Tailings composition effects on shear strength behavior of co-mixed mine waste rock and tailings

The objective of this study was to evaluate the effect of mine tailings composition on shear behavior and shear strength of co-mixed mine waste rock and tailings (WR&T). Crushed gravel was used as a synthetic waste rock and mixed with four types of tailings: (1) fine-grained garnet, (2) coarse-grained garnet, (3) copper, and (4) soda ash. Co-mixed WR&T specimens were prepared to target mixture ratios of mass of waste rock to mass of tailings (R) such that tailings “just filled” interparticle void space of the waste rock (i.e., optimum mixture ratio, R _opt). Triaxial compression tests were conducted on waste rock, tailings, and mixed waste at effective confining stresses (\(\sigma_{\text{c}}^{{\prime }}\)) ranging from 5 to 40 kPa to represent stresses anticipated in final earthen covers for waste containment facilities. Waste rock and co-mixed WR&T specimens were 150 mm in diameter by 300 mm tall, whereas tailings specimens were 38 mm in diameter by 76 mm tall. Shear strength was quantified using effective stress friction angles (?′) from undrained tests: ?′ for waste rock was 37°, ?′ for tailings ranged from 34° to 41°, and ?′ for WR&T mixtures ranged from 38° to 40°. Thus, shear strength of co-mixed WR&T was comparable to waste rock regardless of tailings composition. Shear behavior of WR&T mixtures was a function of R and tailings composition. Tailings influenced shear behavior for R < R _opt and when tailings predominantly were silt. Shear behavior was influenced by waste rock for R ≥ R _opt and when tailings predominantly were sand or included clay particles.     

Heave Studies on Fly Ash-Stabilised Expansive Clay Liners

Clay liners or compacted earthen barriers are important barrier materials used for preventing contaminant transport through soils. A low hydraulic conductivity (k) is a significant parameter that governs the design and construction of clay liners. Compacted expansive clays, which are montmorillonite clays, also have a very low hydraulic conductivity (k). When expansive clays are blended with fly ash, an industrial waste, the hydraulic conductivity (k) further reduces as the ash-clay blends result in increased dry densities at increased fly ash contents. Hence, fly ash-stabilised expansive clay can also be proposed as a unique clay liner material. As expansive clays undergo heave when they come into contact with water, it is necessary to study the heave behaviour of fly ash-stabilised expansive clay liners. This paper presents heave studies on fly ash-stabilised expansive clay liners. Fly ash in different contents by dry weight of the expansive clay was added to the clay, and the ash-clay blend was compacted as a liner overlying a natural field soil layer. Compacted lateritic clay was used for simulating the natural field soil into which contaminants migrate. Calcium chloride (CaCl₂) solution of varying concentration (5, 10, 20, 50, 100 and 500 mM) was used as the permeating fluid in the heave studies. The rate of heave and the amount of heave of the fly ash-stabilised expansive clay liners were monitored. Deionised water (DIW) was also used as inundating fluid for comparative study. Heave (mm) decreased with increase in solute concentration for all fly ash contents. For a given solute concentration, heave decreased up to a fly ash content of 20 % and thereafter it increased when the fly ash content was increased to 30 %. Heave of the fly ash-stabilised expansive clay liners was correlated with their permeability, liquid limit (LL) and free swell index (FSI) pertaining to the respective fly ash content and CaCl₂ concentration.     

