Equation of state of Fe3+-bearing phase-X

We investigated the high-pressure behaviour of Fe³⁺-bearing hydrous phase-X, (K_1.307Na_0.015)(Mg_1.504Fe _0.373 ³⁺ Al_0.053Ti _0.004 ⁴⁺ )Si₂O₇H_0.36, up to 34?GPa at room temperature by synchrotron X-ray powder diffraction. The lattice parameters behave anisotropically, with the [001] direction stiffer than [100]. In the 10^?4 to 22?GPa pressure range, the axial bulk moduli are K _0a ?=?112(3) GPa and K′?=?4, and K _0c ?=?158(2) GPa and K′?=?4, and the anisotropy of the lattice parameters is β_0c :β_0a ?=?0.71:1. The cell volumes are fitted by a second-order Birch–Murnaghan equation of state giving a bulk modulus of K ₀?=?127(1) GPa and K′?=?4 in the same pressure range. After 22?GPa, a discontinuity in volume and lattice parameters can be recognized. Sample did not become amorphous up to 34?GPa. The coupled substitution K?+?Mg?=?[]?+?Fe³⁺ has only a limited influence on the bulk modulus and structural stability of phase-X.     

Adsorption of hexavalent chromium onto activated carbon derived from <Emphasis Type="Italic">Leucaena leucocephala</Emphasis> waste sawdust: kinetics,equilibrium and thermodynamics

The adsorptive removal of Cr(VI) was studied using activated carbon derived from Leucaena leucocephala (ACLL). The physico-chemical properties of ACLL were determined using proximate analysis and N₂ BET surface area analysis. The N₂ BET surface area of ACLL was determined to be 1131 m² g^?1. The point of zero charge (pH_pzc) of 5.42 indicated that ACLL surface was positively charged for pH below the pH_PZC, attracting anions. The effect of experimental operating parameters such as time of contact, ACLL dose, pH, initial concentration and temperature was investigated. The optimum values of parameters such as concentration of 100 mg L^?1, 300 mg of ACLL dose, time of contact of 60 min, pH of 4 indicated the maximum Cr(VI) uptake of 13.85 mg g^?1. The pseudo-second-order kinetic model best fitted with the Cr(VI) adsorption data. Adsorptive removal of Cr(VI) onto ACLL satisfactorily fitted in the order of Redlich–Peterson > Freundlich > Langmuir > Temkin adsorption isotherm model. The thermodynamic parameters showed the adsorption of Cr(VI) onto ACLL was an endothermic and spontaneously occurred process.     

Isopiestic measurement of the osmotic and activity coefficients for the NaOH-NaAl(OH)4-H2O system at 313.2 K

By using a specially designed and constructed isopiestic apparatus, we measured the osmotic coefficients at 313.2 K for the NaOH-NaAl(OH)₄-H₂O system with the total alkali molality, m_NaOHT (m_NaOH + m_NaAl[OH]4), from 0.05 mol/kg H₂O to 12 mol/kg H₂O and α_K (m_NaOHT/m_NaAl(OH)4) from 1.64 to 5.53. The mean standard deviation of the measurements is 0.0038. Several sets of the Pitzer model parameters for NaOH-NaAl(OH)₄-H₂O system were then obtained by regressing the measured osmotic coefficients with the Pitzer model and the Pitzer model parameters for NaOH(aq). One set of the results is as follows: β⁽⁰⁾_NaOH: 0.08669, β⁽¹⁾_NaOH: 0.31446, β⁽²⁾_NaOH: −0.00007367, C^Φ_NaOH: 0.003180, β⁽⁰⁾_NaAl(OH)4: 0.03507, β⁽¹⁾_NaAl(OH)4: 0.02401, C^Φ_NaAl(OH)4: −0.001066, θ_{OH⁻Al(OH)4⁻}: 0.08177, Ψ_Na⁺OH⁻_Al(OH)4⁻: −0.01162. The mean standard difference between the calculated and the measured osmotic coefficients is 0.0088. With the obtained Pitzer model parameters, we calculated the values of K = (γ_{NaAl(OH)4,cal²} · m_{Al(OH)4⁻,exp})/(γ_NaOH,cal² · m_OH⁻,exp) for the gibbsite solubility. The results show that the obtained Pitzer model parameters are reliable, and the relative error of the calculated activity coefficients should be < 2.1%. We also compared the calculated gibbsite solubility data among several activity coefficients models over a range of m_NaOHT at various temperatures. The comparison indicates that our activity coefficients model may be approximately applied in the ranges of temperature from 298.2 to 323.2 K and m_NaOHT from 0 to 8 mol/kg H₂O. We also calculated the stoichiometric activity coefficients of NaOH and NaAl(OH)₄ and the activity of H₂O for the NaOH-NaAl(OH)₄-H₂O system, and these calculations establish their variations with m_NaOHT and α_K. These variations imply that the strengths of the repulsive interactions among various anions are in the following sequence: Al(OH)₄⁻-Al(OH)₄⁻ < Al(OH)₄⁻-OH⁻ < OH⁻-OH⁻, and the attractive interaction between Al(OH)₄⁻ and H₂O is weaker than that between OH⁻ and H₂O.     

