Characterization of arsenate adsorption on amorphous Al gels with Keggin structure by Fourier transformed infrared spectroscopy and MAS <Superscript>27</Superscript>Al NMR

Fourier transformed infrared spectrometry (FTIR) and 27Al Magic Angle spinning (MAS) nuclear magnetic resonance spectroscopy were employed to characterize arsenate adsorption on amorphous Al gels with Keggin structure at pH =4–10. These studies have proven that: the surface complex species of arsenate show significant differences under acidic and alkaline conditions, which was deduced based on the As-O stretching vibration bands located respectively at 774 and 870 cm-1; poorly crystalline Al13 (or Al)-arsen...     

Tracing sources of carbon in urban groundwater using δ<Superscript>13</Superscript>C<Subscript>TDIC</Subscript> ratios

Total dissolved inorganic carbon (TDIC) and its stable isotope ratio δ¹³C_TDIC are used to trace the evolution of the carbon system of groundwater in three UK Permo-Triassic sandstone aquifers. Samples were collected from multilevel piezometers, open boreholes and sewer sampling points in the British Midlands (Nottingham, Birmingham and Doncaster) to evaluate both local and regional variations in δ¹³C_TDIC. δ¹³C samples of matrix and pore water have also been analysed in each aquifer to further constrain the interpretations. Combining δ¹³C_TDIC ratios with measurements of TDIC and pH clearly distinguishes the principal processes underlying the geochemical evolution of groundwater in Triassic sandstone aquifers, where processes can be both natural (e.g. carbonate dissolution) and anthropogenic (sewer-derived recharge). The paper shows that δ¹³C_TDIC resolves ambiguities that arise from the interpretation of TDIC and pH measurements in isolation. Field measurements demonstrate that, under natural conditions, the carbonate system evolves similarly in each aquifer. An open-system evolution during recharge largely saturates the groundwater with carbonate depending upon its availability in the sandstone matrix. The contribution of sewer exfiltration to urban recharge is readily distinguished by lower pH and higher TDIC values without significant changes in δ¹³C_TDIC.     

环境中Al13的研究进展

铝的水解反应及其水解聚合铝形态的研究，特别是具有Keggin结构的Al13聚合形态一直是地球化学、环境科学、形态分析以及生物毒理学等众多领域的研究热点之一。综述了近20年来Al13的分析方法、形成和转化机制、影响因素以及动力学方面研究的进展。     

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⁺.     

Ab-initio calculations of the proton location in topaz-OH,Al<Subscript>2</Subscript>SiO<Subscript>4</Subscript>(OH)<Subscript>2</Subscript>

The position of hydrogen in the structure of topaz-OH was determined by means of ab-initio quantum-mechanic calculations. Static lattice energy calculations predict the existence of four non-equivalent positions of protons, which are characterized by O4–H1... O1, O4–H2... O2, O4–H3... O3 and O4–H4... O4 hydrogen bonds. The distribution of the protons between positions of local equilibrium is controlled by the proton–proton avoidance rule and the strength of the hydrogen bonds. The most favourable configuration of hydrogen atoms is achieved for adjacent protons, which form O4–H3... O3 and O4–H4... O4 hydrogen bonds, respectively. The thermal excitation of atoms at a temperature of 55 K is large enough for the hydrogen atoms occasionally to change their positions to form O4–H1... O1 and O4–H2... O2 bonds. At ambient pressures and higher temperatures the protons are in a dynamic exchange between the allowed positions of local minima. As a consequence, for nearly room-temperature conditions, the dynamic change between different structural configurations leads to the violation of all possible symmetry elements and with that to space group #E5/E5#1. The flipping of the protons between different sites is achieved by simple rotation of the OH-dipole and does not produce any significant distortion of the framework of topaz, whose symmetry remains that of the space group Pbnm. Therefore, no reduction of symmetry has been observed in former X-ray studies on topaz-OH. Calculated IR absorption spectra of topaz-OH were found to be in good agreement with measured spectra. According to the calculations, the two favourable configurations of protons might correspond to the measured peak splitting within the OH-stretching range. An experimentally observed low-frequency band at 3520 cm^–1 was assigned to the OH-stretching of the O4–H3... O3 bond, while the band at 3600 cm^–1 was attributed to OH-stretching of the O4–H4... O4 hydrogen bond. The broad peak in FAR-IR frequency range at 100–150 cm^–1 is attributed to the stretching of H3... O3 and H4... O4 contacts. The rate of proton exchange at 670 K among different sites was estimated by ab-inito molecular dynamic simulations. The calculations predict that flipping of adjacent protons between O4–H3... O3 and O4–H4... O4 bonds at 670 K occur at a rate of about 1.96 THz.     