Studies on Hydraulic Conductivity of Fly Ash-Stabilised Expansive Clay Liners

Earthen barriers or clay liners are a major concern in geo-environmental engineering. They are designed to preclude or reduce leachate migration. Hence, a low hydraulic conductivity (k) is an important parameter in the design of clay liners. Materials such as bentonite and lateritic clays, which have a low hydraulic conductivity at high dry densities, are used in the construction of clay liners. Compacted expansive clays which are high in montmorillonite content also have a very low hydraulic conductivity. When expansive clays are blended with fly ash, an industrial waste, the hydraulic conductivity further reduces as the ash-clay blends result in increased dry densities at increased fly ash contents. Hence, fly ash-stabilised expansive clay can also be proposed as an innovative clay liner material. It is, therefore, required to study various physical and engineering properties of this new clay liner material. Liquid limit (LL) and free swell index (FSI) are important index properties to be studied in the case of this clay liner material. The hydraulic conductivity of this new clay liner material depends on the fly ash content in the blend. Further, parameters such as solute concentration and kinematic viscosity also influence hydraulic conductivity of clay liners. This paper presents experimental results obtained on hydraulic conductivity (k) of fly ash-stabilised expansive clay liner at varying fly ash content and solute concentration. The tests were performed with deionised water (DIW), CaCl₂, NaCl and KCl as permeating fluids. Fly ash content in the blend was varied as 0, 10, 20 and 30 % by weight of the expansive clay, and the solute concentration was varied as 5 mM (milli molar), 10, 20, 50, 100 and 500. It was found that hydraulic conductivity (k) decreased with increasing fly ash content, solute concentration and kinematic viscosity. Further, hydraulic conductivity (k) was correlated with LL and FSI of the clay liner material for different fly ash contents and solute concentrations. Useful correlations were obtained.     

Adsorptive removal of pharmaceuticals and personal care products from aqueous solutions by chemically treated fly ash

This study investigated the removal efficiency of pharmaceuticals from aqueous solutions supported on chemically treated fly ash. The coal fly ash was supplied by the electric power station in Krakow, Poland. There are plenty of studies showing the utilization of fly ash as a low-cost adsorbent for wastewater containing heavy metals or dyes. Adsorption and immobilization of pharmaceuticals and personal care products on fly ash is a relatively new method but it is a very promising one. In this study, the adsorptive removal of diclofenac, ketoprofen, carbamazepine, bezafibrate, bisphenol A, 17α-ethinyl estradiol and estriol by HCl- and NaOH-treated fly ash was assessed. Chemical treatment of fly ash changed structures of particles and enhanced specific surface areas. HCl-treated fly ash was characterized by the highest BET specific surface area 47.9 m² g^?1 and unburned carbon content 8.1%. Isotherms for all compounds except for 17α-ethinyl estradiol (EE2) and estriol (E3) were linear. Higher linear regression coefficients (R ²) obtained for isotherms of EE2 and E3 show that the Freundlich model better describes their sorption. Adsorption coefficients K _d varied between 109.5 (L kg^?1) for bisphenol A and 471.5 (L kg^?1) for bezafibrate. Freundlich constants (K _F) for EE2 and E3 were 62.3 and 119.9 (µg^1?1/n L^1/n kg^?1), respectively. Acid treatment of fly ash increased adsorption of diclofenac, ketoprofen, carbamazepine, bezafibrate and bisphenol A. Comparison of the octanol–water partitioning coefficients (log K _OW) with the partitioning coefficients normalized on unburned carbon content (log K _UC) revealed similarities but no strong correlation. The increasing of unburned carbon increased sorption of compounds to fly ash.     

Synthesis,TEM characterization and thermal behaviour of LiNiSi<Subscript>2</Subscript>O<Subscript>6</Subscript> pyroxene

