Correlations between 11B NMR parameters and structural characters in borate and borosilicate minerals investigated by high-resolution MAS NMR and ab initio calculations

Borates consisting of diverse fundamental building blocks (FBB) formed from complex polymerization of planar triangular [Bϕ₃] groups and tetrahedral [Bϕ₄] groups, where ϕ = O and OH, provide an excellent opportunity for investigation of correlations between the NMR parameters and local structures. However, previous studies suggested that the ¹¹B NMR parameters in borates are insensitive to local structural environments other than the B coordination number, in contrast to those documented for ²⁹Si, ²³Na and ²⁷Al in silicates, and no correlation between ¹¹B chemical shifts and the sum of bond valences has been established for borate minerals with hydroxyl groups or molecular water in the structures. In this study, high-resolution NMR spectra have been acquired at the ultra high field of 21 T as well as at 14 T for selected borate and borosilicate minerals, and have been used to extract high-precision NMR parameters by using combined ab initio theoretical calculations and spectral simulations. These new NMR parameters reveal subtle correlations with various structural characters, especially the effects of the ¹¹B chemical shifts from the bridging oxygen atom(s), site symmetry, symmetry of FBB, the sum of bond valences, as well as the next-nearest-neighbor cations and hydrogen bonding. Also, these results provide new insights into the shielding mechanism for ¹¹B in borate and borosilicate minerals. In particular, this study demonstrates that the small variation in ¹¹B chemical shifts can still be used to probe the local structural environments and that the established correlations can be used to investigate the structural details in borates and amorphous materials.     

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...     

Extraction of potassium from biotite by Ba<Superscript>2+</Superscript>/K<Superscript>+</Superscript> ion exchange and the structural transformation

Potassium has been extracted successfully from biotite by Ba²⁺/K⁺ ion exchange. The potassium release rate increased along S-curve versus reaction time. The maximum of potassium release rate was about 96 %. Powder X-ray diffraction spectroscopy, Fourier transform infrared spectroscopy, and transmission electron microscopy were used to characterize the obtained samples to reveal the exchanging behavior and structural transformation. The results showed that after treated with Ba(NO₃)₂ four times the original biotite transformed to vermiculite-type hydrated Ba-mica. The (001) basal plane was expanded from 1.000 nm of biotite to 1.221 nm of hydrated Ba-mica. Because of the “vacancy effect,” the Ba²⁺ has two different statuses, causing the structural water vibration of vermiculite-type hydrated Ba-mica split. The edge of vermiculite-type hydrated Ba-mica was crimped compared with the flat edge of original biotite. The (001) basal plane of dehydrated Ba-mica was also split, supporting the “vacancy effect.”     

An infrared and <Superscript>1</Superscript>H MAS NMR investigation of strong hydrogen bonding in ussingite,Na<Subscript>2</Subscript>AlSi<Subscript>3</Subscript>O<Subscript>8</Subscript>(OH)

The mineral ussingite, Na₂AlSi₃O₈(OH), an interrupted tectosilicate, has strong hydrogen bonding between OH and the other nonbridging oxygen atom in the structure. Infrared spectra contain a strongly polarized, very broad OH-stretching band with an ill-defined maximum between 1500 and 1800 cm^–1, and a possible OH librational bending mode at 1295 cm^–1. The IR spectra confirm the orientation of the OH vector within the triclinic unit cell as determined from X-ray refinement (Rossi et al. 1974). There are three distinct bands in the ¹H NMR spectrum of ussingite: a predominant band at 13.5 ppm (TMS) representing 90% of the structural hydrogen, a second band at 15.9 ppm corresponding to 8% of the protons, and a third band at 11.0 ppm accounting for the remaining 2% of structural hydrogen. From the correlation between hydrogen bond length and ¹H NMR chemical shift (Sternberg and Brunner 1994), the predominant hydrogen bond length (H...O) was calculated to be 1.49 Å, in comparison to the hydrogen bond length determined from X-ray refinement (1.54 Å). The population of protons at 15.9 ppm is consistent with 5–8% Al–Si disorder. Although the ussingite crystal structure and composition are similar to those of low albite, the bonding environment of OH in low albite and other feldspars, as characterized through IR and ¹H NMR, is fundamentally different from the strong hydrogen bonding found in ussingite.     

