湖北天然绿松石与优化处理绿松石的宝石学鉴别特征

本文主要以湖北天然绿松石、浸胶绿松石和注有色胶绿松石为研究对象,结合优化处理工艺过程及所用的胶水混合液,通过宝石学常规测试以及扫描电子显微镜、红外光谱仪、激光拉曼光谱仪和紫外可见光谱仪等宝石学现代仪器的测试分析,研究有效鉴别湖北天然绿松石和浸胶绿松石、注有色胶绿松石的测试方法。结果表明,注有色胶绿松石的颜色较呆板,浸胶和注有色胶绿松石相对密度较低且在长波紫外荧光灯下显示强至弱的蓝色荧光;扫描电镜下可见浸胶和注有色胶绿松石微晶之间的空隙被不同程度的胶质物充填,但该方法为有损法,不推荐使用;红外光谱中2 930、2 860、1 730、1 460 cm-1附近由有机物基团振动所致的红外吸收谱带可有效区分三者,是最为快速、无损、准确的方法;拉曼光谱中2 942、2 873、1 452、1 620、830 cm-1附近的吸收峰可作为鉴别湖北天然绿松石和浸胶或注有色胶绿松石的重要依据;紫外可见光谱中较弱的429 nm吸收峰和宽缓的677 nm吸收带可作为区分天然绿松石和注有色胶绿松石的鉴别依据,但无法区分天然绿松石和浸胶绿松石。     

Optical absorption and electron spin resonance in blue and green natural beryl

A comparative study of blue and green beryl crystals (from the region of Governador Valadares, Minas Gerais, Brazil) using electron paramagnetic resonance (EPR) and optical absorption (OA) spectroscopy is reported. The EPR spectra show that Fe³⁺ in blue beryl occupies a substitutional Al³⁺ site and in green beryl is localized in the structural channels between two O₆ planes. On the other hand the infrared spectra show that the alkali content in the blue beryl is mostly at substitutional and/or interstitial sites and in green beryl is mostly in the structural channels. The OA spectra show two types of Fe²⁺. Thermal treatments above 200° C in green beryl cause the reduction of Fe³⁺ into Fe²⁺ accompanied by a change of color to blue. The blue beryl color does not change on heating. The kinetics of the thermal conversion of Fe³⁺ into Fe²⁺ is composed of two first order processes; the first one has an activation energy ΔE ₁=0.30 eV and the second one has an activation energy ΔE ₂=0.46 eV.     

Natural iron-containing blue and colorless euclase studied by electron paramagnetic resonance

Natural blue and colorless rare-gem mineral specimens of euclase from Brazil are investigated by electron paramagnetic resonance (EPR). Angular dependences of Fe³⁺ EPR spectra in three mutually perpendicular crystal planes are analyzed revealing g and D tensors with significant low-symmetry effects, as for example, the high asymmetry parameter E/D = 0.28. Fourth-order degree Stevens parameters are also included in analysis. The anisotropy of both g and D tensors is consistent with Fe³⁺ substituting for Al³⁺ ions in strongly distorted AlO₅(OH) octahedra in which the oxygen distances range from 1.85 to 1.98 Å. Fe³⁺ is not responsible for the blue color because colorless and blue euclase show nearly the same Fe³⁺ concentration as measured by EPR. However, total iron content in blue sample is much higher than in the colorless one suggesting that the existing model that Fe²⁺–Fe³⁺ intervalence charge transfer transition may explain the blue color of euclase.     

常见绿松石品种特征及充填处理的鉴定

总结了我国市场上大量常见的不同产地的天然绿松石的特征,同时对比我国市场常见的充填处理绿松石的特征,研究了天然与充填处理绿松石的一般鉴别特征,发现处理绿松石的颜色深浅、颜色分布、包裹体、外观与天然绿松石均有较大的区别。还利用红外光谱对天然的和充填处理的绿松石进行了测试,发现充填处理绿松石在1 735、1 600、1 500 cm^-1附近可见吸收峰,表明绿松石内部充填了人工类树脂,可作为鉴定充填处理绿松石的有力证据。     

Uptake of Cu2+ by the calcium carbonates vaterite and calcite as studied by continuous wave (cw) and pulse electron paramagnetic resonance