A pyroxene with composition LiNiSi₂O₆ was synthesized at T = 1,473 K and P = 2.0 GPa; the cell parameters at T = 298 K are a = 9.4169(6) Å, b = 8.4465(7) Å, c = 5.2464(3) Å, β = 110.534(6)°, V = 390.78(3) Å³. TEM examination of the LiNiSi₂O₆ pyroxene showed the presence of h + k odd reflections indicative of a primitive lattice, and of antiphase domains obtained by dark field imaging of the h + k odd reflections. A HT in situ investigation was performed by examining TEM selected area diffraction patterns collected at high temperature and synchrotron radiation powder diffraction. In HTTEM the LiNiSi₂O₆ was examined together with LiCrSi₂O₆ pyroxene. In LiCrSi₂O₆ the h + k odd critical reflections disappear at about 340 K; they are sharp up to the transition temperature and do not change their shape until they disappear. In LiNiSi₂O₆ the h + k odd reflections are present up to sample deterioration at 650 K. A high temperature synchrotron radiation powder diffraction investigation was performed on LiNiSi₂O₆ between 298 and 773 K. The analysis of critical reflections and of changes in cell parameters shows that the space group is P-centred up to the highest temperature. The comparative analysis of the thermal and spontaneous strain contributions in P2₁/c and C2/c pyroxenes indicates that the high temperature strain in P-LiNiSi₂O₆ is very similar to that due to thermal strain only in C2/c spodumene and that a spontaneous strain contribution related to pre-transition features is not apparent in LiNiSi₂O₆. A different high-temperature behaviour in LiNiSi₂O₆ with respect to other pyroxenes is suggested, possibly in relation with the presence of Jahn–Teller distortion of the M1 polyhedron centred by low-spin Ni³⁺.     

Dewatering Behaviour of a Uranium Ore Slurry Containing Clays

The main objective of this paper was to investigate the dewatering behaviour of a clayey uranium ore slurry. The slurry (containing 28% clay size) exhibited moderate water adsorption (w _l  = 83% and w _p  = 30%). Primarily composed of muscovite (46%) and quartz (30%), the clay minerals included illite (8%), chlorite (5%) and kaolinite (2%) alongside a CEC of 41 (cmol(+)/kg) with Ca²⁺ and Mg²⁺ as the dominant cations. Likewise, the high EC (17,600 μS/cm) and ionic strength (1.15 mol/L) indicated a flocculated microstructure due to the presence of SO₄ ^2? (22,600 mg/L) and Mg²⁺ (1340 mg/L) in the slurry water. Settling included sedimentation and consolidation at low initial solids condition (25–35%) whereas only consolidation was observed at high initial solids contents (40–50%). The average k reduced from 1.2 × 10^?6 m/s (initial s = 25%) to 5.3 × 10^?8 m/s (initial s = 50%) along with a void ratio reduction from 7.4 to 2.6. Due to thixotropic strength, volume compressibility during consolidation showed apparent pre-consolidation at low effective stress (0.3–2 kPa) with a reduction in void ratio from 2.6 to 2.5. The e _s was found to be 2.46 at σ′ = 2 kPa and was followed by a steeper slope with the void ratio reducing to 2.1 at σ′ = 31 kPa. Likewise, the hydraulic conductivity during consolidation decreased from 2.6 × 10^?9 m/s (at e = 2.6) to 2.0 × 10^?10 m/s (at e = 2.1).     

Permeability of granular soil employing flexible wall permeameter

Understanding the changes in permeability of soil, when soil is subjected to high confining pressure and flow pressure, which may alter the textural and geomechanical characteristics of soil, is of great importance to many geo-engineering activities such as, construction of high-rise buildings near the coast or the water bodies, earthen dams, pavement subgrades, reservoir, and shallow repositories. It is now possible to evaluate the changes in permeability of soil samples under varying conditions of confining pressure and flow pressure using flexible wall permeameter (FWP). In the present study, investigation was carried out on a cylindrical sample of granular soil employing FWP under varied conditions of confining pressure (σ₃)—50–300 kPa, which can simulate the stress conditions equivalent to depth of about 20 m under the earth’s crust, and a flow pressure (f_p)—20–120 kPa, which is mainly present near the small earthen embankment dams, landfill liners, and slurry walls near the soft granular soil with high groundwater table. The obtained results indicate a linear relationship between hydraulic conductivity (k) with effective confining pressure (σ_eff.), k, decreasing linearly with an incremental change in σ_eff.. Further, k increases significantly with an increase in f_p corresponding to each σ_eff., and q increases significantly with increase in the f_p corresponding to each (σ₃). It was also observed that corresponding to the low f_p of 20 kPa, the reduction in k is nonlinear with σ_3. The percentage reduction in k is observed to be 9, 13, and 27% corresponding to σ₃ of 50–100, 100–200, and 200-300 kPa, respectively.     

