Incommensurate–normal phase transition in natural melilite: an in situ high-temperature X-ray single-crystal study

The structure of a natural melilite with chemical composition (Ca_1.87Sr_0.02Na_0.10K_0.02)_2.01(Mg_0.96Al_0.07)_1.03(Si_1.98Al_0.02)_2.00O₇ has been investigated by X-ray single-crystal diffraction methods within the temperature range 298–773 K. The values of the coefficient of the modulation wave vector were determined at 298 K, 323 K, 348 K, and 358 K. These values show a continuous linear decrease from 0.2833(6) at 298 K to 0.2763(9) at 358 K. The incommensurate phase undergoes a phase transition to the normal phase at 359 K. The refinements of the structure, carried out at 298 K, 348 K, 359 K, 373 K, 413 K, 463 K, 513 K, 573 K, 673 K, and 773 K, showed that the normal phase (high-temperature phase) does not significantly differ from the basic structure (the average structure of the incommensurate structure). This study confirms that in natural melilites with chemical composition close to that of åkermanite the wavelength of the incommensurate modulation increases when the temperature rises. The different behaviour of the q-vector as a function of temperature in natural and synthetic åkermanite is discussed.     

Local structural relaxation around Co2+ along the hardystonite–Co-?kermanite melilite solid solution

Six pure compounds belonging to the hardystonite (Ca₂ZnSi₂O₇)–Co-?kermanite (Ca₂CoSi₂O₇) solid solution were investigated by the combined application of X-ray powder diffraction and electronic absorption spectroscopy. Structural refinements of the XRPD data revealed a negative excess volume of mixing due to the single isovalent substitution of Co for Zn in the tetrahedral site. In agreement with the diffraction data, deconvolution of the optical spectra showed a progressive decreasing of the crystal field strength parameter 10Dq moving toward the Co-?kermanite end-member, meaning that the local cobalt–oxygen bond distance, $ \langle {\text{Co}}{-}{\text{O}}\rangle^{\text{local}} $ , increased along the join with the amount of cobalt. The calculated structural relaxation coefficient around the fourfold coordinated Co²⁺ in the Ca₂(Zn_1?x Co _x )Si₂O₇ join was ε?=?0.69, very far from the one predicted by the Vegard’s law (ε?=?0) and at variance with ε?=?0.47 previously found for tetrahedrally coordinated Co²⁺ in gahnite–Co-aluminate spinel solid solution. This difference is consistent with the largest constraints existing on the spinel structure, based on cubic closest packing, compared to the more flexible layered melilite structure.     

Single-crystal X-ray diffraction study of synthetic sodium–hydronium jarosite

Na–H₃O jarosite was synthesized hydrothermally at 413 K for 8 days and investigated using single-crystal X-ray diffraction (XRD) and electron microprobe analysis (EMPA). The chemical composition of the studied crystal is [Na_0.57(3) (H₃O)_0.36 (H₂O)_0.07]^A Fe_2.93(3) (SO₄)₂ (OH)_5.70 (H₂O)_0.30, and Fe deficiency was confirmed by both EMPA and XRD analysis. The single-crystal XRD data were collected at 298 and 102 K, and crystal structures were refined in space group \( R\overline{3}m\). The room-temperature data match structural trends of the jarosite group, which vary linearly with the c axis. The low-temperature structure at 102 K shows an anisotropic decrease in the unit cell parameters, with c and a decreasing by 0.45 and 0.03 %, respectively. Structural changes are mainly confined to the A site environment. Only minor changes occur in FeO₆ and SO₄ polyhedra. The structure responds upon cooling by increasing bond length distortion and by decreasing quadratic elongation of the large AO₁₂ polyhedra. The structural parameters at low temperature follow very similar patterns to structural changes that correspond to compositional variation in the jarosite group, which is characterised by the flexibility of AO₁₂ polyhedra and rigidity of Fe(OH)₄O₂–SO₄ layers. The most flexible areas in the jarosite structure are localized at AO₁₂ edges that are not shared with neighbouring FeO₆ octahedra. Importantly, for the application of XRD in planetary settings, the temperature-related changes in jarosite can mimic compositional change.     

High-pressure X-ray diffraction study of ε-FeOOH

An in situ synchrotron X-ray diffraction study was carried out on ε-FeOOH at room temperature up to a pressure of 8.6 GPa using the energy-dispersive method. The linear compressibility was determined to be β _a  = 1.69(3) × 10⁻³ GPa⁻¹, β _b  = 2.86(6) × 10⁻³ GPa⁻¹, and β _c  = 1.73(5) × 10⁻³ GPa⁻¹. The b-axis of the unit cell is more compressible than the a and c axes. The pressure–volume data were fitted to a third-order Birch–Murnaghan equation of state. The best fit was found using a room temperature isothermal bulk modulus of K ₀ = 126(3) GPa and its pressure derivative K′ = 10(1).     

