Adsorption of methylene blue and crystal violet on low-cost adsorbent: waste fruits of <Emphasis Type="Italic">Rapanea ferruginea</Emphasis> (ethanol-treated and H<Subscript>2</Subscript>SO<Subscript>4</Subscript>-treated)

This study assesses the ability of two low-cost adsorbents made from waste of Rapanea ferruginea treated with ethanol (WRf) and its H₂SO₄-treated analog (WRf/H₂SO₄) for the removal of two cationic dyes methylene blue (MB) and crystal violet (CV) from aqueous solutions. The adsorbent was characterized by scanning electron microscopy, Fourier transform infrared spectrometry, thermogravimetric analysis, point of zero charge (pH_pzc), specific surface, and functional groups. The adsorption of dye onto the adsorbents was studied as a function of pH solution (2–12), contact time (up to 120 min) and initial concentration (20–120 mg/L), and temperature (25, 35, and 55 °C). The influence of these parameters on adsorption capacity was studied using the batch process. The response surface methodology (RSM) was used in the experimental design, modeling of the process, and optimizing of the variables and was optimized by the response involving Box–Behnken factorial design (15 runs). The results show that the data correlated well with the Sips isotherm. The maximum adsorption capacities of MB and CV onto WRf were found to be 69 and 106 mg/g, and onto WRf/H₂SO₄, the adsorption capacities were 33 and 125 mg/g, respectively. The kinetic data revealed that adsorption of cationic dyes onto the adsorbents closely follows the pseudo-second-order kinetic model. Regression analysis showed good fit of the experimental data to the second-order polynomial model, with coefficient of determination (R²) values for MB (R²?=?0.9685) and MB (R²?=?0.9832) for WRf and CV (R²?=?0.9685) and CV (R²?=?0.9832) for WRf/H₂SO₄ indicated that regression analysis is able to give a good prediction of response for the adsorption process in the range studied. The results revealed that waste from R. ferruginea is potentially an efficient and low-cost adsorbent for adsorption of MB and CV.     

Chromium solubility in anhydrous Phase B

The crystal structure and chemical composition of a crystal of (Mg_14?x Cr _x )(Si_5?x Cr _x )O₂₄ (x ≈ 0.30) anhydrous Phase B (Anh-B) synthesized in the model system MgCr₂O₄–Mg₂SiO₄ at 12 GPa and 1600 °C have been investigated. The compound was found to be orthorhombic, space group Pmcb, with lattice parameters a = 5.900(1), b = 14.218(2), c = 10.029(2) Å, V = 841.3(2) Å³ and Z = 2. The structure was refined to R ₁ = 0.065 using 1492 independent reflections. Chromium was found to substitute for both Mg at the M3 site (with a mean bond distance of 2.145 Å) and Si at the octahedral Si1 site (mean bond distance: 1.856 Å), according to the reaction Mg²⁺ + Si⁴⁺ = 2Cr³⁺. Such substitutions cause a reduction in the volume of the M3 site and an increase in the volume of the Si-dominant octahedron with respect to the values typically observed for pure Anh-B and Fe²⁺-bearing Anh-B. Taking into account that Cr³⁺ is not expected to be Jahn–Teller active, it appears that both the Cr³⁺–for–Mg and Cr³⁺–for–Si substitutions in the Anh-B structure decrease the distortion of the octahedra. Electron microprobe analysis gave the Mg_13.66(8)Si_4.70(6)Cr_0.62(4)O₂₄ stoichiometry for the studied phase. The successful synthesis of this phase provides new information for the possible mineral assemblages occurring in the Earth’s deep upper mantle and shed new light on the so-called X discontinuity that has been observed at 275–345 km depth in several subcontinental and subduction zone environments.     

