Electron paramagnetic resonance of phytofulgurite

Doklady Earth Sciences -     

Electron paramagnetic resonance studies on clinochlore from Longitudinal Valley area,northeastern Taiwan

A natural sample of clinochlore from the Longitudinal Valley area of northeastern Taiwan has been characterized by using the powder X-ray diffraction (XRD), differential thermal analysis and electron paramagnetic resonance (EPR) spectroscopic techniques. The lattice parameters of the monoclinic (IIb) clinochlore with the composition (Mg_2.988 Al_1.196 Fe_1.6845 Mn_0.026)_5.8945 (Si_2.559 Al_1.441)₄ O₁₀ (OH)₈ have been calculated from the powder XRD data and are found to be a = 5.347 Å, b = 9.223 Å, c = 14.250 Å, β = 97.2° and Z = 2. The thermal behaviour of the sample showed the typical behaviour of clinochlore with a hydroxyl content of 12.5 wt%. The EPR spectrum at room temperature exhibits two resonance signals centred at g ≈ 2.0 and g ≈ 8.0. The signal at g ≈ 2.0 shows a six-line hyperfine structure which is a characteristic of Mn²⁺ ions in octahedral symmetry. The resonance signal at g ≈ 8.0 is a characteristic of Fe³⁺ ions. The EPR spectra have also been recorded at different temperatures (123–295 K). The population of spin levels (N) has been calculated for g ≈ 2.0 and g ≈ 8.0 resonance signals. It is observed that N increases with decreasing temperature. From EPR spectra, the spin-Hamiltonian parameters have been evaluated. The zero-field splitting parameter (D) is found to be temperature dependent. The peak-to-peak width of the g ≈ 8.0 resonance signal is found to increase with decrease in temperature.     

Electron paramagnetic resonance study of iridium in forsterite

Electron paramagnetic resonance of Ir²⁺ in forsterite is studied at Q-band frequency and room temperature. There are four equivalent spectra superimposed along the three crystallographic axes. The individual spectrum consists of four hyperfine lines of approximately equal intensity separated from each other by 42 G; one axis of the g tensor is near the c axis. Ir²⁺ is certainly substituted for Mg²⁺. Because of the fourfold degeneracy of the EPR spectrum, it may be suggested that iridium occurs at M₁. Taking into account that one eigenvector of the g tensor is nearly parallel to c, it seems also possible that the substitution takes place at the M₂ position. In this case, the lattice relaxation of the crystal structure around Ir²⁺ at M₂ must break the point symmetry m at M₂.     

Electron paramagnetic resonance study of new paramagnetic centers in microcline-perthites from pegmatites

Four new types of paramagnetic centers — NH⁺ ₃, N^2?, Al-O^?, E ₁ — have been detected in microcline perthites from pegmatites in the Ukrainian Shield. Values are tabulated for their g and A tensors and limits of thermal stability determined. The NH⁺ ₃ center substitutes the K⁺ ion. It occurs naturally in potash feldspars but is intensified by gamma or X-ray irradiation. It is regarded as a radiational development of the more general NH⁺ ₄ ? K⁺ isomorphism. It disappears after heating to temperatures higher than 470 K. The N^2? center is an uncommon example of isomorphous substitution of a bridging oxygen, being located on a O _D(m) site between T ₂(o) and T ₁(m) silicon sites. It is stable to 820 K. The hole center, Al-O^?, has been detected on an O _A(l) oxygen shared by T ₁(o) and T ₁(m) tetrahedra. It is stable to 590 K. The E ₁ center in these alkali feldspars is similar to the E ₁ center in quartz, being an electron trapped in an oxygen vacancy in the O _B (o) position. It is stable to 420 K. The NH⁺ ₃, Al-O^? and E ₁ centers can be restored from temperatures above their stability limits by gamma radiation. Concentration of centers varies from sample to sample depending on conditions of formation and subsequent history of the minerals.     