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.     

Order–disorder–reorder process in thermally treated dolomite samples: a combined powder and single-crystal X-ray diffraction study

A combined powder and single-crystal X-ray diffraction analysis of dolomite [CaMg(CO₃)₂] heated to 1,200°C at 3 GPa was made to study the order–disorder–reorder process. The order/disorder transition is inferred to start below 1,100°C, and complete disorder is attained at approximately 1,200°C. Twinned crystals characterized by high internal order were found in samples annealed over 1,100°C, and their fraction was found to increase with temperature. Evidences of twinning domains combined with probable remaining disordered portions of the structure imply that reordering processes occur during the quench. Twin domains are hereby proposed as a witness to thermally induced intra-layer-type cation disordering.     

Lattice strain across Na–K interdiffusion fronts in alkali feldspar: an electron back-scatter diffraction study

Cation exchange experiments between gem quality sanidine \((X_\mathrm{Or} = 0.85)\) and KCl melt produced chemical alteration of alkali feldspar starting at the grain surface and propagating inwards by highly anisotropic Na–K interdiffusion on the alkali sublattice. Diffusion fronts developing in b-direction are very sharp, while diffusion fronts within the a–c-plane are comparatively broad. Due to the composition dependence of the lattice parameters of alkali feldspar, the diffusion induced compositional heterogeneity induces coherency stress and elastic strain. Electron back-scatter diffraction combined with the cross-correlation technique was employed to determine the lattice strain distribution across the Na–K interdiffusion fronts in partially exchanged single crystals of alkali feldspar. The strain changes gradually across the broad fronts within the a–c-plane, with a successive extension primarily in a-direction conferring to the composition strain in unstressed alkali feldspar. In contrast, lattice strain characterised by pronounced extension in b-direction is localised at the sharp diffusion fronts parallel to b, followed by a slight expansion in a-direction in the orthoclase-rich rim. This strain pattern does not confer with the composition induced lattice strain in a stress-free alkali feldspar. It may rather be explained by the mechanical coupling of the exchanged surface layer and the mechanically strong substratum. The lattice distortion localised at the sharp diffusion front may have an influence on the diffusion process and appears to produce a self-sharpening feedback, leading to a local reduction of component mobilities.     

In situ Raman observation of the crystallization in NaNO3–Na2SO4–H2O solution droplets

Several double salts have been detected in building materials and most of these salts are incongruently soluble compounds. In contrast to single salts, however, no systematic investigations of the crystallization behavior and deleterious effects of incongruently soluble double salts exist. To assess the damage potential of these salts, a systematic investigation of their highly complex behavior is desirable. This paper deals with the crystallization behavior of various solids in the ternary mixed NaNO₃–Na₂SO₄ system including the formation of the double salt darapskite, Na₃NO₃SO₄·H₂O. The crystallization sequence during droplet evaporation experiments at room conditions was determined using Raman and polarization microscopy. The basic idea of this research is to use deviations of the crystallization sequence of a salt or a mixed salt solution from the equilibrium pathway as an indicator to detect the degree of supersaturation. The observed crystallization pathway includes the formation of the metastable phases Na₂SO₄(III), Na₂SO₄(V) and darapskite. The experimental observations are discussed on the basis of the NaNO₃–Na₂SO₄–H₂O phase diagram and the results provide evidence for crystal growth from highly supersaturated solutions in both systems. If the crystals growing under these conditions are confined, these supersaturations result in substantial crystallization pressures.     

Local structural heterogeneity,mixing behaviour and saturation effects in the grossular–spessartine solid solution

Local structural heterogeneities in crystals of the binary grossular–spessartine solid solution have been analyzed using powder IR absorption spectroscopy. Wavenumber shifts of the highest energy Si–O stretching mode in spectra collected at room temperature are consistent with variations in Si–O bond length from structural data. They show a smaller positive deviation from linearity across the join than is seen for the grossular–pyrope and grossular–almandine binaries. The effective line widths, corr, of three selected wavenumber regions all deviate positively from linear behaviour. An empirical calibration of this excess spectroscopic property, obtained by comparison with calorimetric enthalpy of mixing data, gives an estimate for the symmetric Margules parameter of W^H_spec = 14.4(7) kJ mol^–1 in H^mix = W^H_specX_GrX_Sp. W^H_spec values derived on the same basis for four aluminosilicate garnet solid solutions analyzed by IR spectroscopy vary with V², where V represents the difference in molar volume between the end members of each binary system. Measurements of lattice parameters and IR spectra were made over a range of temperatures for seven samples with different compositions. Positive excess molar volumes of mixing at low temperature (30 K) may be larger than the excess molar volumes at room temperature. The saturation temperatures of the molar volumes show no correlation with composition, however, in contrast with what had been expected on the basis of data for the grossular–pyrope binary. Saturation temperatures for spectroscopic parameters and lattice parameters of samples with compositions Gr15Sp85 and Gr60Sp40 seem to be outliers in all experiments. It is concluded that the data hint at systematic changes in saturation temperatures across the solid solution, with implications for both the excess entropy of mixing and the excess volume of mixing, but more precise data or further sample characterization are needed to prove that this composition dependence is real in garnet solid solutions.     

