Evidence of native radiation-induced paramagnetic defects in natural illites from unconformity-type uranium deposits

This study presents the first unequivocal identification of natural radiation-induced defects in illites. Middle Proterozoic illites related to unconformity-type uranium deposits of Canada and Australia were studied using electron paramagnetic resonance (EPR) spectroscopy at X- and Q-band frequencies. The saturation behaviour of EPR spectra as a function of power demonstrates that native defects of illites are different from those known in other clays as kaolinite, dickite or smectite. Q-band spectra indicate the presence of several––at least two––native defects. The EPR signal is dominated by an axially distorted spectrum with apparent principal components as follows: g _∥ = 2.032 and g _⊥ = 1.993. The corresponding defect is named as A_i center. The study of oriented specimen confirms the strong anisotropy, and shows that the main defect has its g _∥ component perpendicular to the (ab) plane of illite. These defects in illite correspond to electron holes located on oxygen atoms of the structure and likely associated to Si, according to the lack of hyperfine structure. The A_i center in illite has similar EPR parameters to the A center in kaolinite and dickite. The isochronal annealing data suggest that illite can be used as a dosimeter in the geosphere. However, the determination of half-life and activation energy of the A_i center requires additional work.     

Ionizing radiation-induced defects in smectite clays

 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     

Radiation-induced defects in quartz. II. Single-crystal W-band EPR study of a natural citrine quartz

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.     

Radiation-damage-induced defects in quartz. I. Single-crystal W-band EPR study of hole centers in an electron-irradiated quartz

Single-crystal W-band electron paramagnetic resonance (EPR) spectra of an electron-irradiated quartz, measured at room temperature, 110 and 77 K, disclose three previously reported hole centers (#1, G and an ozonide radical). The W-band EPR spectra of these three centers clearly resolve six magnetically nonequivalent sites each, whereas previous X- and Q-band EPR studies reported Centers #1 and the ozonide radical to consist of only three symmetry-related components and interpreted them to reside on twofold symmetry axes in the quartz structure. The calculated g matrices of Center #1 and the ozonide radical show that deviations from twofold symmetry axes are <10°, which are probably attributable to distortion related to neighboring charge compensating ions. The W-band EPR spectra of Center G not only result in improved g matrices but also allow quantitative determination of the nuclear hyperfine (A) and quadrupole (P) matrices of its ²⁷Al hyperfine structure that was incompletely resolved before. In particular, the g-maximum and g-minimum principal axes of Center G are approximately along two pairs of O–O edges of the SiO₄ tetrahedron, while the unique A principal axis is approximately along a Si–Si direction. These new spin-Hamiltonian parameters suggest that Center G most likely involves trapping of a hole between two oxygen atoms related to a silicon vacancy and stabilized by an Al³⁺ ion in the neighboring tetrahedron (hence an O₂ⁿ⁻–Al³⁺ defect, where n is either 1 or 3).     

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

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.     

Mn distribution in sphalerite: an EPR study

A study on Zn replacement in sphalerite by divalent Mn has been performed by using EPR spectroscopy. Twelve natural and synthetic samples with different Mn-contents were selected for the spectroscopic investigation. The EPR spectra vary from an hyperfine sextet to a single broad line according to their Mn-content. Three components, attributed to Mn(II) in different chemical coordination (namely isolated ions, interacting ions, clusters) have been determined by means of spectral simulation. The variations of the EPR signals among the different spectra are due only to the mixing of these components, without any variation of each spectral parameter. Differing distribution of Mn(II) was, therefore, observed at a local scale. Consequently, the specific interactions driving the coalescence of Mn(II) ions to form clusters may be responsible for the banded pattern in sphalerite crystals.     