Electron paramagnetic resonance and ENDOR studies of Cr3+ - Al3+ pairs in forsterite

The electron paramagnetic resonance (EPR) spectrum of Cr³⁺ in synthetic crystals of forsterite consists primarily of lines of Cr³⁺ “isolated” at the M1 and M2 positions in a “perfect” crystal environment without local charge compensation. In addition it shows two nonequivalent superhyperfine-split sextets with different intensities which are due to strong interaction of the Cr³⁺ electron spin S (S=3/2) with an adjacent nuclear spin I(I=5/2). Electron nuclear double resonance (ENDOR) experiments revealed that the sextets result from Cr³⁺ (M1) - Al³⁺ and Cr³⁺ (M2) - Al³⁺ pairs, Al being located at adjacent tetrahedral Si sites. The g, D, A, and A′ tensor components of the Cr³⁺ - Al³⁺ pairs have been determined at room temperature. The values of the pairs are distinct although they are not very different from the corresponding data of “isolated” Cr³⁺. From the intensities of the EPR spectra the relative concentration of the Cr³⁺ - Al³⁺ pairs with respect to “isolated” Cr³⁺ has been estimated.     

Adsorption of oxyanions by spent western oil shale: I. arsenate

The partitioning of arsenate between Paraho indirectly retorted and directly retorted oil shales and a combusted oil shale was examined with batch equilibrium adsorption isotherms. Arsenate adsorption was found to conform to the Freundlich adsorption model, and the combusted oil shale was found to have the greatest affinity for arsenate. The indirectly and directly retorted oil shale samples did not have statistically different affinities for arsenate. The greater adsorption capacity of combusted oil shale for arsenate was attributed to greater surface area and free iron oxide. Arsenate adsorption by combusted oil shale was not reversible. Upon dilution of the solution phase, arsenate did not desorb. Upon dilution of the retorted oil shale solutions, arsenate continued to be removed from solution. An evaluation of metal arsenate stability in the spent oil shale systems indicated that the retorted oil shale solutions were highly supersaturated with respect to magnesium and barium arsenates, whereas the combusted oil shale solutions were not supersaturated. The data were interpreted to indicate that adsorption reactions control arsenate solubility at short reaction times. As reaction times increase, precipitation reactions control soluble arsenate concentrations.     

Electron paramagnetic resonance,optical absorption,and magnetic circular dichroism studies of the CO 3 − molecular-ion in irradiated natural beryl

Room temperature X-irradiation of some natural beryls produced several new absorption lines in the electron paramagnetic resonance (EPR) spectrum, a known series of optical absorption lines in the 500–700 nm range, and a shift of the absorption edge to lower energies. Several of the new EPR lines and part of the irradiation-induced shift of the absorption edge disappeared after a few days at room temperature, and were not examined in detail. However, three of the paramagnetic centres responsible for the new EPR lines were stable at room temperature and two of these have previously been identified as atomic hydrogen and the methyl radical, CH₃. These species were stable to ～150 and ～450°C respectively. The third stable species, hitherto unreported, showed a single-line EPR spectrum of axial symmetry, with g∥=2.0051 and g⊥=2.0152. This spectrum was found to be intensity-correlated with the series of optical bands in the 500–700 nm range, after thermal bleaching at 175°C. The EPR and optical spectra are therefore assigned to the same species. It is argued that this species is the CO ₃ ^? molecular ion, located in the widest part of the structural channel and aligned with the plane of the molecule perpendicular to the c axis. The EPR spectrum is consistent with a ² A′₂ ground state of a CO ₃ ^? molecule with trigonal symmetry, and this requires that the optical transition has a ² A′₂ → ² E′ character. Most of the features in the optical spectrum can be assigned to coupling of a totally symmetric mode of frequency ～1020 cm^?1 onto a zero-phonon line at 14,490 cm^?1 and a second weaker line at 16,020 cm^?1. However, both of these two fundamental lines are structured, and the two components show strong temperature-dependent derivative-shaped magnetic circular dichroism (MCD). Furthermore, the overall sign of the MCD for the line at 16,020 cm^?1 is opposite to that at 14,490 cm^?1. The separation (～120 cm^?1) of the two components of the 14,490 cm^?1 line is much larger than that expected from spin-orbit interaction, and the origin of this splitting is not yet understood.     