Equation of state of adamite up to 11 GPa: a synchrotron X-ray diffraction study

The compression behavior of natural adamite [Zn₂AsO₄OH] has been investigated up to 11.07 GPa at room temperature utilizing in situ angle-dispersive X-ray diffraction and a diamond anvil cell. No phase transition has been observed within the pressure range investigated. A third-order Birch–Murnaghan equation of state fitted to all of the data points yielded V ₀ = 430.1(4) Å³, K ₀ = 80(3) GPa, K′ ₀ = 1.9(5). The K ₀ was obtained as 69(1) GPa when K′ ₀ was fixed at 4. Analysis of axial compressible moduli shows the intense compression anisotropy of adamite: K _a0 = 37(3) GPa, K _b0 = 153(6) GPa, K _c0 = 168(8) GPa; hence, a axis is the most compressible and the compressibility of b and c axis is comparable. Furthermore, the comparisons among the compressional properties of adamite, libethenite (Cu₂PO₄OH, also belongs to olivenite group), and andalusite (Al₂SiO₄O has the similar structure with adamite) at high pressure were made.     

Interaction of Fe and Fe<Subscript>3</Subscript>C with hydrogen and nitrogen at 6–20 GPa: a study by in situ X-ray diffraction

A method of in situ X-ray diffraction at Spring-8 (Japan) was used to analyze simultaneously the hydrogen incorporation into Fe and Fe₃C, as well as to measure the relative stability of carbides, nitrides, sulfides, and hydrides of iron at pressures of 6–20 GPa and temperatures up to 1600 K. The following stability sequence of individual iron compounds was established in the studied pressure and temperature interval: FeS > FeN > FeC > FeH > Fe. A change in the unit-cell volume as compared to the known equations of state was used to estimate the hydrogen contents in carbide Fe₃C and hydride FeH_x. Data on hydride correspond to stoichiometry with x ≈ 1. Unlike iron sulfides and silicides, the solubility of hydrogen in Fe₃C seemed to be negligibly low—within measurement error. Extrapolating obtained data to pressures of the Earth’s core indicates that carbon and hydrogen are mutually incpompatible in the iron–nickel core, while nitrogen easily substitutes carbon and may be an important component of the inner core in the light of the recent models assuming the predominance of iron carbide in its composition.     

X-ray photoelectron study of oxygen bonding in crystalline C–S–H phases

We recorded the photoelectron spectra of various crystalline calcium silicate hydrates (C–S–Hs) and have examined their O 1 s photoelectron spectra. The spectra are asymmetric, with contributions assigned primarily to bridging and non-bridging oxygen species. There is an increased contribution due to the presence of non-bonding oxygen atoms with increasing calcium:silicon ratio. Additionally, there are slight changes in theO 1s-binding energies with changes in calcium:silicon ratio. These changes are explained in terms of bonding and silicate structure.     

Modeling reactive transport in non-ideal aqueous–solid solution system

The numerical simulation of reactive mass transport processes in complex geochemical environments is an important tool for the performance assessment of future waste repositories. A new combination of the multi-component mass transport code GeoSys/RockFlow and the Gibbs Energy Minimization (GEM) equilibrium solver GEM-Selektor is used to calculate the accurate equilibrium of multiple non-ideal solid solutions which are important for the immobilization of radionuclides such as Ra. The coupled code is verified by a widely used benchmark of dissolution–precipitation in a calcite–dolomite system. A more complex application shown in this paper is the transport of Ra in the near-field of a nuclear waste repository. Depending on the initial inventories of Sr, Ba and sulfate, non-ideal sulfate and carbonate solid solutions can fix mobile Ra cations. Due to the complex geochemical interactions, the reactive transport simulations can describe the migration of Ra in a much more realistic way than using the traditional linear K_D approach only.     