Characterization of locally available soil as a liner material for solid waste landfills in Sri Lanka

This study aimed to develop a low-cost and effective clay liner material for solid waste landfills in Sri Lanka. A locally available clayey soil and its admixtures with 5 and 10% bentonite were examined for this purpose. Laboratory experiments to determine soil plasticity and swell index were carried out on the tested samples. Hydraulic conductivity (k) tests were carried out in the laboratory using water and an aqueous solution of CaCl₂ on unconsolidated samples prepared by either dry or slurry packing and pre-consolidated samples with five different consolidation pressures (p) from 10 to 200 kPa. Measured liquid limits for tested admixtures increased with increasing bentonite contents and correlated well with measured values of the swell index. The difference in permeant solutions had little effect on measured k values for both unconsolidated and pre-consolidated samples. The hydraulic conductivities were highly affected by changing p, i.e., the k values decreased on two orders of magnitude as p increased from 10 to 200 kPa. The Kozeny–Carman equation, a theoretical permeability model that expresses the k-porosity relationship, was applied to measured data including reported values. Results showed the Kozeny–Carman equation captured well the porosity-dependent k values for tested soils and their admixtures with bentonite under a wide range of void ratios, suggesting that the Kozeny–Carman equation is a useful tool to estimate the magnitude of k values for differently compacted soil and its bentonite admixtures.     

High-pressure displacive phase transition of a natural Mg-rich pigeonite

A high-pressure single-crystal X-ray diffraction study has been carried out on a P2₁/c natural Mg-rich pigeonite sample with composition ca. Wo₆En₇₆Fs₁₈ using a diamond anvil-cell. The unit-cell parameters were determined at 14 different pressures to 7.14 GPa. The sudden disappearance of the b-type reflections (h + k = odd) and a strong discontinuity (about 2.8%) in the unit-cell volume indicated a first-order P2₁/c–C2/c phase transition between 4.66 and 4.88 GPa. The P(V) data of the P2₁/c phase were fitted to 4.66 GPa by a third-order Birch–Murnaghan equation of state (BM3 EoS), whereas the limited number of experimental data collected within the C2/c phase between 4.88 and 7.14 GPa were fitted using the same equation of state but with K′ constrained to the value obtained for the P2₁/c fitting. The equation of state coefficients are V ₀ = 424.66(6) ų, K _T0 = 104(2) GPa and K′ = 8(1) for the P2₁/c phase, and V ₀ = 423.6(1) ų, K _T0 = 112.4(8) GPa, and K′ fixed to 8(1) for the C2/c phase. The axial moduli for a, b, and c for the P2₁/c phase were obtained using also a BM3-EoS, while for the C2/c phase only a linear calculation could be performed, and therefore the same approach was applied for comparison also to the P2₁/c phase. In general the C2/c phase exhibits axial compressibilities (β _c > β _a >> β _b) lower than those of the P2₁/c phase (β _b > β _c ≈ β _a; similar to those found in previous studies in clinopyroxenes and orthopyroxenes). The lower compressibility of the C2/c phase compared with that of the P2₁/c could be ascribed to the greater stiffness along the b direction. A previously published relationship between P _c and M2 average cation radius (i.r.) has been updated using all the literature data on P2₁/c clinopyroxene containing large cations at M2 site and our new data. The following weighted regression was obtained: P _c (GPa) = 26(4) ? 28(5) ×  i.r (Å), R ² = 0.97. This improved equation can be used to predict the critical pressure of natural P2₁/c clinopyroxene samples just knowing the composition at M2 site.     