Magnetic properties and neutron diffraction study of two manganese sulfosalts: monoclinic MnSb<Subscript>2</Subscript>S<Subscript>4</Subscript> and benavidesite (MnPb<Subscript>4</Subscript>Sb<Subscript>6</Subscript>S<Subscript>14</Subscript>)

Mn²⁺Sb₂S₄, a monoclinic dimorph of clerite, and benavidesite (Mn²⁺Pb₄Sb₆S₁₄) show well-individualized single chains of manganese atoms in octahedral coordination. Their magnetic structures are presented and compared with those of iron derivatives, berthierite (Fe²⁺Sb₂S₄) and jamesonite (Fe²⁺Pb₄Sb₆S₁₄). Within chains, interactions are antiferromagnetic. Like berthierite, MnSb₂S₄ shows a spiral magnetic structure with an incommensurate 1D propagation vector [0, 0.369, 0], unchanged with temperature. In berthierite, the interactions between identical chains are antiferromagnetic, whereas in MnSb₂S₄ interactions between chains are ferromagnetic along c-axis. Below 6 K, jamesonite and benavidesite have commensurate magnetic structures with the same propagation vector [0.5, 0, 0]: jamesonite is a canted ferromagnet and iron magnetic moments are mainly oriented along the a-axis, whereas for benavidesite, no angle of canting is detected, and manganese magnetic moments are oriented along b-axis. Below 30 K, for both compounds, one-dimensional magnetic ordering or correlations are visible in the neutron diagrams and persist down to 1.4 K.     

The electric field gradient in natural iron-doped chrysoberyl Al<Subscript>2</Subscript>BeO<Subscript>4</Subscript> and sinhalite MgAlBO<Subscript>4</Subscript> single crystals

This work reports on the evaluation of the electric field gradient (EFG) in natural chrysoberyl Al₂BeO₄ and sinhalite MgAlBO₄ using two different procedures: (1) experimental, with single crystal Mössbauer spectroscopy (SCMBS) on the three principal sections of each sample and (2) a “fully quantitative” method with cluster molecular orbital calculations based on the density functional theory. Whereas the experimental and theoretical results for the EFG tensor are in quantitative agreement, the calculated isomer shifts and optical d–d-transitions exhibit systematic deviations from the measured values. These deviations indicate that the substitution of Al and Mg with iron should be accompanied by considerable local expansion of the coordination octahedra.     

In situ high-temperature X-ray and neutron powder diffraction study of cation partitioning in synthetic Mg(Fe<Subscript>0.5</Subscript>Al<Subscript>0.5</Subscript>)<Subscript>2</Subscript>O<Subscript>4</Subscript> spinel

The intra-crystalline cation partitioning over T- and M-sites in a synthetic Mg(Fe,Al)₂O₄ spinel sample has been determined as a function of temperature by Rietveld structure refinements from powder diffraction data, combining in situ high-temperature neutron powder diffraction (NPD; POLARIS diffractometer, at ISIS, Rutherford Appleton Laboratory, UK), to determine the Mg and Al occupancy factors, with in situ high-temperature X-ray powder diffraction, to fix the Fe³⁺ distribution. The results obtained agree with a two-stage reaction, in which an initial exchange between Fe³⁺ and Mg, the former leaving and the latter entering tetrahedral sites, is successively followed by a rearrangement involving also Al. The measured cation distribution has then been compared and discussed with that calculated by the Maximum Configuration Entropy principle, for which only NPD patterns have been used. The cation partitioning has finally been interpreted in the light of the configuration model of O’Neill and Navrotsky.     

Thermodynamic properties,low-temperature heat-capacity anomalies,and single-crystal X-ray refinement of hydronium jarosite, (H<Subscript>3</Subscript>O)Fe<Subscript>3</Subscript>(SO<Subscript>4</Subscript>)<Subscript>2</Subscript>(OH)<Subscript>6</Subscript>