High-pressure single-crystal X-ray diffraction and synchrotron Mössbauer study of monoclinic ferrosilite

The phase and spin transitions in single-crystal monoclinic ferrosilite, FeSiO₃, were investigated using X-ray diffraction and Mössbauer spectroscopy up to lower-mantle pressures and room temperature in a helium pressure medium. Using single-crystal X-ray diffraction, we measured the equation of state of ferrosilite up to about 43 GPa. We observed a P2₁/c-to-C2/c phase transition between 1.5 and 1.7 GPa and a phase transition from C2/c to a distinct P2₁/c structure between 30 and 34 GPa. With time-domain Mössbauer spectroscopy, we determined the hyperfine parameters of ferrous iron up to 95 GPa. The phase transitions were correlated with discontinuities in Mössbauer spectral features. We observed the onset of high-spin-to-low-spin transitions in the M1 and M2 sites at ～37 GPa and ～74 GPa, respectively. Understanding the electronic structure of iron in a well-characterized single crystal of ferrosilite may help interpret the behavior of iron in complex dense silicate phases.     

Formation of a solid solution in the MgSiO3–MnSiO3 perovskite system

Experiments using laser-heated diamond anvil cells combined with synchrotron X-ray diffraction and SEM–EDS chemical analyses have confirmed the existence of a complete solid solution in the MgSiO₃–MnSiO₃ perovskite system at high pressure and high temperature. The (Mg, Mn)SiO₃ perovskite produced is orthorhombic, and a linear relationship between the unit cell parameters of this perovskite and the proportion of MnSiO₃ components incorporated seems to obey Vegard’s rule at about 50 GPa. The orthorhombic distortion, judged from the axial ratios of a/b and \( \sqrt{2}\,a/c, \) monotonically decreases from MgSiO₃ to MnSiO₃ perovskite at about 50 GPa. The orthorhombic distortion in (Mg_0.5, Mn_0.5)SiO₃ perovskite is almost unchanged with increasing pressure from 30 to 50 GPa. On the other hand, that distortion in (Mg_0.9, Mn_0.1)SiO₃ perovskite increases with pressure. (Mg, Mn)SiO₃ perovskite incorporating less than 10 mol% of MnSiO₃ component is quenchable. A value of the bulk modulus of 256(2) GPa with a fixed first pressure derivative of four is obtained for (Mg_0.9, Mn_0.1)SiO₃. MnSiO₃ is the first chemical component confirmed to form a complete solid solution with MgSiO₃ perovskite at the P–T conditions present in the lower mantle.     

Thermal expansion of kyanite at ambient pressure: An X-ray powder diffraction study up to 1000 ℃

The thermal expansion coefficients of kyanite at ambient pressure have been investigated by an X-ray powder diffraction technique with temperatures up to 1000 ℃. No phase transition was observed in the experimental temperature range. Data for the unit-cell parameters and temperatures were fitted empirically resulting in the following thermal expansion coefficients: aa = 5.8(3) × 10-5, ab = 5.8 (1) × 10-5, ac% = 5.2(1) × 10-5, and av = 7.4(1) × 10-3 ℃-1, in good agreement with a recent neutron powder diffraction study. On the other hand, the variation of the unit-cell angles a, β and γ of kyanite with increase in temperature is very complicated, and the agreement among all studies is poor. The thermal expansion data at ambient pressure reported here and the compression data at ambient temperature from the literature suggest that, for the kyanite lattice, the most and least thermally expandable directions correspond to the most and least compressible directions, respectively.     

In situ LA-ICP-MS U–Pb titanite dating of Na–Ca metasomatism in orogenic belts: the North Pyrenean example

In the Pyrenees, in association with the rotation of the Iberian plate around Europe during the Mid-Cretaceous, a Na–Ca metasomatism is recognized as a complementary record of the hydrothermal activity that led to Na-metasomatism (albitization) and talc–chlorite mineralization. It affected metasedimentary rocks as well as Hercynian granites. In situ laser ablation ICP-MS U–Pb analyses of titanite grains formed in albitites during metasomatism date the Na–Ca metasomatism between 110 and 92 Ma. The temperature of the Na–Ca metasomatism is estimated to be approximately 550 °C. Both the time constraints and temperature estimates suggest that the Na–Ca metasomatism is related to the low-P high-T North Pyrenean metamorphism.     

Aqueous–solid solution thermodynamic model of U(VI) uptake in C–S–H phases

Reliable thermodynamic models assessing the interaction of radionuclides with cementitious materials are important in connection with long-term predictions of the safe disposal of radioactive waste in cement-based repositories. In this study, a geochemical model of U(VI) interaction with calcium silicate hydrates (C–S–H phases), the main component of hardened cement paste (HCP), has been developed. Uranium(VI) sorption isotherms on C–S–H phases of different Ca:Si ratios (C:S) and structural data from spectroscopic studies provided the indispensable set of experimental data required for the model development. This information suggested that U(VI) is neither adsorbed nor incorporated in the Ca–O octahedral layers of the C–S–H structure, but rather is located in the interlayer, similar to Ca²⁺ and other cations. With a view to the high recrystallisation rates and the cryptocrystalline ‘gel-like’ structure of the C–S–H phases, these observations indicated a U(VI) uptake driven by the formation of a solid solution.