Study of Colombian coals using photoacoustic Fourier transform infrared spectroscopy

Five of the most important Colombian coals were studied using Photoacoustic Fourier transform infrared (PA-FTIR) spectroscopy. The PA-FTIR spectra were used to obtain structural parameters and to determine the analytical potential of this technique. The molecular structural parameters, CH₂/CH₃, f_a, H_al/H_ar, and (R/C)_u were correlated with fixed carbon contained in the samples to determine aliphatic hydrogen, H_al, and the aromatic hydrogen, H_ar in coals studied here. These parameters enabled the determination of aromaticity, f_a, which was found to be between 0.66 and 0.98. The aliphatic and aromatic regions were considered between 3005–2760 cm^?1 and 912–670 cm^?1, respectively. Finally, using the molecular structural parameters, the grade of maturation (rank) of coal samples studied was determined.     

High-pressure behaviour and equation of state of calcite, CaCO3

The high-pressure response of the cell parameters of calcite, CaCO₃, has been investigated by single crystal X-ray diffraction. The unit cell parameters have been refined from 0 to 1.435?GPa, and the linear and volume compressibilities have been measured as β _a =2.62(2)?×?10^?3?GPa^?1,β _c =7.94(7)?×?10^?3?GPa^?1, β _v =13.12?×?10^?3?GPa^?1. The bulk modulus has been obtained from a fit to the Birch-Murnaghan equation of state, giving K ₀=73.46?±?0.27?GPa and V ₀=367.789 ±?0.004?ų with K′=4. Combined with earlier data for magnesite, ankerite and dolomite, these data suggest that K ₀ V ₀ is a constant for the Ca-Mg rhombohedral carbonates.     

Prediction of surface charge on oxides in salt solutions: Revisions for 1:1 (ML) electrolytes

Quantitative characterization of the development of proton surface charge on the surfaces of minerals is necessary for a fundamental understanding of reactions between minerals and aqueous electrolyte solutions. Despite many experimental studies of charge development, few attempts have been made to integrate the results of such studies with a theoretical framework that permits prediction. The present study builds on a theoretical framework to analyze a total of 55 sets of proton surface charge data referring to wide ranges of ionic strengths, and types of electrolyte and oxide. The resulting parameters were interpreted with the aid of crystal chemical, electrostatic, and thermodynamic theory, which enable a number of generalizations. Prediction of values of the pHZPC and ΔpKnθ reduces the number of triple-layer parameters to be estimated. New standard states for the equilibrium constants for electrolyte adsorption (KM+θ and KL−θ) permit direct comparison of samples with a range of surface areas or site densities. Predicted cation binding on high dielectric constant solids (e.g., rutile) shows KM+θ, increasing in the sequence Cs+, Rb+, K+, Na+, Li+. In contrast, on low dielectric constant solids (e.g., amorphous silica), the predicted sequence is Li+, Na+, K+, Rb+, Cs+. The opposite sequences are attributable to the large solvation energy contribution opposing adsorption on low-dielectric constant solids. Cation and anion binding constants are in general different, which enables direct prediction of the point-of-zero-salt effect (pHPZSE) relative to the pristine point-of-zero charge. The inner and outer capacitances in the triple-layer model (C1 and C2) are predictable parameters consistent with physically reasonable distances and interfacial dielectric constants for water. In summary, all the parameters in the triple-layer model can be estimated with the revised equations of this study, which enables prediction of proton surface charge for any oxide in 1:1 electrolyte solutions independent of experiments. Such predictions can serve as a complement to the experimental study of new oxide/electrolyte systems, or more complex systems, where additional mechanisms of charge development are likely.     

