Optical spectroscopy study of variously colored gem-quality topazes from Ouro Preto,Minas Gerais,Brazil

Variously colored gem-quality topazes from Ouro Preto, Minas Gerais, Brazil, were studied by optical absorption spectroscopy and photoluminescence methods. In the near infrared range (750–2500 nm) the absorption spectra display an identical pattern of narrow intense absorption lines caused by overtones and combination vibrations of OH groups, which do not relate to the coloration of the topazes studied. Their colors were found to be caused by combination of three sets of absorption features, (1), (2), and (3) in the visible and near-UV range, which are due to different color center. (1) denotes a pair of broad split bands with maxima 18 000 and 25 000 cm^–1 caused by electronic spin-allowed dd transitions of Cr³⁺ ions. They cause a light rose to deep violet color and characteristic pleochroism of Cr³⁺-containing topazes. Photoluminescence evidences of at least three different types of Cr³⁺ complexes which, most probably, differ by ligand surroundings, O₄F₂, O₄F(OH) and O₄(OH) (2) Corresponds to the intense weakly polarized UV absorption edge. Two different parts, the thermally stable one, caused by ligand-to-metal charge transfer, and the thermally unstable one, caused by some defect center(s), contribute to the edge. (3) denotes a system of two broad unstructured bands with maxima around 19 000 cm^–1 (X>Y Z) and 24 000 cm^–1 (Y Z X). They cause the unique orange color and characteristic pleochroism of Brazilian Imperial topazes. Combinations of (1) and (3) absorption features cause various yellow-rose colors of the samples. Investigations of natural irradiated and thermally treated topazes show that the color centers (1) and (3) transform to each other at annealing and X- or gamma irradiation. The color of natural orange-red Imperial topazes is assumed to be caused by Cr⁴⁺, stabilized by other impurity ions and/or defect irradiation EPR centers. At T=300 °C Cr⁴⁺ reduces to Cr³⁺, the color of Imperial topazes changes to pale rose, caused by spin-allowed bands of Cr³⁺. In artificially irradiated crystals the (3)-center, Cr⁴⁺, may be induced according to the reaction 2Cr³⁺ Cr⁴⁺ + Cr²⁺, which involves chromium pairs in adjacent Al sites of the structure. Such artificially induced color is unstable at room temperature and in daylight. The process of the decay of (3)-centers may be described as a recombination Cr⁴⁺+Cr²⁺ 2Cr³⁺ that results in vanishing of the (3)-bands accompanied by the appearance or increase in Cr³⁺ dd bands, the original orange color turning to a pale rose.     

Order parameter coupling in leucite: a calorimetric study

The thermal anomalies associated with the Ia3d → I4₁/acd → I4₁/a transition sequence of phase transitions in leucite have been studied by differential scanning calorimetry and interpreted with Landau theory. Both transitions are close to the tricritical point. The coupling between the two transitions is biquadratic, and reduces the stability of the I4₁/a phase.     

Application of Visual MODFLOW to simulation of migration in Cr6+ contaminated site

On the basis of site investigation and data collection of a certain electro plating factory, the groundwater flow and solute transport coupled models were established by applying Visual MODFLOW 4.1 software, which was used to conduct a numerical simulation that forecast the transport process of Cr6+ in groundwater. The results show that contamination plume of Cr6+ transports with groundwater flow direction. Without control measures, in 3 650 days, 19 wells for drinking would be contaminated, and the range of transport would be 52 172 m2, the maximum contamination would be 35.8 mg/L     

Correlation of spectroscopic properties and substitutional sites of Cr3+ in aluminosilicates: I. Kyanite

Using the superposition model in conjunction with our crystal field analysis package recently developed for 3d ions doped at arbitrary low symmetry sites in crystals, the energy levels and statevectors have been predicted within the whole 3d ³ configuration of Cr³⁺ at the four possible triclinic sites in kyanite (Al₂O₃∶SiO₂). The values of the ground state zero-field splitting for each of the four Al sites are evaluated. The splittings of the lower excited state ² E as well as the admixture of ⁴ T ₂ state into ² E have also been determined. The predicted results are compared with the available experimental data on the four possible, but so far not uniquely identified, substitutional Cr³⁺ sites in kyanite thus enabling correlation of the spectroscopic properties and substitutional sites.     