Radiation-induced defects in quartz. IV. Thermal properties and implications

The thermal stabilities and decay kinetics of three peroxy radicals (Centers #1, B and B′) and three other radiation-induced defects (#3, C′ and E₁′) in natural quartz from the high-grade McArthur River uranium deposit (Athabasca basin, Canada) have been investigated by isochronal and isothermal annealing experiments and electron paramagnetic resonance (EPR) spectroscopy. Single-crystal EPR spectra of isochronally (2 h) annealed quartz show that these centers all grow in intensity to 280°C and then decay with further increase in temperature, but their disappearance temperatures differ markedly and depend on the initial concentrations (e.g., Center #1 in a dark smoky quartz is annealed out at 380°C, B and B′ at 420°C and #3 and C′ at 580°C). The isothermal decay processes of these centers are all of the second order type. The calculated activation energies for the peroxy radicals [#1 and B + B′ at 0.36 (9) and 0.83 (8) eV, respectively] are smaller than those of Centers #3, C′ and E₁′ [1.09 (8), 1.24 (8) and 1.45 (7) eV, respectively]. Gamma-ray irradiations of thermally bleached quartz restore a fraction of the peroxy radicals, suggesting that their diamagnetic precursors are stable up to at least 800°C. The unusual decay characteristics of “peroxy radicals” in quartz reported in the literature are shown to most likely arise from multiple radiation-induced defects. These results have implications for not only applications of peroxy radicals in quartz for EPR dating but also better understanding of thermoluminescence and cathodoluminescence spectra of this mineral.     

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.     

膨润土防水毯破损条件下渗流特性试验研究

为了从渗流量和渗透稳定角度深入研究膨润土防水毯破损处的防渗问题,开发了由压力控制系统和模型试验系统两部分组成的渗流试验装置,建立了针对坝体防渗工程中的防水毯破损情况的渗流物理试验方法,并通过膨润土防水毯不同破损工况下的渗流试验,初步探讨了影响破损防水毯与坝身土体联合抗渗的因素。结果表明,对破损防水毯和土体的综合渗透系数的影响,孔洞大小比破损率要敏感;对于孔洞修复能力,主要的敏感的因素包括孔洞直径D及防水毯规格（材料本身性能）。在工程中要做好以下两点：（1）工程中刺破孔洞直径D小于0.5 cm,超过0.5 cm的孔洞应当做修补;（2）局部刺破率不宜大于0.5%,尽量保证防水毯接触面的平整。     

Theoretical study of point defects in crystalline zircon

We present a numerical study of point defects in crystalline zircon (ZrSiO₄). Vacancies and interstitials of all the constituents of zircon have been considered. For each defect, the structure and the formation energies have been calculated. Calculations, using the supercell method, are based on the Density Functional Theory in the Local Density Approximation. Empirical potentials have also been considered for comparison with electronic structure results. We find a formation energy for the oxygen interstitial of 1.7 eV. This value is compatible with the experimental activation energy for oxygen diffusion in zircon, which proves an interstitial mechanism for the diffusion of oxygen in zircon. For all other defects the calculated formation energies lead to negligible thermal concentration at equilibrium. Received: 8 January 1999 / Revised, accepted: 14 May 1999     

Influence of montmorillonite on antimicrobial activity of tetracycline and ciprofloxacin

Antibiotics are used not only to fight infections and inhibit bacterial growth, but also as growth promotants in farm livestock. Farm runoff and other farm-linked waste have led to increased antibiotic levels present in the environment, the impact of which is not completely understood. Soil, more specifically clays, that the antibiotic contacts may alter its effectiveness against bacteria. In this study a swelling clay mineral montmorillonite was preloaded with antibiotics tetracycline and ciprofloxacin at varying concentrations and bioassays were conducted to examine whether the antibiotics still inhibited bacterial growth in the presence of montmorillonite. Escherichia coli was incubated with montmorillonite or antibiotic-adsorbed montmorillonite, and then the number of viable bacteria per mL was determined. The antimicrobial activity of tetracycline was affected in the presence of montmorillonite, as the growth of non-resistant bacteria was still found even when extremely high TC doses were used. Conversely, in the presence of montmorillonite, ciprofloxacin did inhibit E. coli bacterial growth at high concentrations. These results suggest that the effectiveness of antimicrobial agents in clayey soils depends on the amount of antibiotic substance present, and on the interactions between the antibiotic and the clays in the soil, as well.     