Fluid-mineral equilibria and thermodynamic mixing properties of fluid systems

The paper presents a review of an experimental method to quantitatively constrain thermodynamic mixing properties of fluid systems at high temperature T and pressure P. The method is based on bracketing equilibrium parameters of simple fluid-mineral reactions. Experimental data obtained with this technique for the H₂O-CO₂, H₂O-N₂, and H₂O-H₂ binary systems were utilized to calculate mixing parameters corresponding to the simplified van Laar model W ₁₂ ^VL , according to which the equation for the integral excess Gibbs free energy of a binary mixture G ^ex is G ^ex =X ₁ X ₂ W ₁₂ ^VL /(X ₁ V ₁ ⁰ + X ₂ V ₂ ⁰ ), where X _i is the mole fractions of the components, and V _i ⁰ are pure species molar volumes at given P and T (in cm³). The W ₁₂ ^VL for the three mixtures correspond to 202, 219, and 331 kJ cm³/mol. The empirical correlation $W_{H_2 O - X}^{VL}$ (kJ cm³/mol) = 887.012 Q _X ? 16.674, where Q = P _c (critical pressure, bar)/T _c (critical temperature, K) for gas X (where X = CH₄, CO, H₂S, O₂, Ar, and NH₃) is used to evaluate the van Laar parameters for a number of petrologically important water-gas mixtures. The H₂O-H₂ system is characterized by the greatest positive deviation from the ideal mixing and can thus decompose into two immiscible fluid phases under the P-T parameters typical of deep lithospheric zones. The exsolution of the H₂O-CO₂ and H₂O-N₂ systems is expected to occur only under high pressure and low temperature. This combination of parameters may be expected only in the environments of cold subduction. Salts (highly soluble simple salts and/or silicates) should significantly expand the exsolution regions in petrologically important fluids.     

The crystal chemistry of birefringent natural uvarovites. Part III. Application of the superposition model of crystal fields with a characterization of synthetic cubic uvarovite

Synthetic, flux-grown uvarovite, Ca₃Cr₂ [SiO₄]₃, was investigated by optical methods, electron microprobe analysis, UV-VIS-IR microspectrometry, and luminescence spectroscopy. The crystal structure was refined using single-crystal X-ray CCD diffraction data. Synthetic uvarovite is optically isotropic and crystallizes in the “usual” cubic garnet space group Ia3¯d [a=11.9973 Å, Z=8; 21524 reflections, R1=2.31% for 454 unique data and 18 variables; Cr–O=1.9942(6), Si–O=1.6447(6), Ca–O_a=2.3504(6), Ca–O_b= 2.4971(6) Å]. The structure of Ca₃Cr₂[SiO₄]₃ complies with crystal-chemical expectations for ugrandite group garnets in general as well as with predictions drawn from “cubically averaged” data of non-cubic uvarovite–grossular solid solutions (Wildner and Andrut 2001). The electronic absorption spectra of Cr³⁺ in trigonally distorted octahedra of synthetic uvarovite were analyzed in terms of the superposition model (SM) of crystal fields. The resulting SM and interelectronic repulsion parameters are =9532 cm^?1, =4650 cm^?1, power law exponent t ₄=6.7, Racah B₃₅=703 cm^?1 at 290 K (reference distance R ₀=1.995 Å; fixed power law exponent t ₂=3 and spin-orbit parameter ζ=135 cm^?1). The interelectronic repulsion parameters Racah B ₅₅=714 cm^?1 and C=3165 cm^?1 were extracted from spin-forbidden transitions. This set of SM parameters was subsequently applied to previously well-characterized natural uvarovite–grossular solid solutions (Andrut and Wildner 2001a; Wildner and Andrut 2001) using their extrapolated Cr–O bond lengths to calculate the energies of the spin-allowed bands. These results are in very good agreement with the experimentally determined band positions and indicate the applicability of the superposition model to natural 3d ^N prevailing systems in geosciences. Single-crystal IR absorption spectra of synthetic uvarovite in the region of the OH-stretching vibration exhibit one isotropic absorption band at 3508 cm^?1 at ambient conditions, which shifts to 3510 cm^?1 at 77 K. This band is caused by structurally incorporated hydroxyl groups via the (O₄H₄)-hydrogarnet substitution. The water content, calculated using an integral extinction coefficient ?=60417 cm^?2 l mol^?1, is c _H2O=33 ppm.     