Arsenic in the groundwater of Ouro Preto (Brazil): its temporal behavior as influenced by the hydric regime and hydrogeology

In the city of Ouro Preto (MG), water catchment for public supply originates from superficial drainage, springs, old abandoned mines and some driven wells. In the rocks of the region, As is originally found in gold-enriched sulphide-bearing mineral deposits. The weathering process introduces As into the hydrological system by dissolution of this element into the leachate. Measurement of the As content in the groundwater of some catchments was carried out during 1 year and these measurements demonstrated high As content—up to 224 μg L⁻¹ of As(V)—during the rainy season (the maximum concentration limit according to World Health Organization is 10 μg L⁻¹). Lower values were observed during the dry season and in some sampling stations, As was not even detected. The As concentration variability during 1 year shows a strict and direct relationship to seasonal and hydrological conditions. For city authorities, responsible for public water supply, it is necessary to perform a complete inventory of the water sources used and constantly monitor the As content in the water.     

Sites occupancy of Fe3+ in Garfield Nontronite: A spectroscopic study

New data on the structure of Garfield nontronite have been produced by the use of different spectroscopic techniques: Mössbauer spectroscopy, optical spectroscopy, X-ray absorption edges and EXAFS and NMR. The tetrahedral iron content is found to be no higher than 1 percent. All iron atoms belong to the octahedral sheet excluding the possibility of the presence of non crystallized phases. Some ambiguities remain about the coherence of the octahedral sheet because of the presence of two doublets in the Mössbauer spectrum and at least two lineshapes in NMR spectra of OH which correspond to different environments.     

Luminescence properties of Pr3+ and Sm3+ ions in natural apatites

The luminescence spectra of Pr³⁺ and Sm³⁺ ions in apatite Ca₅[F∣(PO₄)₃] crystals from Spain and Russia have been compared with those for phosphate glasses doped with Pr³⁺, Sm³⁺ and Pr³⁺, Sm³⁺ ions. Time-resolved spectra measurements confirm that, in apatites, samarium ions occupy two non-equivalent crystal sites; the same is assumed for praseodymium ions. For the first time in minerals, the Stark splitting energy levels ΔE for ³H₆ and ¹D₂ of Pr³⁺ ion and ⁶H_7/2 of Sm³⁺ ion were determined. Some small differences in ΔE values for the Spanish and Russian apatite are discussed. The decay times of the excited levels of Pr³⁺, Sm³⁺ and Pr³⁺, Sm³⁺ doped in phosphate glass were measured at room temperature and at 77 K. The energy transfer process between samarium and praseodymium ions was observed and the energy transfer rate was calculated.     

Luminescence sensitivities of quartz grains from eolian deposits in northern China and their implications for provenance

The thermoluminescence (TL) and optically stimulated luminescence (OSL) sensitivities of quartz grains from deserts and loess–red clay sequences are used to trace eolian provenances in northern China. Our results indicate that the 110°C TL peak and OSL sensitivities of quartz grains show differences among Chinese deserts, which can be subdivided into four groups according to the spatial variations of luminescence sensitivities. Such differences are related mostly to the regional difference in rock types of mountains surrounding or adjacent to the deserts. We also examine the possible provenance changes between the Quaternary loess and the Tertiary eolian red clay, and the results indicate that the luminescence sensitivity of Tertiary red clay is higher than that of Quaternary loess (L1, L15, and L33), implying source materials of the eolian deposits changed relative to those of the Quaternary.     

Correlation of spectroscopic properties and substitutional sites of Cr3+ in aluminosilicates: II. Andalusite and sillimanite

This paper is an extension of the earlier one dealing with kyanite in which the best fitting value of the oxygen ligand distance for Cr³⁺ is adopted to study the spectroscopic properties of Cr³⁺ ions doped at the two possible Al sites in the other two polymorphs of the aluminosilicate group (Al₂O₃ · SiO₂), namely, andalusite and sillimanite. The superposition model and the crystal field analysis package recently developed for 3d ions doped at arbitrary low symmetry sites in crystals are used to predict energy levels and statevectors within the whole 3d ³ configuration. Then the values of the ground state zerofield splitting for Cr³⁺ ions at each Al sites in the two crystals are obtained. The splittings of the lower excited states ² E and ⁴ T ₂ as well as the admixture of ⁴ T ₂ into ² E have also been predicted. Comparison of our results with the available experimental data enable us to correlate the optical and EPR Spectroscopic properties with the substitutional Cr³⁺ sites. The conclusion is that in andalusite and sillimanite only the Al sites with nearly-octahedral six-fold coordination seem to be occupied by Cr³⁺ ions.     