In situ formation of AgNPs on <Emphasis Type="Italic">S. cerevisiae</Emphasis> surface as bionanocomposites for bacteria killing and heavy metal removal

Novel bionanocomposites, S. cerevisiae–AgNPs, were synthesized by in situ formation of AgNPs on S. cerevisiae surface using fulvic acids as reductants under simulated sunlight. S. cerevisiae–AgNPs were characterized using UV–Vis spectroscopy, scanning electron microscope, transmission electron microscope and Fourier transform infrared spectroscopy. These analyses showed that AgNPs were distributed on the surface of S. cerevisiae. The application of S. cerevisiae–AgNPs in bacteria killing and heavy metal removal was studied. S. cerevisiae–AgNPs effectively inhibited the growth of E. coli with increasing concentrations of S. cerevisiae–AgNPs. E. coli was killed completely at high concentration S. cerevisiae–AgNPs (e.g., 100 or 200 µg mL^?1). S. cerevisiae–AgNPs as excellent heavy metal absorbents also have been studied. Using Cd²⁺ as model heavy metal, batch experiments confirmed that the adsorption behavior fitted the Langmuir adsorption isotherms and the Cd²⁺ adsorption capacity of S. cerevisiae–AgNPs was 15.01 mg g^?1. According to adsorption data, the kinetics of Cd²⁺ uptake by S. cerevisiae–AgNPs followed pseudo second-order kinetic model. Moreover, S. cerevisiae–AgNPs possessed ability of different heavy metals’ removal (e.g., Cr⁵⁺, As⁵⁺, Pb²⁺, Cu²⁺, Mn²⁺, Zn²⁺, Hg²⁺, Ni²⁺). The simulated contaminated water containing E. coli, Cd²⁺ and Pb²⁺ was treated using S. cerevisiae–AgNPs. The results indicated that the bionanocomposites can be used to develop antibacterial agents and bioremediation agents for water treatment.     

Efficient removal of Evans blue dye by Zn–Al–NO<Subscript>3</Subscript> layered double hydroxide

Evans blue (EB) dye has been successfully removed from aqueous solution through chemisorption process with synthetic layered double hydroxides (LDH) [Zn_1?x Al _x (OH)₂NO₃·nH₂O, x = 0.2–0.33]. Detailed evaluation of dye adsorption characteristics in aqueous medium has been studied for different layer charged hydroxides. The objective of the study was efficient removal of a dye by LDH and understanding the structure–property relationship of the LDH on its adsorption behaviour. Highest Langmuir monolayer adsorption capacity (Qt) of 113.64 mg g^?1 was observed for highest layer charge x = 0.33, and it is higher than previously reported values for the LDH-EB dye system. Under optimized condition, 99% of EB dye is removed from aqueous solution within 60 min at 313 K. The monotonous increase in Qt value with increasing layer charge is correlated with layer charge density (LCD) and lower particle size of the synthetic LDH. The variation in Qt among different layer charged materials is marginal (3.46–4.17%) with respect to the respective anion exchange capacity (AEC) of LDH NO₃. The limited contribution of AEC surmises the occurrence of surface-only adsorption and absence of intercalation as validated by the XRD analysis. The spontaneity of the EB dye removal increases with increasing temperature and LCD. The chemisorption nature of the adsorption reaction is well supported by the thermodynamics values.     

Formation of one-dimensional composites of poly(<Emphasis Type="Italic">m</Emphasis>-phenylenediamine)s based on <Emphasis Type="Italic">Streptomyces</Emphasis> for adsorption of hexavalent chromium

Here, a novel one-dimensional composite of poly(m-phenylenediamine)s coating on filamentous Streptomyces was successfully constructed via a controllable polymerization reaction. The synthesized composites were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. Their adsorption isotherm and kinetics for aqueous hexavalent chromium were also systematically examined. The results of scanning electron microscopy analysis indicated that the obtained composites based on Streptomyces were showed a uniform and stable one-dimensional morphology with distinct core–shell configuration. Moreover, the Langmuir isotherm model (R ² > 0.96) and pseudo-second-order equation (R ² = 0.9996) described well the equilibrium adsorption behavior and kinetics of hexavalent chromium adsorption by the composites. In addition, bath adsorption experiments demonstrated the highest adsorption capacity of hexavalent chromium by the composites reached 320.03 mg g^?1 in an acid solution, which was 5.6 times as that of the pure Streptomyces filaments. The results of Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy analyses suggested that the adsorption of hexavalent chromium by the composites possibly involved the protonation, redox, and chelation reactions. Therefore, a promising application of these composites in treating acid hexavalent chromium-contaminated wastewater is expectable.     