Synthesis,crystallographic data,solubility and electrokinetic properties of meta-zeunerite,meta-kirchheimerite and nickel-uranylarsenate

{M[UO₂¦AsO₄]₂ · nH₂O} with M=Cu²⁺, Co²⁺, Ni²⁺ has been synthesized from reagent grade chemicals and by ion exchange of trögerite {HUO₂AsO₄ · 4 H₂O}. Synthetic meta-zeunerite (M=Cu²⁺), meta-kirchheimerite (M=Co²⁺) and nickel-uranylarsenate are all tetragonal. The cell parameters determined from Guinier-Hägg diffraction data for {Cu[UO₂¦AsO₄]₂ · 8 H₂O} are a=b=7.10 Å and c=17.42 Å, with Z=2 and the measured density 3.70 g cm^?3. The cell parameters for {Co[UO₂¦AsO₄]₂ · 7 H₂O} and {Ni[UO²¦AsO⁴]² · 7 H₂O} are a=b=20.25 Å and c=17.20 Å, with Z=16 and the measured density 3.82 and 3.74 g cm^?3, respectively. The solubility products for synthetic Cu-, Co- and Ni-uranylarsenate at 25° C are 10^?49.20, 10^?45.34 and 10^?45.10, respectively. The zeta-potential remains negative between pH=2 and pH=9 and is strongly affected by the presence of different cations.     

Supermassive black holes and central star clusters: Connection with the host galaxy kinematics and color

The relationship between the masses of the central, supermassive black holes (M _bh) and of the nuclear star clusters (M _nc) of disk galaxies with various parameters galaxies are considered: the rotational velocity at R = 2 kpc V ₍₂₎, the maximum rotational velocity V _max, the indicative dynamical mass M ₂₅, the integrated mass of the stellar populationM _*, and the integrated color index B-V. The rotational velocities andmasses of the central objects were taken from the literature. ThemassM _nc correlatesmore closely with the kinematic parameters and the disk mass than M _bh, including with the velocity V _max, which is closely related to the virial mass of the dark halo. On average, lenticular galaxies are characterized by higher massesM _bh compared to other types of galaxies with similar characteristics. The dependence of the blackhole mass on the color index is bimodal: galaxies of the red group (red-sequence) with B-V >0.6–0.7 which are mostly early-type galaxies with weak star formation, differ appreciably from blue galaxies, which have higher values of M _nc and M _bh. At the dependences we consider between the masses of the central objects and the parameters of the host galaxies (except for the dependence of M _bh on the central velocity dispersion), the red-group galaxies have systematically higher M _bh values, even when the host-galaxy parameters are similar. In contrast, in the case of nuclear star clusters, the blue and red galaxies form unified sequences. The results agree with scenarios in which most red-group galaxies form as a result of the partial or complete loss of interstellar gas in a stage of high nuclear activity in galaxies whose central black-hole masses exceed 10⁶?10⁷ M _⊙ (depending on the mass of the galaxy itself). The bulk of disk galaxies with M _bh > 10⁷ M _⊙ are lenticular galaxies (types S0, E/S0) whose disks are practically devoid of gas.     

Structure, ordering and cation interactions in Ca-free P2 1 /c clinopyroxenes

A suite of 14 synthetic Ca-free P2 ₁ /c low-clinopyroxenes of compositions across the enstatite-ferrosilite (En-Fs) join have been studied by X-ray powder diffraction and Mössbauer spectroscopy. The crystal structure of one sample with composition X _Fs=0.39 was determined by single-crystal X-ray diffraction. The powder diffraction data show that there is no significant (<0.25% at X _Fs=0.5) excess volume of mixing on the enstatite-ferrosilite join. The molar volumes are described by V=31.261(17)+1.677(23) X _Fs cm³.mol(MSiO₃)^–1. The linear behaviour of volume with composition arises from the compensating effects of non-linear changes in the unit-cell parameters with composition. Unweighted fits to the data yielded the relationships: a=9.6100(15)+0.105(2)X _Fs, b=8.8156(28)+0.218(12)X _Fs+0.0481(117)X ² _Fs , c?=5.1702(4)+0.0879(21)X _Fs–0.0214(21)X ² _Fs , β=108.345(8)+0.947(30)X _Fs–0.805(26)X ² _Fs . The strong positive deviation of β from linearity is directly correlated to the difference in site occupancies between M1 and M2 as determined by Mössbauer spectroscopy and arises directly from the expansion of M2-O1 and M2-O3 bonds upon initial substitution of Fe for Mg in enstatite. The hyperfine parameters from Mössbauer spectra are consistent with variations in the average local environment as recorded by the X-ray data. Asymmetric line broadening of the Mössbauer spectra provides evidence for next-nearest neighbour effects, and is consistent with no significant clustering of Fe or Mg within the samples.     

