements can lead to a stochastic structure which is supposed to bear a fully disordered cation partitioning according to structure refinement. This affects the configuration entropy contributions: the values obtained by conventional refinements can deviate from the correct ones up to 30 %. The analysis of the equivalent reflection intensities brings to light the anomalies hinting at the occurrence of such stacking disorder (using modelled reflections, the mean ratio between standard deviation and average intensity of symmetry equivalent reflections is ideally 0 for perfect crystal structures, but it can amount up to 6 in stochastically disordered phengites). However, taking into account the instrumental uncertainties and the deviations from ideality of actual crystals, such phenomena are very difficult to be detected experimentally.     

Effects of temperature on the crystal structure of epidote: a neutron single-crystal diffraction study at 293 and 1,070 K

The effects of temperature on the crystal structure of a natural epidote [Ca_1.925 Fe_0.745Al_2.265Ti_0.004Si_3.037O₁₂(OH), a = 8.890(6), b = 5.630(4), c = 10.150(6) Å and β = 115.36(5)°, Sp. Gr. P2₁ /m] have been investigated by means of neutron single-crystal diffraction at 293 and 1,070 K. At room conditions, the structural refinement confirms the presence of Fe³⁺ at the M₃ site [%Fe(M3) = 73.1(8)%] and all attempts to refine the amount of Fe at the M(1) site were unsuccessful. Only one independent proton site was located. Two possible hydrogen bonds, with O(2) and O(4) as acceptors [i.e. O(10)–H(1)···O(2) and O(10)–H(1)···O(4)], occur. However, the topological configuration of the bonds suggests that the O(10)–H(1)···O(4) is energetically more favourable, as H(1)···O(4) = 1.9731(28) Å, O(10)···O(4) = 2.9318(22) Å and O(10)–H(1)···O4 = 166.7(2)°, whereas H(1)···O(2) = 2.5921(23) Å, O(10)···O(2) = 2.8221(17) Å and O(10)–H(1)···O2 = 93.3(1)°. The O(10)–H(1) bond distance corrected for “riding motion” is 0.9943 Å. The diffraction data at 1,070 K show that epidote is stable within the T-range investigated, and that its crystallinity is maintained. A positive thermal expansion is observed along all the three crystallographic axes. At 1,070 K the structural refinement again shows that Fe³⁺ share the M(3) site along with Al³⁺ [%Fe(M3)_1,070K = 74(2)%]. The refined amount of Fe³⁺ at the M(1) is not significant [%Fe(M1)_1,070K = 1(2)%]. The tetrahedral and octahedral bond distances and angles show a slight distortion of the polyhedra at high-T, but a significant increase of the bond distances compared to those at room temperature is observed, especially for bond distances corrected for “rigid body motions”. The high-T conditions also affect the inter-polyhedral configurations: the bridging angle Si(2)–O(9)–Si(1) of the Si₂O₇ group increases significantly with T. The high-T structure refinement shows that no dehydration effect occurs at least within the T-range investigated. The configuration of the H-bonding is basically maintained with temperature. However, the hydrogen bond strength changes at 1,070 K, as the O(10)···O(4) and H(1)···O(4) distances are slightly longer than those at 293 K. The anisotropic displacement parameters of the proton site are significantly larger than those at room condition. Reasons for the thermal stability of epidote up to 1,070 K observed in this study, the absence of dehydration and/or non-convergent ordering of Al and Fe³⁺ between different octahedral sites and/or convergent ordering on M(3) are discussed.     

Growth defects in metamorphic biotite

Metamorphic biotites examined by transmission electron microscopy contain planar defects on the (001) plane, superlattices, twins and a microstructure causing streaking of k≠3n rows. Analysis of the fringe contrast shows that the fault vectors associated with the planar defects are either R ₁=±1/3 [010], R ₂=±1/6 [310] or R ₃=±1/6 [3 \(\bar 1\) 0]. Structural considerations indicate that a stacking fault R ₁, R ₂ or R ₃ is most likely to exist in the octahedral layer rather than the potassium layer. The result of such a fault on a unit layer of mica is effectively to rotate it through ±120° about c* (equivalent to the common mica twin law). These stacking faults can provide the mechanism for producing the ±120° rotations associated with the common mica polytypes. Furthermore, many of the observed microstructures can be generated by these stacking faults.     

