The positions of H+, Li+ and Na+ impurities in beryl     

Lars Olov Andersson 《Physics and Chemistry of Minerals》2006,33(6):403-416

Electron Paramagnetic Resonance (EPR) measurements show that Li⁺ impurities are located at two different positions in beryl, one in the crystal lattice and the other in the crystal channel. The position of the Li⁺ impurity in the lattice is generally assumed to be at the site of a missing Be²⁺ ion. It is shown that this is not the case, but that the Li⁺ ion is located in a tetrahedron formed by the oxygens of one side of the Be tetrahedron and the nearest oxygen in the channel ring. This Li site has the coordinates (0.423, 0.344, 0.167) and can only be occupied when the neighbouring Be site is empty. There are four such sites around every Be tetrahedron at the distance of 1.46 Å from the Be site. The distance from the Li site to the oxygens of the Li tetrahedron is 1.84 Å. This compares favourably with the much smaller distance of 1.65 Å in the Be tetrahedron. Protons in beryl are trapped at or near these Li sites. Na⁺ is known to be located at the 2b position at the center of the silicate rings, where it is stabilized by one water molecule located at each of the two surrounding 2a sites. This is also the position of Li⁺ in the beryl channel. It is found that the presence of Na⁺ in the ring of six oxygens reduces the radius of this ring. The Na⁺ impurity has also been supposed to be located at position 2a alone and at 2b stabilized by only one water molecule. It is now proposed that Na⁺ and H₂O are located together in the Al–Be plane when only one water molecule is associated with Na⁺. The water oxygen is located at or near 2a and Na is closer to the Be site in tetrahedral beryl and closer to the Al site in octahedral beryl. It is proposed that the water protons are also located in the Al–Be plane, which would mean that there exists a third type of water in beryl. The origin of protons and OH^? ions in beryl is discussed and it is suggested that the plugs in the beryl channels are CO ₃ ^2? ions. Diffusion of OH^? ions and natural radiation may have led to the creation of NO₃ and the blue colour of Maxixe beryl.  相似文献   

Application of electron paramagnetic resonance spectroscopy to examination of carbonized coal blends     

B. Pilawa  S. Pusz  M. Krzesi&#x;ska  A. Koszorek  B. Kwieci&#x;ska 《International Journal of Coal Geology》2009,77(3-4):372-376

Paramagnetic centers in two- and three-component coal blends carbonized at 1000 °C were studied by X-band (9.3 GHz) electron paramagnetic resonance (EPR) technique. The blends were prepared from three different Polish coals with carbon contents [wt.%]: 88.66, 86.21, and 82.67, respectively. The aim of this work was to compare EPR parameters and concentrations of paramagnetic centers in the initial and carbonized coal samples. Furthermore the spin–spin and spin–lattice interactions were characterized.EPR spectra were measured with magnetic modulation 100 kHz and microwave power 0.7 mW. Amplitudes and linewidths of EPR spectra were obtained. g-Factors were calculated from resonance condition. Concentrations of paramagnetic centers in the samples were determined. Influence of microwave power in the range 0.7–70 mW on EPR spectra was analyzed.All the studied samples revealed paramagnetism. Unpaired electrons are localized in the same atoms, because similar g-values in the range 2.0035–2.0038 were obtained for all the original samples. The EPR parameters of coal blends were additive in comparison with the parent coals. EPR spectra strongly changed after carbonization of the coal samples. Narrower EPR lines were measured for the original coal samples than for carbonized ones. We detected lower concentrations of paramagnetic centers in carbonized three-component coal blends than in two-component carbonized blends. EPR lines of the studied carbonized blends were not saturated at the microwave power used, which suggests fast spin–lattice relaxation processes in the samples. EPR examination proved chemical interactions between coal constituents during carbonization of coal blends.  相似文献   

Radiation-induced defects in quartz. III. Single-crystal EPR,ENDOR and ESEEM study of a peroxy radical     

Mark J. Nilges  Yuanming Pan  Rudolf I. Mashkovtsev 《Physics and Chemistry of Minerals》2009,36(2):61-73

The X- and W-band single-crystal electron paramagnetic resonance spectra of an electron-irradiated natural quartz permit quantitative analysis of a ²⁹Si hyperfine structure (A ~12.6 MHz) and an ²⁷Al hyperfine structure (A ≤ 0.8 MHz) for a previously reported hole-like center. The ²⁹Si hyperfine structure arises from interaction with two equivalent Si atoms and is characterized by the direction of the unique A axis close to a Si–O bond direction. The ²⁷Al hyperfine structure, confirmed by pulsed electron nuclear double resonance and electron spin echo envelope modulation spectra, is characterized by the unique A axis approximately along a twofold symmetry axis. These ²⁹Si and ²⁷Al hyperfine data, together with published theoretical results on peroxy radicals in SiO₂ as well as our own density functional theory (DFT) calculations on model peroxy centers, suggest this hole-like center to have the unpaired spin on a pair of oxygen atoms linked to two symmetrically equivalent Si atoms and a substitutional Al³⁺ ion across the c-axis channel, a first peroxy radical in quartz. The nuclear quadrupole matrix P also suggests that the Al³⁺ ion corresponds closely to the diamagnetic precursor to the [AlO₄]⁰ center. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