Accuracy assessment of near-shore bathymetry information retrieved from Landsat-8 imagery

The improvement in the capabilities of Landsat-8 imagery to retrieve bathymetric information in shallow coastal waters was examined. Landsat-8 images have an additional band named coastal/aerosol, Band 1: 435–451 nm in comparison with former generation of Landsat imagery. The selected Landsat-8 operational land image (OLI) was of Chabahar Bay, located in the southern part of Iran (acquired on February 22, 2014 in calm weather and relatively low turbidity). Accurate and high resolution bathymetric data from the study area, produced by field surveys using a single beam echo-sounder, were selected for calibrating the models and validating the results. Three methods, including traditional linear and ratio transform techniques, as well as a novel proposed integrated method, were used to determine depth values. All possible combinations of the three bands [coastal/aerosol (CB), blue (B), and green (G)] have been considered (11 options) using the traditional linear and ratio transform techniques, together with five model options for the integrated method. The accuracy of each model was assessed by comparing the determined bathymetric information with field measured values. The standard error of the estimates, correlation coefficients (R ² ) for both calibration and validation points, and root mean square errors (RMSE) were calculated for all cases. When compared with the ratio transform method, the method employing linear transformation with a combination of CB, B, and G bands yielded more accurate results (standard error = 1.712 m, R ² _calibration = 0.594, R ² _validation = 0.551, and RMSE =1.80 m). Adding the CB band to the ratio transform methodology also dramatically increased the accuracy of the estimated depths, whereas this increment was not statistically significant when using the linear transform methodology. The integrated transform method in form of Depth = b ₀  + b ₁ X _CB  + b ₂ X _B  + b ₅ ln(R _CB )/ln(R _G ) + b ₆ ln(R _B )/ln(R _G ) yielded the highest accuracy (standard error = 1.634 m, R ² _calibration = 0.634, R ² _validation = 0.595, and RMSE = 1.71 m), where R _i (i = CB, B, or G) refers to atmospherically corrected reflectance values in the i ^th band [X _i  = ln(R _i -R _{deep water})].     

Elastic behavior of vanadinite,Pb<Subscript>10</Subscript>(VO<Subscript>4</Subscript>)<Subscript>6</Subscript>Cl<Subscript>2</Subscript>, a microporous non-zeolitic mineral

The high-pressure behavior of a vanadinite (Pb₁₀(VO₄)₆Cl₂, a = b = 10.3254(5), c = 7.3450(4) Å, space group P6₃/m), a natural microporous mineral, has been investigated using in-situ HP-synchrotron X-ray powder diffraction up to 7.67 GPa with a diamond anvil cell under hydrostatic conditions. No phase transition has been observed within the pressure range investigated. Axial and volume isothermal Equations of State (EoS) of vanadinite were determined. Fitting the P–V data with a third-order Birch-Murnaghan (BM) EoS, using the data weighted by the uncertainties in P and V, we obtained: V ₀ = 681(1) Å³, K ₀ = 41(5) GPa, and K′ = 12.5(2.5). The evolution of the lattice constants with P shows a strong anisotropic compression pattern. The axial bulk moduli were calculated with a third-order “linearized” BM-EoS. The EoS parameters are: a ₀ = 10.3302(2) Å, K ₀(a) = 35(2) GPa and K′(a) = 10(1) for the a-axis; c ₀ = 7.3520(3) Å, K ₀(c) = 98(4) GPa, and K′(c) = 9(2) for the c-axis (K ₀(a):K ₀(c) = 1:2.80). Axial and volume Eulerian-finite strain (fe) at different normalized stress (Fe) were calculated. The weighted linear regression through the data points yields the following intercept values: Fe _a (0) = 35(2) GPa for the a-axis, Fe _c (0) = 98(4) GPa for the c-axis and Fe _V (0) = 45(2) GPa for the unit-cell volume. The slope of the regression lines gives rise to K′ values of 10(1) for the a-axis, 9(2) for the c-axis and 11(1) for the unit cell-volume. A comparison between the HP-elastic response of vanadinite and the iso-structural apatite is carried out. The possible reasons of the elastic anisotropy are discussed.     

