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 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

Electronic structures of iron(III) and manganese(IV) (hydr)oxide minerals: Thermodynamics of photochemical reductive dissolution in aquatic environments

Sunlight-induced reduction and dissolution of colloidal Fe-Mn (hydr)oxide minerals yields elevated concentrations of Fe²⁺ and Mn²⁺ in natural waters. Since these elements may be biolimiting micronutrients, photochemical reactions might play a significant role in biogeochemical cycles. Reductive photodissolution of Fe (hydr)oxide minerals may also release sorbed metals. The reactivity of Fe-Mn (hydr)oxide minerals to sunlight-induced photochemical dissolution is determined by the electronic structure of the mineral-water interface. In this work, oxygen K-edge absorption and emission spectra were used to determine the electronic structures of iron(III) (hydr)oxides (hematite, goethite, lepidocrocite, akaganeite and schwertmannite) and manganese(IV) oxides (pyrolusite, birnessite, cryptomelane). The band gaps in the iron(III) (hydr)oxide minerals are near 2.0-2.5 eV; the band gaps in the manganese (IV) oxide phases are 1.0-1.8 eV. Using published values for the electrochemical flat-band potential for hematite together with experimental pH_pzc values for the (hydr)oxides, it is possible to predict the electrochemical potentials of the conduction and valence bands in aqueous solutions as a function of pH. The band potentials enable semiquantitative predictions of the susceptibilities of these minerals to photochemical dissolution in aqueous solutions. At pH 2 (e.g., acid-mine waters), photoreduction of iron(III) (hydr)oxides could yield millimolal concentrations of aqueous Fe²⁺ (assuming surface detachment of Fe²⁺ is not rate limiting). In seawater (pH 8.3), however, the direct photo-reduction of colloidal iron(III) (hydr)oxides to give nanomolal concentrations of dissolved, uncomplexed, Fe²⁺ is not thermodynamically feasible. This supports the hypothesis that the apparent photodissolution of iron(III) (hydr)oxides in marines systems results from Fe³⁺ reduction by photochemically produced superoxide. In contrast, the direct photoreduction of manganese oxides should be energetically feasible at pH 2 and 8.3.     

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.     

Reduction of crystalline iron(III) oxyhydroxides using hydroquinone: Influence of phase and particle size

Iron oxides and oxyhydroxides are common and important materials in the environment, and they strongly impact the biogeochemical cycle of iron and other species at the Earth's surface. These materials commonly occur as nanoparticles in the 3–10 nm size range. This paper presents quantitative results demonstrating that iron oxide reactivity is particle size dependent. The rate and extent of the reductive dissolution of iron oxyhydroxide nanoparticles by hydroquinone in batch experiments were measured as a function of particle identity, particle loading, and hydroquinone concentration. Rates were normalized to surface areas determined by both transmission electron microscopy and Braunauer-Emmett-Teller surface. Results show that surface-area-normalized rates of reductive dissolution are fastest (by as much as 100 times) in experiments using six-line ferrihydrite versus goethite. Furthermore, the surface-area-normalized rates for 4 nm ferrihydrite nanoparticles are up to 20 times faster than the rates for 6 nm ferrihydrite nanoparticles, and the surface-area-normalized rates for 5 × 64 nm goethite nanoparticles are up to two times faster than the rates for 22 × 367 nm goethite nanoparticles.     

Thermoluminescence,fluorescence and electron paramagnetic resonance properties of synthetic hydrothermal scheelites

Hydrothermal scheelite was synthesized using Na₂WO₄ · 2 H₂O mixed with CaCl₂ · H₂O, CaSO₄ · 2 H₂O or CaF₂ at different temperatures (270–720° C) and 10⁸ Pa. The morphology of the crystals depends on the starting products. The observed faces include the {112}, {114}, {011}, and {013} forms. Pure or REE doped scheelites were studied by thermoluminescence (TL), fluorescence and electron paramagnetic resonance (EPR). The main TL peaks are located near 88, 149, 216, 277, and 315 K. Results obtained with EPR or optical fluorescence have been correlated with TL measurements and show that the trivalent lanthanide elements substitute for calcium ions without site distortion. The differences in TL observed between Eu and the other doping elements are related to the greater stability of Eu²⁺ caused by X-irradiation.     

An electron paramagnetic resonance (EPR) study of the adsorption of copper complexes on montmorillonite and imogolite

The adsorption of three copper species, the hydrated cupric ion, bisglycine Cu(II) and a Cu(II)-humic acid complex, on montmorillonite and imogolite at pH 7 was investigated by electron paramagnetic resonance (EPR) spectroscopy. The spectra of the supernatant solutions indicated that adsorption of the glycine complexes was very much less than that of the uncomplexed ion for both minerals and that montmorillonite adsorbed significantly more Cu from the humic acid solution than did imogolite. In every case the adsorbed Cu was characterized by more than one type of chemical environment and the spectral parameters show differences between the adsorbed species depending on their freedom of movement and their mode and site of adsorption. Qualitatively similar spectra were obtained when the uncomplexed ion was adsorbed on either of the mineral species and it is suggested that simple Cu(II) ions were involved and that their coordination environments comprised water molecules and hydroxyl groups. With the bisglycine Cu(II) complexes, the spectra were characterized by two components which may be accounted for by adsorption at two different types of site in the structures. In each case one component had parameters that are similar to those of the bisglycine Cu(II) in the solid state, but the second component in the spectra of the montmorillonite sample was quite different to that obtained with imogolite. The Cu(II)-humic acid complex with montmorillonite gave spectra that were similar to that from copper humate, but with imogolite the spectra from the Cu(II)-humic acid system were similar to those obtained with the uncomplexed Cu(II) ion, indicating that imogolite is able to extract copper from humic acid.     