Discrimination of explosions and earthquakes: An example based on spectra and source parameters of the 11<Superscript>th</Superscript> May 1998 Pokhran explosion and the 9<Superscript>th</Superscript> April 2009 earthquake

We compare the P-, S- and Lg- spectra of the 11^th May, 1998 Pokhran underground nuclear explosion (NE) with those of an earthquake (EQ) of comparable magnitude that occurred in its vicinity (~100 km west) on 9^th April, 2009, utilizing the waveforms recorded by a Global Seismograph Network station at Nilore (NIL), Pakistan. The contiguous occurrence of these events and the similarity of the travel paths provided a good opportunity to discriminate the nature of the sources. Our results suggest that the Pn/Lg and Pn/Sn amplitude ratios of the explosion and earthquake waveforms exhibit distinct differences in the higher frequency window. Further, since the P-phases have high signal to noise ratio compared to their S counterparts, we utilize their spectra to derive the source parameters of the NE and EQ sources. Our results show that the seismic moment, corner frequency and source dimension of the explosion are ~1.58X10¹⁷ Nm, 1.18 Hz and ~0.793 km respectively. The moment magnitude (M_W) and surface wave magnitude (M_S) for the nuclear explosion are estimated to be ~5.4 and ~3.57 respectively. The values of M_W (5.3) and M_S (4.3) obtained by us for the earthquake are consistent with the estimates in the Harvard catalog and earlier published results. The estimate of M_W for the nuclear explosion was hitherto not available. Lastly, we estimate the yield of the NE to be ~50 kt from the surface wave magnitude and discuss the various limitations related to its estimation.     

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.     

Insights into oxygen-cation bonding in fresnoite-type structures from O <Emphasis Type="Italic">K</Emphasis>- and Ti <Emphasis Type="Italic">L</Emphasis><Subscript>23</Subscript>-electron energy-loss spectra and ab initio calculations of the electronic structure

O K- and Ti L₂₃-core-loss spectra of fresnoite Ba₂TiSi₂O₈ (BTS) and Sr₂TiSi₂O₈ (STS), which is isotypic to BTS, have been measured by electron energy-loss spectroscopy (EELS). The energy-loss near-edge structures (ELNES) of the O K edge have been identified on the basis of theoretical simulations and interpretations of the X-ray absorption near-edge structures (XANES), which have been modelled in the framework of self-consistent full multiple-scattering (FMS) theory using FEFF8. Herewith, the K-absorption spectra of oxygen (E) and the local partial electron density of states (DOS) of all atoms have been calculated. For BTS, the observed spectral features in the O K-edge spectra are interpreted in terms of mixing between the central O p and neighbouring Ba 5d and 4f, Si 3p and 3d, and Ti 3d orbitals. The observed differences in the O K-edge spectra for STS and BTS can mainly be attributed to three properties: (1) The lack of high local partial Sr unoccupied DOS with 4f symmetry near the Fermi level compared to the high Ba 4f unoccupied DOS results in differences of overlapping O 2p – cation orbitals. (2) The differences in the ionic radii of Sr and Ba result in a larger unit cell for BTS and, thus, in larger oxygen-cation bonding distances. (3) In comparison to STS, the strength of the incommensurate 2-D structural modulation is significantly weaker in BTS, i.e. distortions of coordination polyhedra occur to a much lesser extent. All these effects alter the oxygen-cation hybridization and, hence, result in a variation of the O 1s p transition and consequently of the O K-edge spectral shape. The observed peak broadening in Ti L₂₃ ELNES of STS compared to BTS is correlated with strong displacive modulations hosted in STS.     

Probing the relationship between surface waters and aquifers by <Superscript>18</Superscript>O measurements on the top of the Araripe Plateau/NE Brazil

The Araripe Plateau in northeastern Brazil has an area of about 8,000 km², confined by 39°05E and 40°55E, and 7°10S and 7°50S. Due to high permeability of soils, a surface drainage system is practically inexistent. Water is stored in excavations with clayey soil, the barreiros. Monthly samples were taken for ¹⁸O measurements, from September 1999 to August 2000, from four barreiros, three dug wells and five drilled wells. Results show that (1) groundwaters in the eastern part of the plateau are derived from present-day rainfall (¹⁸O–3.2), whereas groundwaters in the western portion are isotopically different (¹⁸O–5.0); (2) barreiros are strongly marked seasonally by elevated ¹⁸O during the dry period due to elevated evaporation; (3) a dug well at a distance of 30 m from a barreiro exhibits ¹⁸O similar to that of the reservoir, indicating a strong interaction between groundwater and surface water; and (4) a tubular well of 242-m depth, located in a fault, exhibits strong seasonal changes in ¹⁸O and electrical conductivity, revealing downward leakage between aquifers.