Comparative study of the absorptive potential of raw and activated carbon <Emphasis Type="Italic">Acacia nilotica</Emphasis> for Reactive Black 5 dye

Acacia nilotica was used for the adsorption of Reactive Black 5 (RB5) dye from an aqueous solution. Both the raw and activated (with H₃PO₄) carbon forms of Acacia nilotica (RAN and ANAC, respectively) were used for comparison. Various parameters (including dye concentration, contact time, temperature, and pH) were optimized to obtain the maximum adsorption capacity. RAN and ANAC were characterized using Fourier transform infrared spectroscopy, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. The maximum experimental adsorption capacities for RAN and ANAC were 34.79 and 41.01 mg g^?1, respectively, which agreed with the maximum adsorption capacities predicted by the Langmuir, Freundlich, and Dubinin–Radushkevich equilibrium isotherm models. The adsorption data of ANAC showed a good fit to the isotherm models based on the coefficient of determination (R ²): Langmuir type II (R ² = 0.99) > Freundlich (R ² = 0.9853) > Dubinin–Radushkevich (R ² = 0.9659). This result suggested monolayer adsorption of RB5 dye. The adsorption of RB5 dye followed pseudo-second-order kinetics. The RAN adsorbent reflected an exothermic reaction (enthalpy change, ΔH = ?0.006 kJ mol^?1) and increased randomness (standard entropy change, ΔS = 0.038 kJ mol^?1) at the solid–solution interface. In contrast, ANAC reflected both exothermic [?0.011 kJ mol^?1 (303–313 K)] and endothermic [0.003 kJ mol^?1 (313–323 K)] reactions. However, the ΔS value of ANAC was lower when the RB5 adsorption increased from 313 to 323 K. The negative values for the Gibbs free energy change at all temperatures indicated that the adsorption of RB5 dye onto RAN and ANAC was spontaneous in the forward direction.     

Sand-supported bio-adsorbent column of activated carbon for removal of coliform bacteria and <Emphasis Type="Italic">Escherichia coli</Emphasis> from water

New bio-adsorbent carbon materials were synthesized from the leaves and veins of Mucuna pruriens and Manihot esculenta plants, which are locally available in abundance. The synthesized carbons were activated using 0.01N HNO₃. Surface area of the activated carbons from M. pruriens and M. esculenta plants was found to be quite high, i.e., 918 and 865 m²/g, respectively. Scanning electron microscopy analysis of the carbons reflects complex disorganized surface structures of different open pore sizes, shapes and dimensions. These properties of the newly synthesized activated carbons led to the development of a sand-supported carbon column, for its possible use in the removal of coliform bacteria and Escherichia coli (E. Coli) from raw water samples. The removal percentage of E. coli was found to be 100% with both the types of carbon adsorbents, as confirmed from the McCardy most probable number table. Similarly, the removal percentage of coliform bacteria was found to be 99 and 98.7% by M. pruriens and M. esculenta carbon columns, respectively. These activated carbons synthesized from locally available plants possess the characteristics of good low-cost adsorbents which can be easily used for the removal of bacteria from water by adsorption method.     

Chemical treatment of teff straw by sodium hydroxide,phosphoric acid and zinc chloride: adsorptive removal of chromium

In this study, teff (Eragrostis tef) straw has been chemically treated and tested as an adsorbent for Cr(VI) removal. Chemically treatment of teff straw was done by NaOH, H₃PO₄ and ZnCl₂ solutions. Scanning electron micrograph and X-ray diffraction were used for anatomical characterization, whereas Fourier transform infrared spectroscopy was used for surface change characterization of adsorbents. Effects of different experimental parameters like pH (2–12), initial Cr(VI) concentration (100–900 mg/L), adsorbent dose (2.5–20 g/L), contact time (15–360 min) and temperature (288–318 K) were studied. Temperature increment was found to stimulate the adsorption process. Langmuir isotherm was found to give better representation over wide range of temperature for untreated, H₃PO₄- as well as ZnCl₂-treated teff straw, and Freundlich isotherm best represented the isotherm data for NaOH-treated teff straw. Maximum Cr(VI) adsorption capacity of untreated, NaOH-, H₃PO₄- and ZnCl₂-treated teff straw was found to be 86.1, 73.8, 89.3 and 88.9 mg/g, respectively. Respective values of average effective diffusion coefficient (D _e) were found to be 2.8 × 10^?13, 2.59 × 10^?14, 1.32 × 10^?13 and 1.14 × 10^?13 m²/s, respectively. The negative value of ΔG _o for all the adsorbents indicates Cr(VI) spontaneous adsorption. Isosteric heat of adsorption (ΔH _st,a) was found to vary with surface coverage (θ). ΔH _st,a increased for untreated, H₃PO₄- and ZnCl₂-treated teff straw, and decreased steadily with θ for NaOH-treated teff straw.     