Rogue events in spatiotemporal numerical simulations of unidirectional waves in basins of different depth

The evolution of unidirectional nonlinear sea surface waves is calculated numerically by means of solution of the Euler equations. The wave dynamics corresponds to quasi-equilibrium states characterized by JONSWAP spectra. The spatiotemporal data are collected and processed providing information about the wave height probability and typical appearance of abnormally high waves (rogue waves). The waves are considered at different water depths ranging from deep to relatively shallow cases (k _p h > 0.8, where k _p is the peak wavenumber, and h is the local depth). The asymmetry between front and rear rogue wave slopes is identified; it becomes apparent for sufficiently high waves in rough sea states at all considered depths k _p h ≥ 1.2. The lifetimes of rogue events may reach up to 30–60 wave periods depending on the water depth. The maximum observed wave has a height of about three significant wave heights. A few randomly chosen in situ time series from the Baltic Sea are in agreement with the general picture of the numerical simulations.     

Compressibility of strontium orthophosphate Sr<Subscript>3</Subscript>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript> at high pressure

High pressure in situ synchrotron X-ray diffraction experiment of strontium orthophosphate Sr₃(PO₄)₂ has been carried out to 20.0 GPa at room temperature using multianvil apparatus. Fitting a third-order Birch–Murnaghan equation of state to the P–V data yields a volume of V ₀ = 498.0 ± 0.1 Å³, an isothermal bulk modulus of K _T  = 89.5 ± 1.7 GPa, and first pressure derivative of K _T ′ = 6.57 ± 0.34. If K _T ′ is fixed at 4, K _T is obtained as 104.4 ± 1.2 GPa. Analysis of axial compressible modulus shows that the a-axis (K _a  = 79.6 ± 3.2 GPa) is more compressible than the c-axis (K _c  = 116.4 ± 4.3 GPa). Based on the high pressure Raman spectroscopic results, the mode Grüneisen parameters are determined and the average mode Grüneisen parameter of PO₄ vibrations of Sr₃(PO₄)₂ is calculated to be 0.30(2).     

Electro-chemical mineralization of recalcitrant indole by platinum-coated titanium electrode: multi-response optimization,mechanistic and sludge disposal study

Indole is a highly recalcitrant aromatic heterocyclic organic compound consisting of a five-membered nitrogen-containing pyrrole ring fused to a six-membered benzene ring. This study presents the results of the electro-chemical mineralization of indole in an aqueous solution using platinum-coated titanium (Pt/Ti) electrode. A central composite design was used to investigate the effect of four parameters namely initial pH (pH_o), current density (j), conductivity (k) and treatment time (t) at 5 levels. Multiple responses namely chemical oxygen demand (COD) removal (Y ₁) and specific energy consumption (Y ₂) were simultaneously maximized and minimized, respectively, by optimizing the parameters affecting the mineralization of indole by using the desirability function approach. At the operating conditions of pH 8.6, j = 161 A/m², k = 6.7 mS/cm and t = 150 min, 83.8% COD removal with specific energy consumption of 36.3 kWh/kg of COD removed was observed. Ultra performance liquid chromatography, UV–visible spectroscopy, Fourier transform infrared spectroscopy and cyclic voltammetry of the indole solution were performed at the optimum condition of the treatment so as to report a plausible mechanism of indole degradation. Field emission scanning electron microscopy analysis of electrodes before and after treatment was performed for determining the changes on anode surface during the treatment. Thermal analysis of the solid residue (scum) obtained was also performed for exploring its disposal prospects. Present study shows that electro-chemical oxidation can be used for mineralization of nitrogenous heterocyclic compounds such as indole.     