Structural change in lead fluorapatite at high pressure

The structure of lead fluorapatite [PbFAP; Pb₁₀(PO₄)₆F₂], crystallized from the melt in a platinum capsule at 1,000°C and 1 atm, has been investigated by single-crystal X-ray diffraction. Crystal data are a = 9.7638 (6), c = 7.2866 (4) Å, space group P6₃/m, R = 0.043, R _w = 0.034. We have also studied the compressional behaviour of the c-axis channel of PbFAP up to 9 GPa at 25°C, using a diamond-anvil cell, synchrotron X-radiation, and Rietveld powder structure refinement. Pressure–volume data for the channel polyhedron of PbFAP fitted to the third-order Birch–Murnaghan equation resulted in K _T  = 33.2 ± 1.2 GPa when K _T ′ is fixed at 4. The c-axis channel of PbFAP is about twice as compressible as the unit-cell volume of PbFAP and the channel of calcium apatites. This is attributed to the anomalous narrowing of the channel of PbFAP with increase in confining pressure. Flexibility of the apatite channel is a key factor in the scavenging of toxic heavy metals by calcium apatites.     

An example of multicomponent magnetization in welded tuffs: a case study of Upper Cretaceous welded tuffs of eastern Russia

Four distinct components of natural remanent magnetization were isolated from a single site in welded tuffs in the Upper Cretaceous Kisin Group of the Sikhote Alin mountain range, Russia. In order to contribute toward a basis for an interpretation of multicomponent magnetization, rock magnetic experiments were performed on the welded tuffs. All four magnetization components essentially reside in magnetite. The lowest-temperature component up to 300 °C (component A: D=349.3°, I=60.9°, α₉₅=7.3°, N=7) is a present day viscous magnetization. The third-removed component (component C: D=41.4°, I=51.8°, α₉₅=3.5°, N=8), isolated over the temperature range of 450–560 °C, is a primary remanence. The second- and fourth-demagnetized components (component B: D=174.7°, I=−53.1°, α₉₅=21.2°, N=3 and component D: D=188.1°, I=−64.5°, α₉₅=4.0°, N=8, respectively) are secondary magnetizations related to a thermal event in Sikhote Alin between 66 and 51 Ma. Components B and D were acquired through different remagnetization processes. Component B is ascribed to a thermoviscous remanent magnetization carried by single-domain magnetite, and component D is a chemical remanent magnetization.     

Structural evolution of a 2M 1 phengite mica up to 11 GPa: an in situ single-crystal X-ray diffraction study