黄土中蜗牛壳Mn^2＋的EPR研究及其古气候意义

对黄土高原陕西省洛川和甘肃省西峰剖面中黄土－古土壤层中的蜗牛壳进行了EPR波谱分析，同时对洛川地区的现代蜗牛壳也进行了测定。结果显示：（1）不同种类的蜗牛壳具有相近的EPR信号强度，表明不同种类的蜗牛对Mn^2+的吸收没有差异性。（2）黄土层中蜗牛壳的EPR信号强度远大于占土壤中的，即黄土中蜗牛壳所含的Mn^2+远大于古土壤中的蜗牛壳的Mn^2+的含量，说明前者生活在比较还原的条件下，后者形成环境的氧化性较高。因此本认为为蜗牛壳中Mn^2+的含量可反映其生长环境中Mn^2+的含量和氧化还原条件，对古气候的重建具有重要意义。     

蒙脱石热处理产物的电子顺磁共振研究

本文对广东和平蒙脱石及其热处理产物进行了化学分析、差热和热重分析、Ｘ射线粉末衍射分析、红外吸收光谱分析及电子顺磁共振研究。结果表明,在热处理过程中,蒙脱石的结构发生很大的变化。蒙脱石的电子顺磁共振谱中有两个主要的特征信号,其ｇ值分别为４１６和２．１,前者对应于蒙脱石八面体片中Ｆｅ３＋的结构信号,后者对应于蒙脱石晶体表面吸附的某种超微粒富铁相———无定形的氧化物和氢氧化物中的Ｆｅ３＋的结构信号。随着蒙脱石热处理温度的不同,两者的信号强度发生很大的变化。这种变化反映出蒙脱石结构中的Ｆｅ和吸附的Ｆｅ在相变过程中所发生的价态和结构变化及迁移。     

An EPR and SQUID magnetometry study of bornite

A magnetic and spectroscopic characterisation has been performed on a natural bornite sample from the Natural History Museum of the University of Florence. The combination of magnetic measurements and continuous-wave electron paramagnetic resonance (cw-EPR) spectroscopy at different temperatures and frequencies provided information about the distribution and valence states of Cu and Fe in bornite. The studied sample was found to obey the Curie–Weiss law with a transition from a paramagnetic to an antiferromagnetic phase at 64 K; its possible attribution to a disordered spin glass phase was ruled out by ac susceptibility measurements. Q- and X-band cw-EPR measurements confirmed the presence of Fe(III) as fundamental valence state in bornite: the single EPR line registered in the temperature range from 300 to 65 K can be assigned, in fact, to the Fe(III) single ions. Some Cu(II) signals were revealed in the low temperature EPR spectra and attributed to an early stage of the surface alteration. The width of the Fe(III) EPR spectrum, which hinders any characteristic spectral structure, can be ascribed to the exchange interaction. The pure antiferromagnetic character of the magnetic transition confirms the ordering between Fe and Cu in the bornite structure, at least at low temperature (≤70 K). Moreover, the relatively high Nèel temperature suggests the accepted model of Collins et al.’s (Can J Phys 59:535–539, 1981) to conveniently explain the overall magnetic properties in the range 298–4 K. Despite the increasing of the susceptibility in the paramagnetic range, in fact, the integrated EPR line area decreases by lowering the temperature, thus suggesting a progressive rising of the antiferromagnetic interactions among next-nearest-neighbouring paramagnetic centres.     

蒙脱石中性化改性实验研究

使用表面活性剂HDTMAB对含有蒙脱石等粘土矿物的膨润土进行不同程度的有机改性,并利用自由膨胀率的实验方法定量描述改性膨润土在水以及甲苯介质中的膨胀规律。对实验结果进行数学分析后发现,随着改性剂用量的加大,改性膨润土在水介质中的自由膨胀率明显降低,而在甲苯介质中的自由膨胀率显著上升,当改性剂用量约为15%时,改性膨润土在水以及甲苯介质中都没有发生剧烈膨胀。依照上述膨润土的改性方法,对胜利油田提供的岩心样品进行了有机改性,并得到了相同的规律。由此得出,严格控制改性剂用量可以实现蒙脱石的中性化改性。利用这一规律,将适量的改性剂注入地下,既能够缓解油气田储层中蒙脱石的水敏膨胀危害,又不会造成过量的油脂分子吸附于矿物表面。     

Iron distribution in the octahedral sheet of dioctahedral smectites. An Fe K-edge X-ray absorption spectroscopy study

The distribution of iron atoms in the octahedral sheet of a series of dioctahedral smectites with varying unit-cell composition and iron content was investigated by Fe K-edge XAS spectroscopy. First-step analysis reveals that the patterns corresponding to backscattering by atoms located between 3 and 4 Å from the absorbing atom are very sensitive to the relative amount of light (Si, Al, Mg) and heavy (Fe) atoms. Detailed modelling of this domain then provides valuable information on the number of iron atoms surrounding octahedral iron. By comparing the number of iron neighbours deduced from EXAFS with that determined from unit-cell composition assuming a statistical distribution, three groups of montmorillonites can be distinguished: (1) clay samples from Wyoming display an ordered distribution of iron atoms; (2) clay samples from Georgia, Milos, China and Washington exhibit a close to random distribution of iron atoms; (3) clay samples from North Africa, Germany, Texas and Arizona display extensive iron clustering. These results complement previously obtained IR results and show that the combination of these two spectroscopic techniques could provide an additional crystal-chemistry-based framework for typological analysis of montmorillonite deposits.     