The investigation of the Cu²⁺ uptake by the calcium carbonate minerals vaterite and calcite with continuous wave and pulse electron paramagnetic resonance (EPR) yields information on a molecular scale about the relevant complexation reactions at the mineral–water interface. The structural assignment is based on changes in the coordination geometry of the copper complexes. Magnetic interactions of the unpaired Cu²⁺ electron with nuclei of ¹³C-labeled carbonate ligands and protons from water or hydroxyl ligands in the first and second coordination spheres of the cation are detected by pulse EPR techniques. Our results show that the Cu²⁺ ions are rapidly dehydrated upon adsorption on the mineral surface. The strong surface binding is due to monodentate coordination to three or four carbonate surface ions, comparable to chelate complexation in solution. The formation of square-planar or square-pyramidal copper complexes at exposed surface sites like kinks and steps yields a convincing explanation for the inhibition of calcium carbonate growth and dissolution. Upon recrystallization the Cu²⁺ ions are integrated into the calcite lattice where they exhibit a dynamic Jahn–Teller effect. The resulting local lattice distortions are expected to destabilize the Cu_xCa_(1−x)CO₃(s) solid solution. Our results support the concept of a dynamic calcium carbonate surface, covered by a thin, structured surface layer. The detailed structural information obtained for Cu²⁺ provides a better understanding of the interaction of other metal ions with calcium carbonate minerals.     

On the origin of natural sapphire color

An attempt has been made to interpret natural sapphire optical absorption spectra with regard to the exchange-coupled pairs of iron impurities in their ferric and ferrous states. Level schemes have been calculated for Fe³⁺-Fe³⁺ and Fe²⁺-Fe²⁺ pairs of all the orders, their symmetry being observed. The selection rules are discussed. EPR and infrared spectroscopy information has been used to assist the optical spectroscopy data. The sapphire color has been interpreted as a function of Fe²⁺/Fe³⁺ ratios and of the presence of their pairs in the stone. The various types of charge compensation in Fe²⁺→Al³⁺ isomorphism are discussed.     

云南磷铝石谱学特征研究

使用电子探针、X射线粉晶衍射仪、傅里叶变换红外光谱仪、激光拉曼光谱仪、紫外可见分光光度计等仪器,对最近在云南发现的一种达到宝石级别的磷铝石进行了化学成分、矿物组成、红外吸收光谱、拉曼光谱、紫外可见吸收光谱等方面的研究。化学成分分析结果表明,该磷铝石的主要化学成分为P和Al,并含有少量的Fe和V;X射线粉晶衍射结果显示,该磷铝石的矿物成分主要为磷铝石,杂质较少;红外光谱与拉曼光谱分析均检出磷酸根基团的特征峰,红外光谱分析还显示有结晶水与结构水的存在;紫外可见吸收光谱在300和420 nm附近的吸收归属于Fe3+,630 nm附近较宽缓的吸收带由Fe3+和V3+共同产生。并将磷铝石与绿松石进行了谱学方面的对比分析,以便更好地区分两者。     

Determination of Fe3+ and Fe2+ concentrations in feldspar by optical absorption and EPR spectroscopy

Ferrous and ferric iron concentrations in feldspars with low total iron content (<0.32 wt% total Fe) were determined from optical and electron paramagnetic resonance (EPR) spectra to better than ±15 percent of the amount present. Optical spectra indicate that Fe²⁺ occupies two distorted M-sites in plagioclases of intermediate structural state. The linear dependence of the Fe²⁺/Fe total ratio on An content demonstrates that Fe²⁺ substitutes for Ca (not Na) so that the number of Ca-sites is a principal factor in iron partitioning in plagioclase. EPR powder spectra show that the number of sites for Fe³⁺ depends on structural state rather than on plagioclase chemistry. The observed linear correspondence of EPR double-integrated intensities with optical peak areas shows that all Fe³⁺ is tetrahedrally coordinated in both plagioclase and disordered potassium feldspar. Microcline perthites show, in addition to tetrahedral Fe³⁺, a signal due to axially coordinated ferric iron, which we associate with formation of hematite inclusions.     