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.     

Stability at high-pressure,elastic behaviour and pressure-induced structural evolution of CsAlSi<Subscript>5</Subscript>O<Subscript>12</Subscript>, a potential host for nuclear waste

The elastic and structural behaviour of the synthetic zeolite CsAlSi₅O₁₂ (a = 16.753(4), b = 13.797(3) and c = 5.0235(17) Å, space group Ama2, Z = 2) were investigated up to 8.5 GPa by in situ single-crystal X-ray diffraction with a diamond anvil cell under hydrostatic conditions. No phase-transition occurs within the P-range investigated. Fitting the volume data with a third-order Birch–Murnaghan equation-of-state gives: V ₀ = 1,155(4) ų, K _T0 = 20(1) GPa and K′ = 6.5(7). The “axial moduli” were calculated with a third-order “linearized” BM-EoS, substituting the cube of the individual lattice parameter (a ³, b ³, c ³) for the volume. The refined axial-EoS parameters are: a ₀ = 16.701(44) Å, K _T0a = 14(2) GPa (β_a = 0.024(3) GPa^?1), K′ _a = 6.2(8) for the a-axis; b ₀ = 13.778(20) Å, K _T0b = 21(3) GPa (β_b = 0.016(2) GPa^?1), K′ _b = 10(2) for the b-axis; c ₀ = 5.018(7) Å, K _T0c = 33(3) GPa (β_c = 0.010(1) GPa^?1), K′ _c = 3.2(8) for the c-axis (K _T0a:K _T0b:K _T0c = 1:1.50:2.36). The HP-crystal structure evolution was studied on the basis of several structural refinements at different pressures: 0.0001 GPa (with crystal in DAC without any pressure medium), 1.58(3), 1.75(4), 1.94(6), 3.25(4), 4.69(5), 7.36(6), 8.45(5) and 0.0001 GPa (after decompression). The main deformation mechanisms at high-pressure are basically driven by tetrahedral tilting, the tetrahedra behaving as rigid-units. A change in the compressional mechanisms was observed at P ≤ 2 GPa. The P-induced structural rearrangement up to 8.5 GPa is completely reversible. The high thermo-elastic stability of CsAlSi₅O_12, the immobility of Cs at HT/HP-conditions, the preservation of crystallinity at least up to 8.5 GPa and 1,000°C in elastic regime and the extremely low leaching rate of Cs from CsAlSi₅O₁₂ allow to consider this open-framework silicate as functional material potentially usable for fixation and deposition of Cs radioisotopes.     

The stress regime in a Rotliegend reservoir of the Northeast German Basin

In-situ stresses have significant impact, either positive or negative, on the short and long term behaviour of fractured reservoirs. The knowledge of the stress conditions are therefore important for planning and utilization of man-made geothermal reservoirs. The geothermal field Groß Schönebeck (40 km north of Berlin/Germany) belongs to the key sites in the northeastern German Basin. We present a stress state determination for this Lower Permian (Rotliegend) reservoir by an integrated approach of 3D structural modelling, 3D fault mapping, stress ratio definition based on frictional constraints, and slip-tendency analysis. The results indicate stress ratios of the minimum horizontal stress S _hmin being equal or increasing 0.55 times the amount of the vertical stress S _V (S _hmin ≥ 0.55S _V ) and of the maximum horizontal stress S _Hmax ≤ 0.78–1.00S _V in stress regimes from normal to strike slip faulting. Thus, acting stresses in the 4,100-m deep reservoir are S _V  = 100 MPa, S _hmin = 55 MPa and S _Hmax = 78?100 MPa. Values from hydraulic fracturing support these results. Various fault sets of the reservoir are characterized in terms of their potential to conduct geothermal fluids based on their slip and dilatation tendency. This combined approach can be adopted to any other geothermal site investigation.     