Stability and P–V–T equation of state of KAlSi3O8-hollandite determined by in situ X-ray observations and implications for dynamics of subducted continental crust material

In situ X-ray diffraction measurements of KAlSi₃O₈-hollandite (K-hollandite) were performed at pressures of 15–27 GPa and temperatures of 300–1,800 K using a Kawai-type apparatus. Unit-cell volumes obtained at various pressure and temperature conditions in a series of measurements were fitted to the high-temperature Birch-Murnaghan equation of state and a complete set of thermoelastic parameters was obtained with an assumed K′_300,0=4. The determined parameters are V _300,0=237.6(2) Å³, K _300,0=183(3) GPa, (?K _T,0/?T) _P =?0.033(2) GPa K^?1, a ₀=3.32(5)×10^?5 K^?1, and b ₀=1.09(1)×10^?8 K^?2, where a ₀ and b ₀ are coefficients describing the zero-pressure thermal expansion: α _T,0 = a ₀ + b ₀ T. We observed broadening and splitting of diffraction peaks of K-hollandite at pressures of 20–23 GPa and temperatures of 300–1,000 K. We attribute this to the phase transitions from hollandite to hollandite II that is an unquenchable high-pressure phase recently found. We determined the phase boundary to be P (GPa)=16.6 + 0.007 T (K). Using the equation of state parameters of K-hollandite determined in the present study, we calculated a density profile of a hypothetical continental crust (HCC), which consists only of K-hollandite, majorite garnet, and stishovite with 1:1:1 ratio in volume. Density of HCC is higher than the surrounding mantle by about 0.2 g cm^?3 in the mantle transition zone while this relation is reversed below 660-km depth and HCC becomes less dense than the surrounding mantle by about 0.15 g cm^?3 in the uppermost lower mantle. Thus the 660-km seismic discontinuity can be a barrier to prevent the transportation of subducted continental crust materials to the lower mantle and the subducted continental crust may reside at the bottom of the mantle transition zone.     

Physical parameters and dynamical properties of the multiple system ι UMa (ADS 7114)

We analyze the physical parameters, orbital elements, and dynamic stability of the multiple system ?? UMa (HD 76644 = ADS 7114). We have used the positions from the WDS catalog and our own observations on the 6-m telescope of the Special Astrophysical Observatory of the Russian Academy of Sciences and the 1.5-m Russian-Turkish Telescope (Antalya, Turkey). We have obtained more precise orbital parameters of the subsystems, and spectral types, absolute magnitudes, and masses of the components. The primary has Sp = F0 V?CIV, M = 1.7 ± 0.1M _??, T _eff = 7260 ± 70 K, and log g = 4.30 ± 0.07. The companion in the close Aa subsystem is most likely a white dwarf with a mass of approximately 1.0 ± 0.3M _??. The spectral types and masses of the components in the BC subsystem are M3V, M4V and 0.35 ± 0.05M _??, 0.30 ± 0.05M _??, respectively. The total mass is 3.4 ± 0.4M _??. The Aa subsystem probably has an orbital period of 4470^d = 12.2^y and an eccentricity of approximately 0.6. The outer subsystem seems to have a period of approximately 2084 yrs and an eccentricity of approximately 0.9. We have carried out simulations using the stability criteria and shown that for all possible variations in the component parameters, the multiple system is unstable on a time scale of less than 10⁶ years with a probability exceeding 0.98. Possible reasons for this instability are discussed.     

Refinement of the crystal structure of fornacite using the rietveld method

The crystal structure of fornacite Pb₂(Cu,Fe)[CrO₄(As,P)O₄OH] from the Berezovskii deposit (Central Urals, Russia) was refined by X-ray powder diffraction data using the Rietveld method. Fornacite is monoclinic, space group P2₁/c, the unit cell dimensions are a = 8.09015(12), b = 5.90913(9), c = 17.4839(2) Å, β = 109.99(2), V = 785.5(3) ų, and Z = 4. The structure was refined in the isotropic approximation of the atomic displacement parameters up to R _p = 0.0516, R _wp = 0.0692, R _B = 0.0229, and R _F = 0.0200. The fornacite structure is similar to that of minerals of the brackebuschite-group and consists of heteropolyhedral chains, built by the columns of edge-sharing Cu²⁺O₆ octahedra connected with isolated Cr⁶⁺O₄ and As⁵⁺O₄ tetrahedra. The chains are linked by ninefold Pb²⁺ polyhedra.     