Measurements of iron concentration in kaolinites considering disorder broadening of EPR lines

Only one part of the EPR lines of a kaolinite spectrum of structural Fe³⁺ is clearly observable because of the overlapping of other lines with other spectra. For this reason, to determine the structural Fe³⁺ concentration we used the line near g=9, although it is not intense. A standard is needed: powders of ZnS containing given concentrations of Mn²⁺ (isoelectronic to Fe³⁺) were used for this purpose. Using the simulations of the EPR spectra, the concentration (number of Fe³⁺ per Al³⁺) is determined; it is in the range 10^?5 to 10^?4 for our samples. Considering that the crystal-field disorder around Fe³⁺ is responsible for line broadening, we looked for a possible effect of the broadening on the intensity of the EPR spectra. This effect is taken as a distribution of the parameter λ=B₂²/B₂⁰. The influence of the parameter λ and its statistical distribution on the position, shape, width and intensity of the EPR line has been calculated using simulation procedures. The correction due to the disorder on the calculated concentration is of the same order of magnitude as the precision measurement. This method can be applied for other kaolinites by comparing the area of their g=9 lines with known ones.     

Electron paramagnetic resonance spectroscopy of Fe<Superscript>3+</Superscript> ions in amethyst: thermodynamic potentials and magnetic susceptibility

Single-crystal and powder electron paramagnetic resonance (EPR) spectroscopic studies of natural amethyst quartz, before and after isochronal annealing between 573 and 1,173 K, have been made from 90 to 294 K. Single-crystal EPR spectra confirm the presence of two substitutional Fe³⁺ centers. Powder EPR spectra are characterized by two broad resonance signals at g = ~10.8 and 4.0 and a sharp signal at g = 2.002. The sharp signal is readily attributed to the well-established oxygen vacancy electron center E ₁′. However, the two broad signals do not correspond to any known Fe³⁺ centers in the quartz lattice, but are most likely attributable to Fe³⁺ clusters on surfaces. The absolute numbers of spins of the Fe³⁺ species at g = ~10.8 have been calculated from powder EPR spectra measured at temperatures from 90 to 294 K. These results have been used to extract thermodynamic potentials, including Gibbs energy of activation ΔG, activation energy E _a, entropy of activation ΔS and enthalpy of activation ΔH for the Fe³⁺ species in amethyst. In addition, magnetic susceptibilities (χ) have been calculated from EPR data at different temperatures. A linear relationship between magnetic susceptibility and temperature is consistent with the Curie–Weiss law. Knowledge about the stability and properties of Fe³⁺ species on the surfaces of quartz is important to better understanding of the reactivity, bioavailability and heath effects of iron in silica particles.     

Origin of the color in cobalt-doped quartz

Synthetic Co-doped quartz was grown hydrothermally in steel autoclaves at the Technological Center of Minas Gerais (CETEC), Brazil. The quartz samples, originally yellow in the as-grown state acquired blue coloration after prolonged heat treatment times at 500°C near the alpha–beta transition temperature. UV–VIS–NIR absorption spectroscopy shows the characteristic spectra of Co³⁺ before heat treatment. After heat treatment, the optical absorption spectrum is dominated by two split-triplet bands the first in the near infrared region centered at about 6,700 cm⁻¹ (1,490 nm) and the second in the visible spectral range at about 16,900 cm⁻¹ (590 nm). Both split-triplet bands are typical for Co²⁺ ions in tetrahedral coordination environments. From the absence of electron paramagnetic resonance (EPR) spectra, we conclude that the Co²⁺ found in the optical absorption spectra of the blue quartz is not due to an isolated structural site in the quartz lattice. Instead, the blue color is associated with electronic transitions of Co²⁺ in small inclusions in which the Co site has tetrahedral symmetry. The non-observation of polarization-depend optical absorption spectra is also in agreement with this model. The results for Co²⁺ in quartz are different from Co-bearing spinel and staurolite and other silicates like orthopyroxene, olivine, and beryls. The formation process of the color center is discussed.     