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).     

Structural investigations of (Ca,Sr)ZrO<Subscript>3</Subscript> and Ca(Sn,Zr)O<Subscript>3</Subscript> perovskite compounds

(Ca _x ,Sr_1?x )ZrO₃ and Ca(Sn _y ,Zr_1-y )O₃ solid solutions were synthesized by solid-state reaction at high temperature before to be studied by powder X-ray diffraction and Raman Spectroscopy. Diffraction data allow the distortion of the ABO₃ perovskite structure to be investigated according to cations substitution on A and B-sites. It is shown that distortion, characterized by Φ, the tilt angle of BO₆ octahedra, slightly increases with decreasing y content in Ca(Sn _y ,Zr_1?y )O₃ compounds and strongly decreases with decreasing x content in (Ca _x ,Sr_1?x )ZrO₃ compounds. Such results are discussed in view of the relative A and B cation sizes. Raman data show that vibrational spectra are strongly affected by the cation substitution on A-site; the frequencies of most vibrational modes increase with increasing x content in (Ca _x ,Sr_1?x )ZrO₃ compounds, i.e. with the decreasing mean size of the A-cation; the upper shift is observed for the 358 cm^?1 mode (?ν/?r = ?60.1 cm^?1/Å). On the other hand, the cation substitution on B-sites, slightly affect the spectra; it is shown that in most cases, the frequency of vibrational modes increases with increasing y content in Ca(Sn _y ,Zr_1?y )O₃ compounds, i.e. with the decreasing mean size of the B-cation, but that two modes (287 and 358 cm^?1) behave differently: their frequencies decrease with the decreasing mean size of the B-cation, with a shift respectively equal to +314 and +162 cm^?1/Å. Such results could be used to predict the location of different elements such as trivalent cations or radwaste elements on A- or B-site, in the perovskite structure.     

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.     

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⁺.     

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})].     

Copper Adsorption by Chernozem Soils and Parent Rocks in Southern Russia

Laboratory data in Cu²⁺ adsorption by chernozems and parent rocks in Rostov region show that adsorption isotherms can be approximated by the Langmuir equation, whose parameters (K_l and C_∞) were calculated for all of the samples. The values of C_∞ show a strong negative correlation with the values of cationexchange capacity (CEC) (r =–0.88 at Р = 0.95), and K_l is correlated with the content of physical clay (particles <0.01 mm) (r = 0.78) and with clay (particles <0.001 mm) content in ordinary chernozem and southern chernozems of various particle size distribution (r = 0.80). Even stronger correlations were detected between these parameters in southern chernozems (r = 0.89 for the physical clay (PC) and r = 0.91 for the silt). However, none of the samples displays a significant correlation of C_∞ and K_l with the contents of physical clay and silt. This led us to conclude that the composition of the samples, for example, their organic matter, can affect Cu²⁺ adsorption by the soils and parent rocks. Acidification mechanisms of the equilibrium solutions during the Cu²⁺ adsorption by soils are discussed, as also are the reasons for the absence of balance between Cu²⁺ adsorbed by soils and exchangeable cations transferred into solution. Analysis of the fine structures of the XANES and EXAFS spectra suggests that Cu²⁺ can form coordinated chelate complex compounds with humic acids (HA) of soils and can substitute Al³⁺ at octahedral sites when interacting with clay minerals in soils.     