Adsorption of oxyanions by spent western oil shale: II. selenite

The adsorption and desorption behavior of selenite by processed Green River Formation oil shales were examined. The selenite adsorption data could be quantitatively described by both the Freundlich and Langmuir isotherms. However, greaterR ² values were obtained for the Freundlich isotherms. Furthermore, selenite adsorption was not a function of the extraction process. The adsorption of selenite by the processed oil shales was irreversible. Upon dilution of the equilibrium systems, additional selenite removal from solution occurred. A thermochemical analysis of the adsorption and desorption equilibrium solutions indicated that the solutions were undersaturated with respect to a number of metal selenite solids. This indicates that precipitation processes are not influencing selenite behavior. However, not all selenite minerals were examined in the evaluation because of the lack of thermochemical data. An insufficient equilibration period for the adsorption study or the alteration of processed oil shale solids as a result of hydration reactions may also have hastened the additional removal of selenite during the desorption studies.     

Electron paramagnetic resonance and electron spin echo spectroscopy study of natural bornite

Summary A minero-chemical and spectroscopic characterisation has been performed on a natural bornite sample from the Natural History Museum of the University of Florence, through the use of EPMA, XRD, continuous-wave (cw) and pulsed EPR spectroscopy. The use of different EPR techniques allowed to fully investigate the distribution and valence states of Cu and Fe and to study the early oxidation products of bornite. The microanalytical and XRD characterisation proved bornite to be homogeneous and stoichiometric. Cw-EPR measurements confirmed the presence of Fe(III) as fundamental valence state in bornite; moreover, no evidence of Cu(II) as a bulk transient species, due to a charge transfer process, has been revealed. The broadening of the Fe(III) EPR spectrum is ascribed to a partial transfer of spin density from Fe(III) to the surrounding cationic sublattice. In contrast, the pulsed EPR experiments, registered at 4.2 K, revealed the presence of both Fe(III) and Cu(II). These species were supposed to be present at the early stage of the surface alteration. The data provided by the electron spin-echo decay and modulation suggest both the oxidised Cu(II) and Fe(III) species to belong to premature surface water adducts (evidenced by proton nuclear modulation), which may evolve to sulphate species.     

Electron paramagnetic resonance characteristics of the humic acids from a podzol

A study has been made of solid and solution electron paramagnetic resonance (EPR) spectra of humic acids from different horizons in a podzolic soil. Hyperfine splitting was observed in the solution spectra of humic acids from all horizons and depended on the strength of alkali and the period of dissolution. The upper organic horizons L, F and O₁ contained humic acids with some spectral characteristics in common with lignin. Humic acid from the lower horizons showed different spectra. At least 5 different radical signals were present.     

Electron paramagnetic resonance of the SO 4 3- radical in barite and celestite

The electron paramagnetic resonance (EPR) study of gammaor x-ray-irradiated natural barite and celestite has revealed the presence of a radiation center with principal values of the g tensor and the A tensor [MHz] of hyperfine interaction (from the ³³S isotope): g_xx=1.9963, g_yy=2.0073, g_zz=2.0025, A_xx=434, A_yy=447, A_zz=528 in BaSO₄, g_xx=1.9990, g_yy=2.0075, g_zz=2.0027, A_xx=426, A_yy=439, A_zz=520 in SrSO₄. The center has been identified as SO _3- ⁴ radical. The electron centers SO ₄ ^3- in barite have been found to be produced along with the hole centers SO ₄ ^3- , and maximum concentration of both centers is reached at a gamma-ray-radiation dose of about 5·10⁵ Gy. UV or thermal treatment causes both centers to disappear. The SO ₄ ^3- radicals proved to be more thermally stable than the SO ₄ ^3- radicals: within about 0.5 h the latter disappear at 125° C, whereas the former do so at 180° C.     