Cordierite III: the site occupation and concentration of Fe3+

Cordierite has the ideal formula (Mg,Fe)₂Al₄Si₅O₁₈ ^.x(H₂O,CO₂), but it must contain some Fe³⁺ to account for its blue color and strong pleochroism. The site occupation and concentration of Fe³⁺ in two Mg-rich natural cordierites have been investigated by EPR and ⁵⁷Fe Mössbauer spectroscopy. In addition, powder IR spectroscopy, X-ray diffraction, and TEM examination were used to characterize the samples. Single-crystal and powder EPR spectra indicate that Fe³⁺ is located on T₁1 in natural cordierites and not in the channels. The amount in Mg-rich cordierites is very small with an upper limit set by Mössbauer spectroscopy giving less than 0.004 cations per formula unit (pfu). Fe³⁺ in cordierite can, therefore, be considered insignificant for most petrologic calculations. Heat-treating cordierite in air at 1,000?°C for 2?days causes an oxidation and/or loss of Fe²⁺ on T₁1, together with an expulsion of Na⁺ from the channels, whereas heating at the Fe–FeO buffer produces little Fe³⁺ in cordierite. Heating at 1,000?°C removes all class I H₂O, but small amounts of class II H₂O remain as shown by the IR measurements. No evidence for channel Fe²⁺ or Fe³⁺ in the heat-treated samples was found. The blue color in cordierite arises from a broad absorption band (E//b and weaker with E//a) around 18,000?cm^?1 originating from charge-transfer between Fe²⁺ in the octahedron and Fe³⁺ in the edge-shared T₁1 tetrahedron. It therefore appears that all natural cordierites contain some tetrahedral Fe³⁺. The brown color of samples heated in air may be due to the formation of very small amounts of submicroscopic magnetite and possibly hematite. These inclusions in cordierite can only be identified through TEM study.     

A model for the irradiative coloration of smoky feldspar and the inhibiting influence of water

Radiation-induced smoky color and associatedelectron paramagnetic resonance (EPR) signals develop only in potassium feldspar (KAlSi₃O₈) free of structurally bound molecular water. Fluid inclusion water does not influence coloration. The integrated intensity of each of the four bands (11,600, 16,200, 19,100, and 27,200 cm^?1) in the optical absorption spectra are linearly correlated with the doubly-integrated intensity of a broad, asymmetric first derivative atg _eff=2.027 in EPR spectra. In microcline, the EPR pattern is resolved into an asymmetric six-line pattern atg _eff=2.024 and a single derivative atg _eff=2.009 which, based on analogy to alkali-silicate glass, are due respectively to [SiO₄/K⁺]²⁺ and a hole shared between two nonbonding oxygens on Si. We propose that structural water inhibits formation of smoky centers in feldspar by releasing atomic hydrogen during irradiation which destroys centers while diffusing towards a stable site.     

Chromium and vanadium impurities in natural green euclase and their relation to the color

Natural specimens of green gemological euclase (chemical formula BeAlSiO₄(OH)) from Brazil were investigated by electron paramagnetic resonance (EPR) and optical absorption. In addition to iron-related EPR spectra, analyzed recently in blue and colorless euclase, chromium and vanadium-related EPR spectra were also detected in green euclase. Their role as color causing centers is discussed. The results indicate that Cr³⁺ ions substitute for Al³⁺ ions in the euclase structure. The EPR rotation patterns of Cr³⁺ with electron spin S = 3/2 were analyzed with monoclinic spin Hamiltonian leading to the parameters of g _xx , g _yy and g _zz equal to 2.018, 2.001 and 1.956 and electronic fine structure parameters of D = −8.27 GHz and E = 1.11 GHz, respectively, with high asymmetry ratio E/D = 0.13. For the vanadium-related EPR spectra the situation is different. It is concluded that vanadium is incorporated as the vanadyl radical VO²⁺ with electron spin S = 1/2 with nearly axial spin Hamiltonian parameters g_zz = 1.9447, g _xx  = 1.9740 g _yy  = 1.9669 and axial hyperfine interactions due to the nuclear spin I = 7/2 of the ⁵¹V isotope leading to A _zz  = 502 MHz, A _xx  = 150 MHz and A _yy  = 163 MHz. The green color of euclase is caused by two strong broad absorption bands centered at 17,185 and 24,345 cm⁻¹ which are attributed to the ⁴A_2g → ⁴T_2g, ⁴T_1g transitions of Cr³⁺, respectively. Vanadyl radicals may introduce some absorption bands centered in the near infrared with tail extending into the visible spectral range.     