Thermodynamic parameters of CaMgSi2O6-Mg2Si2O6 pyroxenes based on regular solution and cooperative disordering models

Thermodynamic parameters for the reaction: $$\begin{gathered} Mg_2 Si_2 O_6 = Mg_2 Si_2 O_6 \hfill \\ enstatite clinopyroxene \hfill \\ \end{gathered} $$ in the system CaO-MgO-SiO₂ have been deduced from phase equilibrium and enthalpy of solution data. From the regular solution theory, the seventeen currently available reversed experimental compositions of coexisting enstatite and clinopyroxene, presumed to be ordered diopside, lead, by a statistical regression, to the following best fit parameters: ΔH ^o=6.80 kJ ΔS ^o=2.75 J/K W _H ^Cpx =24.47 kJ (regular solution enthalpy parameter) W _V ^Cpx =0.105 J/bar (regular solution volume parameter). The derived parameters are not significantly affected by the (necessary) choice of W ^Opx in the range 20–50 kJ. The above values are in very good agreement with deductions from the solution calorimetry on synthetic CaMgSi₂O₆-Mg₂Si₂O₆ clinopyroxenes of Newton et al. (1979), which also places bounds on possible departures from the optimal values of these parameters. The calorimetric data may also be interpreted in terms of a Bragg-Williams cooperative-disordering model (Navrotsky and Loucks, 1977), in which diopside-structure clinopyroxene and a ‘relaxed’ low-Ca clinopyroxene (‘Fe-free pigeonite’) approach each other in composition, structural state, and stability with increasing temperature. The ΔH ^o parameter deduced from the regular solution theory is reinterpreted as the enthalpy change of enstatite to Mg₂Si₂O₆ pigeonite; the ΔH ^o of the transformation of enstatite to the diopside structure would, in this case, be considerably larger than 6.8 kJ. The curvature of the enthalpy of solution data, explained by the regular solution theory in terms of M2-site energetics (involving W _H ^cpx ), is reinterpreted as due to disordering and ‘relaxation’ in the Navrotsky-Loucks model. Although the regular solution theory with the best-fit parameters accounts for all of the reversed enstatite and diopside compositions to within 18 ° C, and is a convenient representation of the phase equilibria for purposes of geothermometry, the disordering model is, at the present level of knowledge, equally valid and allows for a region of stability of two coexisting clinopyroxenes.     

Polarized electronic absorption spectra of 3d3-configurated tetravalent manganese in octahedral fields of Mn(SeO3)2

Polarized optical absorption spectra of Mn(IV) in octahedral crystal fields of Mn(SeO₃)₂ have been studied by means of microscope-spectrometry in the range 40000-4000 cm^?1 and at temperatures between 113 K and 293 K. Intense charge-transfer absorptions (linear absorption coefficient α ? 30000 cm^?1) completely mask the d-d transitions in the UV and VIS region above ≈23000 cm^?1. The optical electronegativity χ _opt of Mn(IV) in Mn(SeO₃)₂ is estimated to be 2.7. In accordance with the d ₃ configuration of tetravalent manganese three d-d bands observed at ambient temperatures at 13250, 14137 (α≈50 cm^?1) and ≈18500 cm^?1 (α≈500–800 cm^?1) are assigned to the spin forbidden ⁴ A _2g →² E _g and ⁴ A _2g →² T _1g transitions as well as to the first spin allowed ⁴ A _2g →⁴ T ^2g transition, respectively. These assignments allow the calculation of the following ligand field parameters: Dq ≈ 1850 cm^?1, B ₅₅ = 869 cm^?1 (β ₅₅ = 0.82), and C = 2346 cm^?1 (293 K).     