On the crystal chemistry and elastic behavior of a phlogopite 3<Emphasis Type="Italic">T</Emphasis>

The crystal chemistry and the elastic behavior under isothermal conditions up to 9 GPa of a natural, and extremely rare, 3T-phlogopite from Traversella (Valchiusella, Turin, Western Alps) [(K_0.99Na_0.05Ba_0.01)(Mg_2.60Al_0.20Fe _0.21 ²⁺ )[Si_2.71Al_1.29O₁₀](OH)₂, space group P3₁12, with a = 5.3167(4), c = 30.440(2) Å, and V = 745.16(9) ų] have been investigated by electron microprobe analysis in wavelength dispersion mode, single-crystal X-ray diffraction at 100 K, and in situ high-pressure synchrotron radiation powder diffraction (at room temperature) with a diamond anvil cell. The single-crystal refinement confirms the general structure features expected for trioctahedral micas, with the inter-layer site partially occupied by potassium and sodium, iron almost homogeneously distributed over the three independent octahedral sites, and the average bond distances of the two unique tetrahedra suggesting a disordered Si/Al-distribution (i.e., 〈T1-O〉 ~ 1.658 and 〈T2-O〉 ~ 1.656 Å). The location of the H-site confirms the orientation of the O–H vector nearly perpendicular to (0001). The refinement converged with R ₁(F) = 0.0382, 846 unique reflections with F _O > 4σ(F _O) and 61 refined parameters, and not significant residuals in the final difference-Fourier map of the electron density (+0.77/?0.37 e ^?/ų). The high-pressure experiments showed no phase transition within the pressure range investigated. The P–V data were fitted with a Murnaghan (M-EoS) and a third-order Birch-Murnaghan equation of state (BM-EoS), yielding: (1) M-EoS, V ₀ = 747.0(3) ų, K _T0 = 44.5(24) GPa, and K′ = 8.0(9); (2) BM-EoS, V ₀ = 747.0(3) ų, K _T0 = 42.8(29) GPa, and K′ = 9.9(17). A comparison between the elastic behavior in response to pressure observed in 1M- and 3T-phlogopite is made.     

High-pressure phase transitions of CaRhO<Subscript>3</Subscript> perovskite

High-pressure phase transitions of CaRhO₃ perovskite were examined at pressures of 6–27 GPa and temperatures of 1,000–1,930°C, using a multi-anvil apparatus. The results indicate that CaRhO₃ perovskite successively transforms to two new high-pressure phases with increasing pressure. Rietveld analysis of powder X-ray diffraction data indicated that, in the two new phases, the phase stable at higher pressure possesses the CaIrO₃-type post-perovskite structure (space group Cmcm) with lattice parameters: a = 3.1013(1) Å, b = 9.8555(2) Å, c = 7.2643(1) Å, V _m  = 33.43(1) cm³/mol. The Rietveld analysis also indicated that CaRhO₃ perovskite has the GdFeO₃-type structure (space group Pnma) with lattice parameters: a = 5.5631(1) Å, b = 7.6308(1) Å, c = 5.3267(1) Å, V _m  = 34.04(1) cm³/mol. The third phase stable in the intermediate P, T conditions between perovskite and post-perovskite has monoclinic symmetry with the cell parameters: a = 12.490(3) Å, b = 3.1233(3) Å, c = 8.8630(7) Å, β = 103.96(1)°, V _m  = 33.66(1) cm³/mol (Z = 6). Molar volume changes from perovskite to the intermediate phase and from the intermediate phase to post-perovskite are –1.1 and –0.7%, respectively. The equilibrium phase relations determined indicate that the boundary slopes are large positive values: 29 ± 2 MPa/K for the perovskite—intermediate phase transition and 62 ± 6 MPa/K for the intermediate phase—post-perovskite transition. The structural features of the CaRhO₃ intermediate phase suggest that the phase has edge-sharing RhO₆ octahedra and may have an intermediate structure between perovskite and post-perovskite.