Crystals of hydronium jarosite were synthesized by hydrothermal treatment of Fe(III)–SO₄ solutions. Single-crystal XRD refinement with R₁=0.0232 for the unique observed reflections (|F_o| > 4_F) and wR₂=0.0451 for all data gave a=7.3559(8) Å, c=17.019(3) Å, V^o=160.11(4) cm³, and fractional positions for all atoms except the H in the H₃O groups. The chemical composition of this sample is described by the formula (H₃O)_0.91Fe_2.91(SO₄)₂[(OH)_5.64(H₂O)_0.18]. The enthalpy of formation (H^o_f) is –3694.5 ± 4.6 kJ mol^–1, calculated from acid (5.0 N HCl) solution calorimetry data for hydronium jarosite, -FeOOH, MgO, H₂O, and -MgSO₄. The entropy at standard temperature and pressure (S^o) is 438.9±0.7 J mol^–1 K^–1, calculated from adiabatic and semi-adiabatic calorimetry data. The heat capacity (C_p) data between 273 and 400 K were fitted to a Maier-Kelley polynomial C_p(T in K)=280.6 + 0.6149T–3199700T^–2. The Gibbs free energy of formation is –3162.2 ± 4.6 kJ mol^–1. Speciation and activity calculations for Fe(III)–SO₄ solutions show that these new thermodynamic data reproduce the results of solubility experiments with hydronium jarosite. A spin-glass freezing transition was manifested as a broad anomaly in the C_p data, and as a broad maximum in the zero-field-cooled magnetic susceptibility data at 16.5 K. Another anomaly in C_p, below 0.7 K, has been tentatively attributed to spin cluster tunneling. A set of thermodynamic values for an ideal composition end member (H₃O)Fe₃(SO₄)₂(OH)₆ was estimated: G^o_f= –3226.4 ± 4.6 kJ mol^–1, H^o_f=–3770.2 ± 4.6 kJ mol^–1, S^o=448.2 ± 0.7 J mol^–1 K^–1, C_p (T in K)=287.2 + 0.6281T–3286000T^–2 (between 273 and 400 K).     

The crystal structure of alumoklyuchevskite,K<Subscript>3</Subscript>Cu<Subscript>3</Subscript>AlO<Subscript>2</Subscript>(SO<Subscript>4</Subscript>)<Subscript>4</Subscript>

The crystal structure of the unstable mineral alumoklyuchevskite K₃Cu₃AlO₂(SO₄)₄ [monoclinic, I2, a = 18.772(7), b = 4.967(2), c = 18.468(7) Å, β = 101.66(1)°, V = 1686(1) Å] was refined to R ₁ = 0.131 for 2450 unique reflections with F ≥ 4σF _hkl. The structure is based on oxocentered tetrahedrons (OAlCu ₃ ⁷⁺ ) linked into chains via edges. Each chain is surrounded by SO₄ tetrahedrons forming a structural complex. Each complex is elongated along the b axis. This type of crystal structure was also found in other fumarole minerals of the Great Tolbachik Fissure Eruption (GTFE, Kamchatka Peninsula, Russia, 1975–1976), klyuchevskite, K₃Cu₃Fe³⁺O₂(SO₄)₄; and piypite, K₂Cu₂O(SO₄)₂.     

Crystal chemistry of natural and synthetic lead oxyhalides. Part I. Crystal structure of Pb<Subscript>13</Subscript>O<Subscript>10</Subscript>Cl<Subscript>6</Subscript>

Crystals of lead oxychloride Pb₁₃O₁₀Cl₆ have been synthesized on the basis of high-temperature solid-state reactions. The Pb₁₃O₁₀Cl₆ structure was studied using X-ray single-crystal diffraction analysis. The compound is monoclinic, and the space group is C2/c; the unit-cell dimensions are a = 16.1699(14), b = 7.0086(6), c = 23.578(2) Å, β = 97.75°, and V = 2647.6(4) ų. The structure has been solved by direct methods and refined to R ₁ = 0.0505 for 2671 observed unique reflections. The structure is a 3D framework consisting of OPb₄ tetrahedrons. Chlorine atoms are located in the framework channels. The structure contains seven symmetrically independent Pb atoms, which are coordinated by 2 to 4 O^2? and 2 to 4 Cl^? anions. The synthesized compound is compared with other natural and synthetic lead oxyhalides.     

High-pressure thermo-elastic properties of beryl (Al<Subscript>4</Subscript>Be<Subscript>6</Subscript>Si<Subscript>12</Subscript>O<Subscript>36</Subscript>) from ab initio calculations,and observations about the source of thermal expansion

Ab initio calculations of thermo-elastic properties of beryl (Al₄Be₆Si₁₂O₃₆) have been carried out at the hybrid HF/DFT level by using the B3LYP and WC1LYP Hamiltonians. Static geometries and vibrational frequencies were calculated at different values of the unit cell volume to get static pressure and mode-γ Grüneisen’s parameters. Zero point and thermal pressures were calculated by following a standard statistical-thermodynamics approach, within the limit of the quasi-harmonic approximation, and added to the static pressure at each volume, to get the total pressure (P) as a function of both temperature (T) and cell volume (V). The resulting P(V, T) curves were fitted by appropriate EoS’, to get bulk modulus (K ₀) and its derivative (K′), at different temperatures. The calculation successfully reproduced the available experimental data concerning compressibility at room temperature (the WC1LYP Hamiltonian provided K ₀ and K′ values of 180.2 Gpa and 4.0, respectively) and the low values observed for the thermal expansion coefficient. A zone-centre soft mode \( P6/mcc \to P\bar{1} \) phase transition was predicted to occur at a pressure of about 14 GPa; the reduction of the frequency of the soft vibrational mode, as the pressure is increased, and the similar behaviour of the majority of the low-frequency modes, provided an explanation of the thermal behaviour of the crystal, which is consistent with the RUM model (Rigid Unit Model; Dove et al. in Miner Mag 59:629–639, 1995), where the negative contribution to thermal expansion is ascribed to a geometric effect connected to the tilting of rigid polyhedra in framework silicates.     