EPR and SQUID magnetometry study of Cu2FeSnS4 (stannite) and Cu2ZnSnS4 (kesterite)

An EPR and SQUID magnetometry study of Cu₂FeSnS₄ (stannite) and Cu₂ZnSnS₄ (kesterite) has been performed in order to gain a deeper insight into the crystal chemistry of these minerals, in which the mixed character of bonds lends uncertainty to the determination of the metal valence states. EPR investigations were performed down to almost liquid nitrogen temperature on both natural and synthetic samples of stannite and kesterite. The interpretation of their parameters (g- and T-tensors) was refined by computer simulation. The main feature of all the spectra is the unstructured signal centered at about 0.310 T due to the presence of Cu(II). The absence of structure in the signal is due to spin-spin exchange interaction between Cu(II) and Fe(II), pointing to a diluted distribution of Cu(II). The temperature dependence of the Cu(II) signal can be related to a topological variation of the first-neighbors coordination. The SQUID measurements, while allowing a more precise interpretation of the EPR data, led to a full characterization of magnetic behavior of stannite and kesterite down to liquid helium temperature, evidencing antiferromagnetic interactions between the Fe(II) ions in all samples but in synthetic kesterite. From the EPR and SQUID experimental data no evidence was provided for the existence of two different structures for stannite and kesterite. Received: 2 August 1999 / Accepted: 7 January 2000     

9 and 34 GHz EPR study of the free radicals in various asphaltenes: Statistical correlation of the g-values with heteroatom content

The 9 and 34 GHz EPR spectra of eight asphaltenes from different locations have been studied at 294 K in an attempt to correlate the observed g-values with the heteroatom content. It is found that the EPR linewidths are larger and the g-values are smaller at 34 GHz than at 9 GHz. Quantitative statistical analysis of the g-values observed in those asphaltenes derived from tar sand bitumens and crude oils shows that they are uncorrelated with the heteroatom content, unlike those from coal. It is concluded that g-values may not be a good analytical tool for elucidating the structure of those asphaltenes not derived from coal.     

铝钛柱撑改性膨润土处理两种模拟废水的实验研究

以钠基膨润土为原料制备了铝钛无机柱撑、铝钛有机柱撑改性膨润土，确定了改性膨润土的最佳铝钛比和铝土比，并将其应用于模拟废水、化学实验室废水的处理。与原土进行比较，探讨了用量、pH值、搅拌时间等对COD去除率、色度去除率、浊度去除率的影响，通过正交实验对实验条件进行了优化。结果表明：有机柱撑改性膨润土、无机柱撑改性膨润土对废水的处理效果均明显好于原土，对废水色度、浊度的去除率均大于93％；对废水COD的去除效果，有机柱撑改性膨润土比无机柱撑改性膨润土有较大提高，去除率最高达66．31％，结果令人满意。     

Linear relationship between thermo-dehydroxylation and induced-strain by mechanical processing in vacuum: The case of industrial kaolinite, talc and montmorillonite

The thermal behaviour and the structural properties of three important industrial phyllosilicates, such as kaolinite, talc and Ca-rich montmorillonite, have been examined after mechanical treatment in a specifically built planetary ball mill working in vacuum (P = 0.13 Pa) at room temperature (25 °C). It is found that, on increasing the grinding time, the temperature of the dehydroxylation reaction decreases linearly as a result of a decrease of the crystallite size and structural order. To be noted that the mechanical treatment in our milling conditions did not induce significant amorphization. The temperature at which there is the maximum of dehydroxylation and the weight losses of the intralayer OH are linearly related to the increase of the FWHM of the 001 basal plane. These results are useful for predicting the thermal behaviour of layer silicates to be subjected to mechanical processing in industrial application.