The structural evolution at high pressure of a natural 2M ₁-phengite [(K_0.98Na_0.02)_Σ=1.00(Al_1.55Mg_0.24Fe_0.21Ti_0.02)_Σ=2.01(Si_3.38Al_0.62)O₁₀(OH)₂; a = 5.228(2), b = 9.057(3), c = 19.971(6)Å, β = 95.76(2)°; space group: C2/c] from the metamorphic complex of Cima Pal (Sesia Zone, Western Alps, Italy) was studied by single-crystal X-ray diffraction with a diamond anvil cell under hydrostatic conditions up to ~11 GPa. A series of 12 structure refinements were performed at selected pressures within the P range investigated. The compressional behaviour of the same phengite sample was previously studied up to ~25 GPa by synchrotron X-ray powder diffraction, showing an irreversible transformation with a drastic decrease of the crystallinity at P > 15–17 GPa. The elastic behaviour between 0.0001 and 17 GPa was modelled by a third-order Birch–Murnaghan Equation of State (BM-EoS), yielding to K _T0 = 57.3(10) GPa and K′ = ?K _T0/?P = 6.97(24). The single-crystal structure refinements showed that the significant elastic anisotropy of the 2M ₁-phengite (with β(a):β(b):β(c) = 1:1.17:4.60) is mainly controlled by the anisotropic compression of the K-polyhedra. The evolution of the volume of the inter-layer K-polyhedron as a function of P shows a negative slope, Fitting the P–V(K-polyhedron) data with a truncated second-order BM-EoS we obtain a bulk modulus value of K _T0(K-polyhedron) = 26(1) GPa. Tetrahedra and octahedra are significantly stiffer than the K-polyhedron. Tetrahedra behave as quasi-rigid units within the P range investigated. In contrast, a monotonic decrease is observed for the octahedron volume, with K _T0 = 120(10) GPa derived by a BM-EoS. The anisotropic response to pressure of the K-polyhedron affects the P-induced deformation mechanism on the tetrahedral sheet, consisting in a cooperative rotation of the tetrahedra and producing a significant ditrigonalization of the six-membered rings. The volume of the K-polyhedron and the value of the ditrigonal rotation parameter (α) show a high negative correlation (about 93%), though a slight discontinuity is observed at P >8 GPa. α increases linearly with P up to 7–8 GPa (with ?α/?P ≈ 0.7°/GPa), whereas at higher Ps a “saturation plateau” is visible. A comparison between the main deformation mechanisms as a function of pressure observed in 2M ₁- and 3T-phengite is discussed.     

Expansivity and compressibility of wadeite-type K2Si4O9 determined by in situ high T/P experiments, and their implication

Wadeite-type K₂Si₄O₉ was synthesized with a cubic press at 5.4 GPa and 900 °C for 3 h. Its unit-cell parameters were measured by in situ high-T powder X-ray diffraction up to 600 °C at ambient P. The T–V data were fitted with a polynomial expression for the volumetric thermal expansion coefficient (α_T = a ₀ + a ₁ T), yielding a ₀ = 2.47(21) × 10^?5 K^?1 and a ₁ = 1.45(36) × 10^?8 K^?2. Compression experiments at ambient T were conducted up to 10.40 GPa with a diamond-anvil cell combined with synchrotron X-ray radiation. A second-order Birch–Murnaghan equation of state was used to fit the P–V data, yielding K _T = 97(3) GPa and V ₀ = 360.55(9) Å³. These newly determined thermal expansion data and compression data were used to thermodynamically calculate the P–T curves of the following reactions: 2 sanidine (KAlSi₃O₈) = wadeite (K₂Si₄O₉) + kyanite (Al₂SiO₅) + coesite (SiO₂) and wadeite (K₂Si₄O₉) + kyanite (Al₂SiO₅) + coesite/stishovite (SiO₂) = 2 hollandite (KAlSi₃O₈). The calculated phase boundaries are generally consistent with previous experimental determinations.     

Dielectric loss in ore-forming chromium spinel at temperatures from 20 to 800 °C

Physical, physicochemical, and mineralogical-petrographic methods have been applied to samples of ophiolite-hosted chromite ore from different deposits and occurrences in the Urals. Temperature dependences of dielectric loss obtained for nine chromite ore samples consisting of 95–98% Cr spinel show prominent peaks indicating a relaxation origin of the loss. The analyzed samples have the loss peaks at different temperatures depending mainly on H = (FeO/Fe₂O₃)^? : (FeO/Fe₂O₃)^??, where (FeO/Fe₂O₃)^? and (FeO/Fe₂O₃)^?? are, respectively, the ferrous/ferric oxide ratios in the samples before and after heating to 800 °C, and H is thus the heating-induced relative change in the FeO/Fe₂O₃ ratio. These peak temperatures vary from 550 °C (sample 1, high-Cr chromium spinel with more than 52% Cr₂O₃) to 750 °C (sample 2, aluminous and magnesian spinel with less than 30% Cr₂O₃), and H ranges correspondingly from 1.61 to 5.49. The temperature of the loss peaks is related with H as H = 34.30 ? 11.52N + 1.20N², with an error of σ = 0.19 (N = T · 10^?2, T is temperature in °C).     