Electron paramagnetic resonance and polarized optical absorption spectra of Ni2+ in synthetic forsterite

The investigated Ni doped forsterite was grown with the floating zone technique. The EPR spectra were taken at room temperature using both 9.5 and 35 GHz. All specimens show EPR signals resulting from Mn²⁺ at M2 and Fe³⁺ at M1, M2, and Si positions. Ni²⁺ EPR signals are observed at 35 GHz but not at 9.5 GHz. The Ni²⁺ spectra are described by the spin Hamiltonian

Electron paramagnetic resonance of PO 2 2− and SO 2 − radicals in barite

Electron paramagnetic resonance (EPR) measurements of natural barite BaSO₄ have revealed the presence of PO ₂ ^2– and SO ₂ ^– ionic radicals. For the latter a hyperfine structure from the ³³S isotope has been detected and measured for the first time. The temperature dependence of the hyperfine interaction (HFI) constant of the PO ₂ ^2– and SO ₂ ^– radicals has been investigated in the 100–400 K range.     

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

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.     

Electron paramagnetic resonance spectroscopy: A suggested approach to trace metal analysis in marine environments

Electron paramagnetic resonance (EPR) spectroscopy analysis of marine samples from different environments appears to differentiate between adsorbed and structural Mn (II) and Fe (III) sites in the sediment. This suggests that EPR may provide a means of distinguishing different environmental influences on sediment. Acid extract solutions from sediment samples exhibit clearly defined EPR spectra due to Mn(II), Ti(III), Fe(III), and VO(IV), which are amenable to qualitative and quantitative analysis at concentrations below one part per million. Spectra of several shellfish vary considerably, both between species, and within a species, depending on sampling localities. Resonances from Mn(II), Mo(V), and Fe(III) can be obtained. Mn(II) is substituted for Ca(II) in the calcite structure of some shells. The low detection limits, small sample size, required and identification of oxidation states by EPR complement other analytical techniques and may prove useful in marine systems.     

Electron spin resonance and related studies of lignite and ball clay from South Devon,England

Electron spin resonance and infrared spectroscopic studies of lignite and ball clay from South Devon, and of extracts obtained from them by solvent fractionation, revealed similarities between corresponding organic components associated with both materials. All fractions exhibited a free radical resonance at g = 2.0037, which occurred with greatest intensity in the humic acids. Additional ESR features due to Fe³⁺, Mn²⁺ and VO²⁺ complexes were observed. Ferric ions give rise to resonances at g = 4.2 which have not been previously reported in the case of natural carbonaceous materials. It is shown that the paramagnetic species associated with the ball clay and lignite extracts do not significantly contribute to the observed ESR spectra of kaolinites, the latter being attributable to substituted Fe³⁺ ions and defect centres within the kaolinite lattice.     

页岩油分类与评价

页岩油是以游离(含凝析态)、吸附及溶解(可溶解于天然气、干酪根和残余水等)态等多种方式赋存于有效生烃泥页岩地层层系中且具有勘探开发意义的非气态烃类。根据泥页岩地层中所含烃类相态、成因机理及勘探开发等特点,将页岩类油气划分为页岩气和页岩油等两类八种。结合页岩油特点,指出了我国页岩油形成条件和分布规律,即规模分布的有效生烃泥页岩、形成于深水-半深水相的富有机质泥页岩、较高的有机质丰度和适当的热演化程度以及较好的基质物性条件等是页岩油形成的主要条件。建立了中国陆相断陷湖盆页岩油发育模式,指出概率体积法可以作为页岩油资源评价的主要方法,提出了页岩油远景区、有利区及目标区优选的参数体系和标准。作为非常规油气能源的主要类型之一,页岩油将会对我国能源结构产生重要影响。