Luminescence dating of loessic sediments from the Loess plateau, China

Loess/palaeosol sequences from the Loess plateau in China were investigated by combined infrared optically stimulated luminescence (IRSL) and thermoluminescence (TL) dating techniques in order to study the luminescence properties of the loessic sediments and to provide a direct chronological link for correlation and position of the last interglacial soil in Central Asia and the Loess plateau in China. Sensitivity changes were found for all samples through artificial bleaching of the samples. The greatest sensitivity changes, of up to 50%, were found for very old loess samples designated to be older than the Matu-yama/Brunhes magnetic boundary and hence older than 788,000±1,800 years. The upper dating limit, as investigated by the very old loess samples, ranges from 250,000 to 300,000 years, if the TL additive dose method is applied. The chronological position of the last interglacial soil S1 at the section near Lanzhou indicates luminescence age estimates ranging from 82,000 to 75,000 years for the marine-isotope stage 5 to 4 transition. However, the loess from below S1 yielded luminescence age estimates between 153,200±14,200 and 110,100±20,100 years for TL and IRSL additive dose methods, respectively. Thus, a direct correlation between the S1 and the first intercalated pedocomplex PC1 in Central Asia is most likely. Received: 31 March 1998 / Accepted: 25 October 1998     

EPR study of chromium-doped forsterite crystals: Cr3+(M1) with associated trivalent ions Al3+ and Sc3+

Electron paramagnetic resonance (EPR) study of single crystals of forsterite co-doped with chromium and scandium has revealed, apart from the known paramagnetic centers Cr³⁺(M1) and Cr³⁺(M1)– $ V_{{{\text{Mg}}^{2 + } }} $ (M2) (Ryabov in Phys Chem Miner 38:177–184, 2011), a new center Cr³⁺(M1)– $ V_{{{\text{Mg}}^{2 + } }} $ (M2)–Sc³⁺ formed by a Cr³⁺ ion substituting for Mg²⁺ at the M1 structural position with a nearest-neighbor Mg²⁺ vacancy at the M2 position and a Sc³⁺ ion presumably at the nearest-neighbor M1 position. For this center, the conventional zero-field splitting parameters D and E and the principal g values have been determined as follows: D?=?33,172(29) MHz, E?=?8,482(13) MHz, g?=?[1.9808(2), 1.9778(2), 1.9739(2)]. The center has been compared with the known ion pair Cr³⁺(M1)–Al³⁺ (Bershov et al. in Phys Chem Miner 9:95–101, 1983), for which the refined EPR data have been obtained. Based on these data, the known sharp M1″ line at 13,967?cm^?1 (with the splitting of 1.8?cm^?1), observed in low-temperature luminescence spectra of chromium-doped forsterite crystals (Glynn et al. in J Lumin 48, 49:541–544, 1991), has been ascribed to the Cr³⁺(M1)–Al³⁺ center. It has been found that the concentration of the new center increases from 0 up to 4.4?×?10¹⁵?mg^?1, whereas that of the Cr³⁺(M1) and Cr³⁺(M1)– $ V_{{{\text{Mg}}^{2 + } }} $ (M2) centers quickly decreases from 7.4?×?10¹⁵?mg^?1 down to 3?×?10¹⁵?mg^?1 and from 2.7?×?10¹⁵?mg^?1 down to 0.5?×?10¹⁵?mg^?1, i.e., by a factor of 2.5 and 5.4, respectively, with an increase of the Sc content from 0 up to 0.22 wt?% (at the same Cr content 0.25 wt?%) in the melt. When the Sc content exceeds that of Cr, the concentration of the new center decreases most likely due to the formation of the Sc³⁺(M1)– $ V_{{{\text{Mg}}^{2 + } }} $ (M2)–Sc³⁺ complex instead of the Cr³⁺(M1)– $ V_{{{\text{Mg}}^{2 + } }} $ (M2)–Sc³⁺ center. The formation of such ordered neutral complex is in agreement with the experimental results, concerning the incorporation of Sc into olivine, recently obtained by Grant and Wood (Geochim Cosmochim Acta 74:2412–2428, 2010).     