Adsorption kinetics and thermodynamics of organophosphorus profenofos pesticide onto Fe/Ni bimetallic nanoparticles

Bimetallic Fe/Ni nanoparticles were synthesized and used for the removal of profenofos organophosphorus pesticide from aqueous solution. These novel bimetallic nanoparticles (Fe/Ni) were characterized by scanning electron microscopy, energy-dispersive X-ray analysis spectroscopy, X-ray diffraction, and Fourier transform infrared spectroscopy. The effect of the parameters of initial pesticide concentration, pH of the solution, adsorbent dosage, temperature, and contact time on adsorption was investigated. The adsorbent exhibited high efficiency for profenofos adsorption, and equilibrium was achieved in 8 min. The Langmuir, Freundlich, and Temkin isotherm models were used to determine equilibrium. The Langmuir model showed the best fit with the experimental data (R ² = 0.9988). Pseudo-first-order, pseudo-second-order, and intra-particle diffusion models were tested to determine absorption kinetics. The pseudo-second-order model provided the best correlation with the results (R ² = 0.99936). The changes in the thermodynamic parameters of Gibb’s free energy, enthalpy, and entropy of the adsorption process were also evaluated. Thermodynamic parameters indicate that profenofos adsorption using Fe/Ni nanoparticles is a spontaneous and endothermic process. The value of the activation energy (E _a = 109.57 kJ/mol) confirms the nature of the chemisorption of profenofos onto Fe/Ni adsorbent.     

Effect of 2-D Random Field Discretization on Failure Probability and Failure Mechanism in Probabilistic Slope Stability

This paper investigates, using the random field theory and Monte Carlo simulation, the effects of random field discretization on failure probability, p _f, and failure mechanism of cohesive soil slope stability. The spatial sizes of the discretized elements in random field Δx, Δy in horizontal and vertical directions, respectively, are assigned a series of combinational values in order to model the discretization accuracy. The p _f of deterministic critical slip surface (DCSS) and that of the slope system both are analyzed. The numerical simulation results have demonstrated that both the ratios of Δy/λ _y (λ _y  = scale of fluctuation in vertical direction) and Δx/λ _x (λ _x  = scale of fluctuation in horizontal direction) contribute in a similar manner to the accuracy of p _f of DCSS. The effect of random field discretization on the p _f can be negligible if both the ratios of Δx/λ _x and Δy/λ _y are no greater than 0.1. The normalized discrepancy tends to increase at a linear rate with Δy/λ _y when Δx/λ _x is larger than 0.1, and vice versa for p _f of DCSS. The random field discretization tends to have more considerable influence on the p _f of DCSS than on that of the slope system. The variation of p _f versus λ _x and λ _y may exhibit opposite trends for the cases where the limit state functions of slope failure are defined on DCSS and on the slope system as well. Finally, the p _f of slope system converges in a more rapid manner to that of DCSS than the failure mechanism does to DCSS as the spatial variability of soil property grows from significant to negligible.     

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.     

The potential use of OH-defects in enstatite as geobarometer

In this study, single crystals of pure enstatite (Mg₂Si₂O₆) were synthesised under water-saturated conditions at 4 and 8 GPa and 1,150°C with variable silica activity, leading to phase assemblages enstatite + forsterite, enstatite or enstatite + coesite. Run products were investigated using an FTIR spectrometer equipped with a focal plane array detector enabling IR imaging with a lateral pixel resolution of 2.7 μm. IR spectra within the OH-absorption region show two different groups of absorption bands: group 1 (wavenumbers at 3,592 and 3,687 cm^?1) shows strongest absorptions for E||n _β, whereas group 2 (wavenumbers at 3,067 and 3,362 cm^?1) shows strongest absorptions for E||n _γ. The groups are related to different defect types, group 1 to tetrahedral defects (T-site vacancies) and group 2 to octahedral defects (M-site vacancies). The intensity ratio of the bands within one group (i.e. A ₃₀₆₇/A ₃₃₆₂ and A ₃₅₉₂/A ₃₆₈₇) and the intensity ratio of E||n _γ and E||n _α in group 2 bands remain constant within error. In contrast, the intensity ratio of group 2 to group 1 absorption bands [e.g. (A ₃₃₆₂)/(A ₃₆₈₇)] is sensitive to the SiO₂ activity and pressure. On the basis of the results of this and previous studies, a barometer for pure orthoenstatite coexisting with forsterite can be formulated:\( P\,[{\text{GPa}}] = 1.056 + \sqrt {{\frac{{1.025 - A_{{\left( {3362} \right)/\left[ {(3362) + (3687)} \right]}} }}{0.009}}} , \) where A ₍₃₃₆₂₎ and A ₍₃₆₈₇₎ are the integral absorbances of the component E||n _γ of the absorption bands at 3,362 cm^?1 and the component E||n _β of the absorption band at 3,687 cm^?1, respectively.