Removal of acetaminophen from hospital wastewater using electro-Fenton process

The current work deals with efficient removal of acetaminophen (AC) from hospital wastewater using electro-Fenton (EF) process. The degradation yield of 99.5% was obtained under optimal experimental conditions, namely 5.75 mg L^?1 initial AC concentration, 2.75 pH solution, 3-cm inter-electrode distance, 100 mg L^?1 KCl electrolyte, 122.5 µL L^?1 H₂O₂, 8 mA cm^?2 current density at equilibrium time of 8 min. Analysis of variance (ANOVA) suggested that the effect of mentioned operating parameters was statistically significant on the AC removal. The low probability amount of P value (P < 0.0001), the Fisher’s F-value of 65.91, and correlation coefficient of the model (R² = 0.9545) revealed a satisfactory correlation between the experimental and the predicted values of AC removal. The predicted removal efficiency of 99.4% was in satisfactory agreement with the obtained experimental removal efficiency of 98.7%. The AC degradation during the EF followed a first-order kinetic model with rate constants (K_app) of 0.6718 min^?1. Using the ordinary radical scavengers revealed that main mechanism of AC degradation controlled by the hydroxyl free radicals produced throughout the EF process. The excess amount of iron (II) scavenged the active radicals and diminished the concentration of ^·OH available to react with AC. The optimum molar ratio of H₂O₂ to Fe²⁺ was found to be 2.5. The developed EF process as a promising technique applied for treatment of real samples.     

Magnetization and 57Fe Mössbauer study of obsidians

Magnetic analysis and ⁵⁷Fe Mössbauer spectroscopy were used to find characteristic properties of obsidian samples collected from various localities in the Mediterranean area. Magnetic hysteresis parameters of ≈ 30 different obsidian samples, recorded at 294 K, and plotted in the form σ _r /σ _s versus H _c /H _cr (σ _r =saturation remanent magnetization, σ _s =saturation magnetization of ferrimagnetic phases in the obsidian samples, H _c =coercive force, H _cr =remanent coercive force) cluster in certain areas of the plot for obsidian samples of a given region. This property results from the formation of ferrimagnetic ore grains of various grain sizes, which appear to be Fe₃O₄-rich spinels (Curie temperatures T _c ≈520–580°C), during the rapid cooling process of the silica-rich magma. For single domain, pseudosingle domain and multidomain particles of magnetic minerals, corresponding to different grain sizes, the data points are usually in different areas of the plot. The results show that there is obviously a characteristic difference in the ore grain size and in the grain size distribution for obsidian samples from different regions. ⁵⁷Fe Mössbauer absorption spectra revealed two distinct kinds of patterns, characterized by contributions from Fe²⁺ and Fe³⁺ cations preferentially inside the glassy matrix. The poor resolution of the spectra precludes the application of this method for identification purposes. The Mössbauer parameters of quadrupole splitting, isomer shift and linewidth are compatible with the respective values for Fe²⁺ and Fe³⁺ cations in alkali and alkaline-earth silicate glasses.     

Chemical and structural study of 1M- and 2M 1-phlogopites coexisting in the same Kasenyi kamafugitic rock (SW Uganda)

In the present work, crystal chemical variations between 1M and 2M ₁ phlogopites coexisting in the same rock sample from kamafugite of Kasenyi (southwest Uganda, west branch of the East African Rift) were explored by electron probe microanalyses, single crystal X-ray diffraction and M?ssbauer spectroscopy. Chemical analyses revealed close similarity both within and between the two polytypic arrangements as well as high TiO₂ (~4.9?wt%) and Al₂O₃ (~12.9?wt%), and low Cr₂O₃ (~0.8?wt%), F (~0.3?wt%) and BaO (~0.2?wt%) contents. Room temperature ⁵⁷Fe M?ssbauer investigation proved that the studied mica is a tetraferriphlogopite with: ^IVFe³⁺?=?19(1)?%, ^VIFe²⁺?=?58(1)?%, ^VIFe³⁺?=?23(1)?%. Single crystal refinement showed that both polytypes have narrow range of variation in terms of some relevant unit cell parameters and similar values in terms of mean bond lengths, mean atomic numbers and distortion parameters. Similar substitutions were active in the structure of the 1M and 2M ₁ studied phlogopites. However, in 2M ₁ polytypes the oxy-type substitutions were found to occur to a greater extent. Comparison of unit layer of 1M mica (in the 2M ₁ setting) with that of the 2M ₁ ones showed that the 2M ₁ polytypes are affected to different extent by relative shifts of the upper and lower triads of octahedral oxygens along the ±b directions. This effect did not cause any symmetry lowering in the T-O-T layer of the studied samples.