Induced modifications of kaolinite under ionizing radiation: an infrared spectroscopic study     

C. Fourdrin  E. Balan  T. Allard  C. Boukari  G. Calas 《Physics and Chemistry of Minerals》2009,36(5):291-299

Radiation effects on kaolinite were investigated using He⁺ ions of 1.5 MeV at radiation doses up to 4.3 × 10⁸ Gy, which are comparable to the doses expected for clay barriers in high-level nuclear waste repositories. The concentration of paramagnetic radiation-induced defects in kaolinite reaches 2 × 10¹⁶ spins/mg (400 at. ppm), as determined by electron paramagnetic resonance spectroscopy. The broadening of X-ray diffraction patterns and transmission infrared (IR) absorption bands is mostly related to the structural strain induced by radiation-induced point defects. The broadening of IR absorption spectra is analyzed using an autocorrelation approach and is related to a change in the distribution of vibrational frequencies due to crystal heterogeneities. We theoretically analyze how the effective dielectric properties of kaolinite samples depend on macroscopic parameters and how irradiation can modify some of them. Irradiation leads to an increase in the electronic polarizability of kaolinite particles, related to the accumulation of radiation-induced electronic point defects.  相似文献   

Electron paramagnetic resonance (EPR) spectroscopy in massive sulphide exploration, Rosebery mine area, western Tasmania, Australia     

Aung Pwa  J. C. van Moort 《Journal of Geochemical Exploration》1999,65(2):291

Electron paramagnetic resonance (EPR) spectroscopy of hot HNO₃ insoluble residues of rock powders is used as a new exploration technique for the volcanic-hosted massive sulphide (VHMS) deposit in the Rosebery mine area. The EPR signal intensities measured in 326.5±5 mT sweeps are strong in the altered rocks, and show a negative correlation with Ca, Na and Sr, and a positive correlation with K/Na, Rb/Sr and (K × Rb)/(Ca × Na × Sr). The EPR intensities measured in 326.5±100 mT sweeps show high values in the footwall pyroclastics, host rocks and hanging wall pyroclastics near and around the Rosebery deposit, and correlate positively with K, Fe, Mn, Ba, F, Rb, Zn, Pb and Zr. The Rosebery deposit and associated footwall alteration zone are located at the intersection of two elongated paramagnetic halos. The first is characterized by strong intensities of [AlO₄]° signals measured at magnetic flux density sweeps over 326.5±5 mT, trends NE–SW, and passes discordantly from the west to the east the White Spur Formation, altered footwall (footwall alteration zone), host rock of the Rosebery deposit, hanging wall and Mount Black Volcanics. The second, largely stratabound, halo is defined by strong intensities of Mn²⁺ sextets observed at magnetic flux density sweeps over 326.5±100 mT, runs N–S following the stratigraphic trend, and outlines the mineralized host rock and footwall alteration zone. It also extends toward the south into the unaltered footwall and hanging wall rocks. The first type of halo is considered to be related to wall rock alteration due to the VHMS mineralization processes as well to later Devonian metamorphism, and the second is thought to be related to massive sulphide mineralization alone.  相似文献   

太湖流域排污权交易优化目标模型及方案配置研究     

朱德明  李洁 《湖泊科学》2004,16(Z1):182-187

根据江苏省太湖流域水环境与社会经济特征,建立主要污染物排污权交易优化目标模型;以重点工业污染企业为样本,对排污权交易初始方案实施的预期效果进行定量分析,提出开展排污权交易制度的政策建议.  相似文献   

Spectroscopic Characterization of Organic Structures and Organic‐Inorganic Interactions in Paper Mill Sludge     

Claudia M. B. F. Maia  Fabio Simonelli  Antinio S. Mangrich 《洁净——土壤、空气、水》2001,28(7):372-377

The organic composition and organic‐inorganic interaction in paper mill sludge (PS) solvent extracts (hexane, ethyl acetate, acetone and ethanol) and humic fractions, humic acid (HA) and humin (HU) were studied by electron paramagnetic resonance spectroscopy (EPR), proton and carbon‐13 nuclear magnetic resonance spectroscopy (¹H NMR; ¹³C NMR), Fourier‐transformed infrared spectroscopy (FTIR), and ultraviolet‐visible spectroscopy (UV‐vis). The strategy of fractionating the PS, sequentially, with organic solvents of increasing polarity is a reliable analytical procedure for humic substance sample separation because it results in more purified fractions. FTIR, ¹H NMR and ¹³C NMR results showed that hexane extract consisted mainly of aliphatic hydrocarbon structures. Their contents in the extracts decreased as the polarity of the extracting solvent increased and the content of oxygen functional groups increased. Carboxylic and carboxylate functional groups were found in the acetone extract, and ester and ether functions were predominantly found in the ethanol extract. EPR spectra revealed some Fe³⁺ complexes with rhombic structure (g₁ = 4.3; g₂ = 9.0) in the humic fractions and in all solvent extracts, except hexane. Quasi‐octahedral Fe³⁺ complexes (g = 2.3; ΔH_pp ≤ 400 G) were found in the HU fraction and in the acetone extract. The organic free radical content in the HA fraction was higher than the non‐fractionated PS sample and HU fraction.  相似文献   