高温高压下石膏脱水相变的原位拉曼光谱研究

本文运用激光拉曼光谱仪,利用水热金刚石压腔装置对高温高压条件下石膏-水体系中的石膏脱水相变进行拉曼光谱研究.在压力0.1 MPa～837.9 MPa和温度16～200 ℃条件下通过系列实验对相变的过程进行了原位光谱分析.与人们已知的无水条件下石膏分两步脱水的过程不同,高压下石膏在饱和水环境下倾向于一次性的脱去所有结晶水而形成无水石膏,实验中没有观察到半水石膏的出现.通过实验数据得到石膏和无水石膏的转折温度和平衡压力间的关系式为P(MPa)=19.56·T(℃)-2926.5.     

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.     

Incorporation of Cr<Superscript>3+</Superscript> in dickite: a spectroscopic study

 We have investigated a well-ordered sample of natural Cr-bearing dickite from Nowa Ruda (Lower Silesia, Poland) using electron paramagnetic resonance (EPR) at X- and Q-band frequencies (9.42 and 33.97 GHz, respectively) and optical diffuse reflectance spectroscopy. The observation of the spin-forbidden transitions at 15500 and 14690 cm⁻¹ allows us to unambiguously identify the major contribution of octahedrally coordinated Cr³⁺ ions in the optical spectrum. The X- and Q-band EPR spectra show two superposed Cr³⁺ signals. The corresponding fine-structure parameters were determined at room temperature and 145 K. These results suggest the substitution of Cr³⁺ for Al³⁺ in equal proportions in the two unequivalent octahedral sites of the dickite structure. In kaolin group minerals, the distortion around Cr³⁺ ions (λ≈ 0.2–0.4) in Al sites is significantly less rhombic than that observed around Fe³⁺ ions (λ≈ 0.6–0.8). Received: 29 June 2001 / Accepted: 22 October 2001     

Electronic absorption spectra of Cr3+ ions in natural clinopyroxenes

The polarized (E‖a′, E‖b and E‖c) electronic absorption spectra of five natural chromium-containing clinopyroxenes with compositions close to chromdiopside, omphacite, ureyite-jadeite (12.8% Cr₂O₃), jadeite, and spodumene (hiddenite) were studied. The polarization dependence of the intensities of the Cr³⁺ bands in the clinopyroxene spectra cannot be explained by the selection rules for the point groups C ₂ or C _2v but can be accounted for satisfactorily with the help of the higher order pseudosymmetry model, i.e. with selection rules for the point symmetry group C _3v. The trigonal axis of the pseudosymmetry crystal field forms an angle of 20.5° with the crystallographic direction c in the (010) plane. D _q increases from diopside (1542 cm^?1) through omphacite (1552 cm^?1), jadeite (1574 cm^?1) to spodumene (1592 cm^?1). The parameter B which is a measure of covalency for Cr³⁺-O bonds at M1 sites in clinopyroxene depends on the Cr³⁺ concentration and the cations at M2 sites.     

Absorption spectra of Cr3+ in Al2O3 under shock compression

Unpolarized absorption spectra of single crystals of Cr³⁺ doped Al₂O₃ (synthetic ruby) have measured using a new, time-resolving, dispersive, streak photographic system over the range ～350 to ～700 nm during a series of shock loading experiments. The crystal field absorptions assigned to the transition ⁴ A _2g→⁴ T _2g were observed to shift in a series of experiments from 555±1 nm at atmospheric pressure to 503±5 nm at 46 GPa. In a single experiment at 32 GPa the ⁴ A _2g→⁴ T _1g transition was observed to shift from 405±1 to 386±5 nm. The present data extrapolate downwards in compression toward the 10 GPa data of Stephens and Drickamer (1961) although both crystal field absorption energies increase considerably less with compression than predicted by the simple ionic point charge model. The single datum observed for the Racah parameter B, 588±38 cm^?1 at 32 GPa, is consistant with previous results to 10 GPa and the trend of decreasing B, with compression expected from the divergence of the data from the point charge model due to increasing covalancy.     