Thermoluminescence, electron paramagnetic resonance and optical absorption in natural and synthetic rhodonite crystals

Thermoluminescence, electron paramagnetic resonance and optical absorption properties of rhodonite, a natural silicate mineral, have been investigated and compared to those of synthetic crystal, pure and doped. The TL peaks grow linearly for radiation dose up to 4 kGy, and then saturate. In all the synthetic samples, 140 and 340°C TL peaks are observed; the difference occurs in their relative intensities, but only 340°C peak grows strongly for high doses. Al₂O₃ and Al₂O₃ + CaO-doped synthetic samples presented several decades intenser TL compared to that of synthetic samples doped with other impurities. A heating rate of 4°C/s has been used in all the TL readings. The EPR spectrum of natural rhodonite mineral has only one huge signal around g = 2.0 with width extending from 1,000 to 6,000 G. This is due to Mn dipolar interaction, a fact proved by numerical calculation based on Van Vleck dipolar broadening expression. The optical absorption spectrum is rich in absorption bands in near-UV, visible and near-IR intervals. Several bands in the region from 540 to 340 nm are interpreted as being due to Mn³⁺ in distorted octahedral environment. A broad and intense band around 1,040 nm is due to Fe²⁺. It decays under heating up to 900°C. At this temperature it is reduced by 80% of its original intensity. The pink, natural rhodonite, heated in air starts becoming black at approximately 600°C.     

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.     

Cathodoluminescence (CL) and electron paramagnetic resonance (EPR) studies of clay minerals

Summary ?Sheet silicates of the serpentine–kaolin-group (serpentine, kaolinite, dickite, nacrite, halloysite), the talc–pyrophyllite-group (talc, pyrophyllite), the smectite-group (montmorillonite), and illite (as a mineral of the mica-group) were investigated to obtain information concerning their cathodoluminescence behaviour. The study included analyses by cathodoluminescence (CL microscopy and spectroscopy), electron paramagnetic resonance (EPR), X-Ray diffraction (XRD), scanning electron microscopy (SEM) and trace element analysis. In general, all dioctahedral clay minerals exhibit a visible CL. Kaolinite, dickite, nacrite and pyrophyllite have a characteristic deep blue CL, whereas halloysite emission is in the greenish-blue region. On the contrary, the trioctahedral minerals (serpentine, talc) and illite do not show visible CL. The characteristic blue CL is caused by an intense emission band around 400 nm (double peak with two maxima at 375 and 410 nm). EPR measurements indicate that this blue emission can be related to radiation induced defect centres (RID), which occur as electron holes trapped on apical oxygens (Si–O centre) or located at the Al–O–Al group (Al substituting Si in the tetrahedron). Additional CL emission bands were detected at 580 nm in halloysite and kaolinite, and between 700 and 800 nm in kaolinite, dickite, nacrite and pyrophyllite. Time-resolved spectral CL measurements show typical luminescence kinetics for the different clay minerals, which enable differentiation between the various dioctahedral minerals (e.g. kaolinite and dickite), even in thin section. Received December 3, 2001; revised version accepted February 27, 2002     

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.     

Densification of iron(III) sludge in neutralization

Acid mine drainage (AMD), of which iron is a substantial component, is a potential by-product in the mining industry. Conventional neutralization is a common approach to treat AMD, although it creates a major disposal problem due to the generation of voluminous sludge. Sludge recirculation improves solid density by slowing down the rate of neutralization and allowing the growth of precipitates, while existing solids act as seed particles by providing necessary surface area for precipitation. The mechanisms of iron sludge densification are not fully understood, mainly because of the complex nature of iron chemistry, and the variety of amorphous, polymeric oxides that could be formed. In this work, the effects of alkaline reagents, flocculant addition, and dosing sequence, on the precipitation of iron (III) hydroxide and densification of the recycled sludge were investigated. Slowly dissolving lime (Ca(OH)₂) was found to be more effective than caustic (NaOH) in producing sludge with higher solid contents. Polymers addition created stronger aggregates that could withstand shearing without significant size reduction, but the overall sludge density was lower than those produced without flocculant. Conditioning the sludge at pH between 3.5 and 4.5 by adding fresh lime in a specific dosing manner appeared to be conducive to the growth of large agglomerates. The final sludge solid content of ∼15 wt.% was considerably higher than others produced under different conditions. The plate-like structures of precipitates generated with more recycles in this instance, possibly helped ease the release of entrapped water between solids during shearing, thus producing sludge with higher solid density.     

Cathodoluminescence of synthetic and natural calcite: the effects of manganese and iron on orange emission

Summary The orange cathodoluminescence (CL) of calcite is known to be due to the presence of Mn²⁺ cations. It has been demonstrated here using CL and electron paramagnetic resonance (EPR) crossed analysis from synthetic calcite that neither Fe²⁺ nor Fe³⁺ ions influence this luminescence emission. More complex natural calcium carbonates have been investigated to check whether or not this conclusion can be applied to them. For this purpose, different white marbles from Greek quarries were analysed with CL. The data are completed with neutron activation analysis (NAA) for manganese and iron contents. Again it is shown that only manganese plays a role in the orange CL of these white marbles. This result provides an important clue in the wide field of provenance determination of calcium carbonate used in ancient art.Received February 19, 2002; revised version accepted October 22, 2002 Published online March 10, 2003