Calculations of crystal-field spectra of Cu2+ ions in some low-symmetry minerals

The expressions of the crystal-field potential energies and perturbation matrix elements corresponding to the point symmetriesC _4v ,D _2h andC _i are given in this paper. The crystal-field transition frequencies of Cu²⁺ ions in metatorbernite, conichalcite and turquoise calculated by using these expressions are also reported. The calculated results are essentially consistent with experimental data.     

Identifying characteristics of charge transfer transitions in minerals

Criteria used to identify Fe²⁺-Fe³⁺ and Fe²⁺-Ti⁴⁺ intervalence charge transfer absorption bands in electronic spectra are reviewed and compared to the characteristics of unperturbed Fe²⁺ crystal field bands and those that are intensified by interaction with Fe³⁺. Band energy is the least definitive diagnostic criterion. Changes in band intensity with temperature are also of limited value. Large widths are the most reliable characteristic of charge transfer bands. New optical absorption spectra are presented for euclase, as well as 80 K spectra of rockbridgeite, babingtonite and lazulite. Comparison of optical spectra to magnetic susceptibility measurements for rockbridgeite and babingtonite provides support for recent theories regarding the effect of magnetic coupling on the variation of charge transfer intensity with temperature.     

秘鲁蓝色蛋白石矿物学性质及致色机理初探

近年来蓝色蛋白石的研究仅限于矿物成分及致色机理,并未对其化学成分、红外光谱、拉曼光谱等开展较为深入的分析。本文在前人的研究基础上,通过傅里叶变换红外光谱(FTIR)、X射线粉晶衍射(XRD)、电子探针分析(EMPA)、紫外可见分光光谱、拉曼光谱等技术对样品的振动光谱、官能团表征、矿物组成及呈色机理进行研究。研究结果表明:蓝色蛋白石的主要组成矿物为非晶态蛋白石,且振动光谱与天然蛋白石存在一定程度的频率位移。EMPA分析结果显示蓝色蛋白石主要元素为Si和Cu,且紫外可见分光光谱表征为742 nm附近一吸收强度较高的宽谱带。综合电子探针和紫外可见吸收光谱的测试结果得出,蓝色蛋白石的致色元素为Cu,在其内部呈典型平面正方形结构的[Cu~(2+)(H_2O)_4]~(2+),且Cu含量与其蓝色的体色存在一定的正相关性,即随着Cu含量增加蓝色体色更加浓艳。     

Mineral formation and redox-sensitive trace elements in a near-surface hydrothermal alteration system

A recent hydrothermal mudpool at the southwestern slope of the Rincón de la Vieja volcano in Northwest Costa Rica exhibits an argillic alteration system formed by intense interaction of sulfuric acidic fluids with wall rock materials. Detailed mineralogical analysis revealed an assemblage with kaolinite, alunite, and opal-C as the major mineral phases. Electron paramagnetic resonance spectroscopy (EPR) showed 3 different redox-sensitive cations associated with the mineral phases, Cu⁺ is structure-bound in opal-C, whereas VO²⁺ and Fe³⁺ are located in the kaolinte structure. The location of the redox-sensitive cations in different minerals of the assemblage is indicative of different chemical conditions. The formation of the alteration products can be described schematically as a 2-step process. In a first step alunite and opal-C were precipitated in a fluid with slightly reducing conditions and a low chloride availability. The second step is characterized by a decrease in K⁺ activity and subsequent formation of kaolinite under weakly oxidizing to oxidizing redox conditions as indicated by structure-bound VO²⁺ and Fe³⁺.The detection of paramagnetic trace elements structure-bound in mineral phases by EPR provide direct information about the prevailing redox conditions during alteration and can, therefore, be used as additional insight into the genesis of the hydrothermal, near-surface system.     

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     

An EPR spectroscopic examination of heavy metals in humic and fulvic acid soil fractions

Electron paramagnetic spectra of humic acid and various fractions of fulvic acid from a deep peat soil were studied and related to some of the metals present. In fulvic acid, VO²⁺ occurred in complexed form. The Mn²⁺ components all had a high degree of ionicity. In the humic acid fraction Cu²⁺ was present as a copper porphyrin-type complex.