富含Na+ 、Ca2+、Al3+、Cr3+蒙脱石对垃圾渗滤液中有机物的吸附

由于层间含有高价态金属阳离子的蒙脱石对特定有机物的吸附能力可大大增强,故分别用层间含有Na+、Ca2+、Al3+和Cr3+的蒙脱石对垃圾渗滤液中的有机物进行吸附实验,研究它们吸附苯酚、二甲苯和COD的能力及离子形态对吸附效果的影响.结果表明,含高价金属阳离子的蒙脱石对苯酚和COD的吸附能力较高,吸附能力由小到大的顺序为Na+<Ca2+<Al3+<Cr3+蒙脱石;各种类型蒙脱石对二甲苯的吸附能力相对较低,并且没有一定的规律可循.并对氢键吸附机制进行了探讨.     

Electronic absorption and luminescence spectroscopic studies of kyanite single crystals: differentiation between excitation of FeTi charge transfer and Cr3+ dd transitions

A selected set of five different kyanite samples was analysed by electron microprobe and found to contain chromium between <0.001 and 0.055 per formula unit (pfu). Polarized electronic absorption spectroscopy on oriented single crystals, R₁, R₂-sharp line luminescence and spectra of excitation of λ₃- and λ₄-components of R₁-line of Cr³⁺-emission had the following results: (1) The Fe²⁺–Ti⁴⁺ charge transfer in c-parallel chains of edge connected M(1) and M(2) octahedra shows up in the electronic absorption spectra as an almost exclusively c(||Z′)-polarized, very strong and broad band at 16000 cm⁻¹ if <, in this case the only band in the spectrum, and at an invariably lower energy of 15400 cm⁻¹ in crystals with  ≥ . The energy difference is explained by an expansion of the O_f–O_k, and O_b–O_m edges, by which the M(1) and M(2) octahedra are interconnected (Burnham 1963), when Cr³⁺ substitutes for Al compared to the chromium-free case. (2) The Cr³⁺ is proven in two greatly differing crystal fields a and b, giving rise to two sets of bands, derived from the well known dd transitions of Cr^{3+ 4}A_2g→⁴T_2g(F)(I), →⁴T_1g(F)(II), and →⁴T_1g(P)(III). Band energies in the two sets a and b, as obtained by absorption, A, and excitation, E, agree well: I: 17300(a, A), 17200(a, E), 16000(b, A), 16200(b, E); II: 24800(a, A), 24400(a, E); 22300(b, A), 22200(b, E); III: 28800(b,A) cm⁻¹. Evaluation of crystal field parameters from the bands in the electronic spectra yield Dq(a)=1730 cm⁻¹, Dq(b)=1600 cm⁻¹, B(a)=790 cm⁻¹, B(b)=620 cm⁻¹ (errors ca. ±10 cm⁻¹), again in agreement with values extracted from the λ³, λ⁴ excitation spectra. The CF-values of set a are close to those typical of Cr³⁺ substituting for Al in octahedra of other silicate minerals without constitutional OH⁻ as for sapphirine, mantle garnets or beryl, and are, therefore, interpreted as caused by Cr³⁺ substituting for Al in some or all of the M(1) to M(4) octaheda of the kyanite structure, which are crystallographically different but close in their mean Al–O distances, ranging from 1.896 to 1.919 A (Burnham 1963), and slight degrees of distortion. Hence, band set a originates from substitutive Cr³⁺ in the kyanite structural matrix. The CF-data of Cr³⁺ type b, expecially B, resemble those of Cr³⁺ in oxides, especially of corundum type solid solutions or eskolaite. This may be interpreted by the assumption that a fraction of the total chromium contents might be allocated in a precursor of a corundum type exsolution. Received: 3 January 1997 / Revised, accepted: 2 May 1997