Stability of (Cs,K)Al<Subscript>4</Subscript>Be<Subscript>5</Subscript>B<Subscript>11</Subscript>O<Subscript>28</Subscript> (londonite) at high pressure and high temperature: a potential neutron absorber material

The stability and the thermo-elastic behaviour of a natural londonite

Minerals at high pressure. Mechanics of compression from quantum mechanical calculations in a case study: the beryl (Al<Subscript>4</Subscript>Be<Subscript>6</Subscript>Si<Subscript>12</Subscript>O<Subscript>36</Subscript>)

The Bader topological analysis has been applied to ab initio computed electron densities of beryl, in order to clarify its mechanism of compression. Full structural optimization and total energy (E) calculations were performed at different cell volumes (V _c). The pressure at each volume and the equation of state were estimated from the first and second derivatives of the resultant E(V _c) curve. The total (negative) potential energy of the crystal, sum of both attractive and repulsive electrostatic terms, was found to systematically decrease (i.e., it moved to more negative values) up to the highest pressure considered (28.4 GPa), indicating that interelectronic and internuclear repulsions are not the only terms controlling the compressibility, at least in the pressure range investigated. Electronic kinetic energy increases as the cell volume is reduced, leading to a parallel increase of the total energy. Both structure at equilibrium and compressibility are therefore due to the balance between the opposing kinetic and potential energy terms. The Bader theory has been used to identify the topological atoms within the structure and to calculate their properties, with particular attention to the forces driving the structural relaxation at high pressure. On a qualitative basis, the obtained results are expected to be transferable to the discussion of compressibility of other mineral phases.     

Fine structure in photoluminescence spectrum of S<Subscript>2</Subscript><Superscript>−</Superscript> center in sodalite

The photoluminescence and excitation spectra of sodalites from Greenland, Canada and Xinjiang (China) are observed at 300 and 10 K in detail. The features of the emission and excitation spectra of the orange-yellow fluorescence of these sodalites are independent of the locality. The emission spectra at 300 and 10 K consist of a broad band with a series of peaks and a maximum peak at 648 and 645.9 nm, respectively. The excitation spectra obtained by monitoring the orange-yellow fluorescence at 300 and 10 K consist of a main band with a peak at 392 nm. The luminescence efficiency of the heat-treated sodalite from Xinjiang is about seven times as high as that of untreated natural sodalite. The emission spectrum of the S₂ ⁻ center in sodalite at 10 K consists of a band with a clearly resolved structure with a series of maxima spaced about 560 cm⁻¹ (20–25 nm) apart. Each narrow band at 10 K shows a fine structure consisting of a small peak due to the stretching vibration of the isotopic species of ³²S³⁴S⁻, a main peak due to that of the isotopic species of ³²S₂ ⁻ and five peaks due to phonon sidebands of the main peak.     

Elasticity of CaIrO<Subscript>3</Subscript> with perovskite and post-perovskite structure

Compression behaviors of CaIrO₃ with perovskite (Pv) and post-perovskite (pPv) structures have been investigated up to 31.0(1.0) and 35.3(1) GPa at room temperature, respectively, in a diamond-anvil cell with hydrostatic pressure media. CaIrO₃ Pv and pPv phases were compressed with the axial compressibility of β _a > β _c > β _b and β _b > β _a > β _c, respectively and no phase transition was observed in both phases up to the highest pressure in the present study. The order of axial compressibility for pPv phase is consistent with the crystallographic consideration for layer structured materials and previous experimental results. On the other hand, Pv phase shows anomalous compression behavior in b axis, which exhibit constant or slightly expanded above 13 GPa, although the applied pressure remained hydrostatic. Volume difference between Pv and pPv phases was gradually decreased with increasing pressure and this is consistent with the results of theoretical study based on the ab initio calculation. Present results, combined with theoretical study, suggest that these complicate compression behaviors in CaIrO₃ under high pressure might be caused by the partially filled electron of Ir⁴⁺. Special attention must be paid in case of using CaIrO₃ as analog materials to MgSiO₃, although CaIrO₃ exhibits interesting physical properties under high pressure.