Structural systematics of Ge substitution in primitive pyroxenes

Pyroxenes of general stoichiometry Mg(Ge _x Si_1?x )O₃ were encountered in attempts to synthesise Ge-substituted talcs at 0.2 GPa, 650–700 °C. Orthopyroxenes (Pbca) of compositions x = 0.21, 0.30, and 0.34 were identified, and also a P2₁/c clinopyroxene of composition x = 0.63, and C2/c clinopyroxenes of compositions x = 0.91 and 1. End-member clinoenstatite MgSiO₃-P2₁/c synthesised at 16 GPa, 1300 °C and transformed from C2/c was also included in the study. Crystal structure refinements using single-crystal XRD data showed that unit-cell parameters vary linearly with Si–Ge for the Pbca and P2₁/c pyroxenes, both of which have two symmetrically non-equivalent tetrahedral chains. Refinement of Si–Ge occupancies at tetrahedral sites showed that the two chains of all primitive pyroxenes have very different compositions, with X_Ge(TB) ? X_Ge(TA). This difference arises from the greater flexibility of the B-chain to rotate in response to tetrahedral expansion due to increasing Ge content. The TA-M2 shared polyhedral edge imposes significant constraints on the flexibility of the A-chain, which can accommodate much less Ge than the B-chain. Linear trends of cell parameters, site occupancies, and structural parameters for the primitive pyroxenes, when extrapolated to published data for MgGeO₃–Pbca, extend across the entire Si–Ge join.     

The composition,structure, and stability of guinier-preston zones in lunar and terrestrial orthopyroxene

Lunar and terrestrial orthopyroxenes (Mg,Fe,Ca)₂Si₂O₆ contain varying abundances of coherent, Ca-enriched Guinier-Preston (G.P.) zones. G.P. zones 5–6 unit cells thick have been found in one lunar sample whereas all other examples (lunar and terrestrial) are only one unit-cell-thick. Electron diffraction maxima from the larger lunar G.P. zones indicate that d ₁₀₀=18.52 Å whereas, d ₁₀₀=18.2 Å for the host. This increase in the a direction corresponds to an increase in calcium content in the G.P. zones over that of the host of ～25 mol% Ca₂Si₂O₆. Diffraction patterns of the hk0 net from an area containing G.P. zones show extra spots (h=2n+1) not observed in the host orthopyroxene (Pbca), that violate the a-glide of the host. The G.P. zones, therefore, have space group Pbc2₁ if it is assumed that the c-glide of pyroxene is retained and the space group of the G.P. zone is a subgroup of Pbca. The loss of the a-glide in the G.P. zones results in 4 distinct silica chains and 4 distinct cation sites M1A, M1B, M2A, M2B; by symmetry, equivalent M2A or M2B sites are clustered together in only one-half of the unit cell. As one-fourth of the divalent cations in the G.P. zones are calcium, ordering of Ca on M2A or M2B would produce a zone 9 Å thick extended parallel to (100) with the composition of Ca(Mg,Fe)Si₂O₆, but constrained by the host to the structure of orthopyroxene. This zone and the Ca-poor half-unit-cell then constitute an 18 Å thick G.P. zone. Heating experiments of varying duration indicate that the zones become unstable with respect to the host orthopyroxene at ～950°C for Wo_0.6 and ～1,050°C for Wo_2.5. The zones are interpreted in terms of the pyroxene subsolidus as a metastable phase having either a solvus relationship with orthopyroxene or originating as a distinct phase. The size, distribution, composition and structure of G.P. zones may be an important indicator of the low-temperature thermal history of orthopyroxene.