Radiation-induced defects in quartz. II. Single-crystal W-band EPR study of a natural citrine quartz   总被引：1，自引：1，他引：0  

Yuanming Pan  Mark J. Nilges  Rudolf I. Mashkovtsev 《Physics and Chemistry of Minerals》2008,35(7):387-397

Single-crystal electron paramagnetic resonance (EPR) spectra of a natural citrine quartz without any artificial irradiation, measured at W-band frequencies (∼94 GHz) and temperatures of 77, 110 and 298 K, allow better characterization of three previously-reported Centers (#6, #7 and B) and discovery of three new defects (B′, C′ and G′). The W-band EPR spectra reveal that Centers #6 and #7 do not reside on twofold symmetry axes, contrary to results from a previous X-band EPR study. The W-band spectra also show that the previously reported Center B is a mixture of two defects (B and B′) with similar g matrices but different-sized ²⁷Al hyperfine structures. Center C′ has similar principal g values to the previously reported Center C but is distinct from the latter by a larger ²⁷Al hyperfine structure with splittings from 0.10 to 0.22 mT. Also, Center G′ has a similar g matrix to the previously reported Center G but a different ²⁷Al hyperfine structure with splittings from 0.41 to 0.53 mT. These spin-Hamiltonian parameters, together with observed thermal properties and microwave-power dependence, suggest that Centers #6 and #7 probably represent O₂³⁻ type defects. Centers B and B′ are probably superoxide radicals (O₂⁻) with the unpaired spin localized on the same pair of oxygen atoms around a missing Si atom but linked to a substitutional Al³⁺ ion each at different neighboring tetrahedral sites. Similarly, Centers G and G′ are most likely superoxide radicals with the unpaired spin localized on another pair of oxygen atoms around a missing Si atom and linked to a substitutional Al³⁺ ion each at different neighboring tetrahedral sites. Center C′ is probably an ozonide radical associated with a missing Si atom and linked to a substitutional Al³⁺ ion at the neighboring tetrahedral site. This study exemplifies the value of  high-frequency EPR for discrimination of  similar defect centers and determination of  small local structural distortions that are often difficult to resolve in conventional  X- and Q-band EPR studies.  相似文献   

EPR study of coordination of Ag and Pb cations in BaB<Subscript>2</Subscript>O<Subscript>4</Subscript> crystals and barium borate glasses     

V. P. Solntsev  R. I. Mashkovtsev  A. V. Davydov  E. G. Tsvetkov 《Physics and Chemistry of Minerals》2008,35(6):311-320

It is shown the possibility to determine the coordination of paramagnetic ions in disordered solid structures, e.g., in barium borate glasses. For this purpose the electron paramagnetic resonance (EPR) method was used to study α-and β-BaB₂O₄ crystals and glasses of 45·BaO × 55·B₂O₃ and 40·BaO × 60·B₂O₃ (mol%) composition activated by Ag⁺ and Pb²⁺ ions. After the samples were exposed to X-rays at 77 K, different EPR centers were observed in them. In α-and β-BaB₂O₄ crystals and glasses the EPR centers Ag²⁺, Ag⁰, Pb⁺, Pb³⁺, and hole centers of O⁻ type were studied. The EPR parameters of these centers and their arrangement in crystal structure were determined. It is shown that Pb³⁺ ions in β-BaB₂O₄ crystals occupy Ba²⁺ position in an irregular polyhedron from the eight oxygen, whereas in α-BaB₂O₄ crystals they occupy Bа₂ position in a sixfold coordination. Pb⁺ ions in α-BaB₂O₄ crystals occupy Bа₁ position in a ninefold coordination from oxygen. In barium borate glasses, Pb³⁺ ions were studied in coordination polyhedron from six oxygen atoms and in a polyhedron from nine to ten oxygen atoms. It is assumed that the established difference in the structural position of Pb³⁺ ions in glasses is due to their previous incorporation in associative cation–anion complexes (AC) and “free” structure-forming cations (FC). Computer simulations have been performed to analyze the stability of specific associative complexes and to compare their bond lengths with experimental data.  相似文献   

Ionizing radiation-induced defects in smectite clays     

D. Gournis  A. E. Mantaka-Marketou  M. A. Karakassides  D. Petridis 《Physics and Chemistry of Minerals》2001,28(4):285-290

 The interaction of γ-rays with smectites induces paramagnetic defects in the structure of these clay minerals. The EPR spectra of three different smectites detect the creation of structural defects and trapping of organic free radicals in the clay structure upon irradiation. The defects are assigned to positive holes or trapped electrons stabilised by existing local charge imbalances in the mineral lattice. The organic radicals are derived from organic compounds present as impurities in the crystal lattice of the clay minerals. In addition, γ-rays cause migration of small interlayer cations (such as Li⁺) into the layers, as clearly evidenced by EPR and FT-IR reflectance spectroscopies. Received: 20 April 2000 / Accepted: 2 December 2000  相似文献