Spectroscopic evidence for pressure-induced phase transitions in diopside

 Raman spectra of diopside were collected from atmospheric pressure to 71 GPa. The pressure dependences of 22 modes were determined. Changes occurred in the spectra at three different pressures. First, at approximately 10 GPa, the two Raman modes at 356 and 875 cm⁻¹ disappeared, while the mode at 324 cm⁻¹ split into two modes, diverging at this pressure with significantly different pressure shifts; second, at approximately 15 GPa, a small (1 to 2 cm⁻¹) drop in several of the frequencies was observed accompanied by changes in the pressure dependency of some of the modes; and third, above 55 GPa, the modes characteristic of chains of tetrahedrally coordinated silicon disappeared, while those for octahedrally coordinated silicon appeared. The first change at 10 GPa appears to be a C2/c to C2/c transition involving a change in the Ca coordination. The third change above 55 GPa appears to be a change in the silicon coordination. At 15 GPa, it is suggested that a change in compressional mechanism takes place. Received: 14 November 2000 / Accepted: 9 January 2002     

Surface chemical analysis in coal preparation research: complementary information from XPS and ToF-SIMS

The application of X-ray photoelectron spectroscopy (XPS) to coal surface characterisation for preparation research is described. Progress towards the acquisition of complementary surface chemical information by time-of-flight secondary ion mass spectrometry (ToF-SIMS) is also discussed. Surface-based beneficiation techniques such as flotation are assuming greater importance as the proportion of fines in raw coal increases due to the proliferation of high capacity mining methods. A necessary condition for the floatability of a coal particle is adequate hydrophobicity, and the degree of hydrophobicity of the flotation concentrate is one factor influencing the ease with which its dewatering can be affected. The hydrophobicity of a coal is very difficult to measure directly because of microporosity, and it is often necessary to deduce the degree of hydrophobicity from a knowledge of the surface chemistry. XPS is able to provide sufficient analytical data to allow relative levels of hydrophobicity to be estimated. In principle, ToF-SIMS should be able to supply additional information enabling refinement of such estimates; however, there are insufficient data at present to allow the ionic fragments detected to be related to specific functional groups at the coal surface.     

Al hematites prepared by homogeneous precipitation of oxinates: material characterization and determination of the Morin transition

A novel method for synthesis of aluminium hematites, based upon the homogeneous precipitation of Fe and Al oxinates in various proportions, is presented. The precursor precipitates are heated in air at 700?°C. X-ray diffraction, thermal analyses, BET, FTIR, optical reflection analysis, TEM and Mössbauer spectroscopy at room temperature and 80?K of the resulting products indicate that single-phase hematites are formed with structural Al substitution of up to 10 at%. Interestingly, the particle size (>100?nm) is not substantially reduced by the Al content. Although it remains difficult to obtain a homogeneously distributed Al substitution in the final hematite, this processing line offers a unique opportunity to separate the effects of grain size and Al substitution on the Morin transition temperature (T _M) of Al hematite. From the comparison between the present hematites and a series of Al-substituted hematites with lepidocrocite as precursor, it could be shown that the effect on T _M, associated with a change of a factor 10 in grain size, is about 1/3 of the effect caused by a change of 10 in the degree of substitution. Finally, it is suggested that proper thermal treatments under different conditions of the same precursors are likely to produce spinel phases.     

Isothermal annealing of partially metamict zircon: evidence for a three-stage recovery process

 Raman spectroscopy and the powder diffraction technique have been used to monitor the recovery process of two partially metamict zircons (2.6 and 4.8 × 10¹⁸ α-decays g⁻¹) from Sri Lanka during a series of isothermal annealing experiments in the temperature range from 870 to 1622 K. These experiments show for the first time that structural recovery in partially metamict zircon proceeds via three distinct recovery stages, each of which occurs within a distinct time-temperature regime. Whereas the first two stages have previously been recognized (recovery of damaged crystalline remnants and epitaxial recrystallization), the third stage has not yet been identified as a single activated process. It is suggested that anisotropic defect annealing during the first stage at low temperatures, where the structure recovers preferentially along the a(b) plane, produces a geometrical situation where large structural rearrangements are necessary to remove the remaining defects inside the crystalline material. This situation is approximately reached when the amorphous domains start to recrystallize. The reason for anisotropic annealing can be found in a different connectivity between polyhedral linkages in both directions of the zircon lattice. High apparent activation energies, in the range of 6.4 to 7.9 eV, were determined for the third recovery stage from the Raman data, which are interpreted to reflect large structural rearrangements (i.e. polyhedral tilting) associated with the final recovery of the c axis. This explains the occurrence of a distinct recrystallization stage without defect annealing. Finally, it should be mentioned that the first recovery stage is not necessarily expected to occur in less damaged zircon crystals (<∼2 × 10¹⁸ α-decays g⁻¹), since less stable defects along the basal plane might have already been self-annealed during radiation damage accumulation under ambient temperatures. Received: 6 September 2001 / Accepted: 25 February 2002     

Diamonds from placers in western and central Africa: A problem of primary sources

This paper discusses diamonds and their accessory minerals from the Koidu kimberlites, placers on the Bafit River in Sierra Leone, and Chikapa placers in the Democratic Republic of Congo. Minerals from the placers are characterized by fine preservation and bear no evidence of long-term transportation. In placers, garnet, ilmenite and zircon have been found, but the specific features of their chemical composition do not coincide with those of minerals from kimberlites. Diamonds from the placers are of a mantle origin, but they have no direct analogs in the known kimberlite and lamproite pipes.     

Sorption Characteristics of Rare Earth Element Eu^3＋ onto Silica-Water Interfaces Studied by Fluorescence Spectroscopy

The sorption of Eu species onto nano-size silica-water interfaces was investigated using fluorescence spectroscopy for Ph ranges of 1-8.5 and an initial Eu concentration (Ceu) of 2×10-4 M. The sorption rate of Eu was initially low, but significantly increased at Ph>4. The sorption density of Eu species on a silica surface was ～1.58×10-7 mol/m2 when the dissolved Eu species were completely sorbed onto silica-water interfaces at Ph=～5.8. The sorbed Eu species at Ph<6 is aquo Eu3 , which is sorbed onto silica-water interfaces as an outer-sphere complex at Ph<5, but may be sorbed as an inner-sphere bidentate complex at 5相似文献   

合浦珠母贝铁的穆斯堡尔谱学研究

应用^57Fe穆斯堡尔谱学的方法研究了四个不同生长期合浦珠母贝铁的化学状态和Fe^2 /Fe^3 的值，它们的Fe^2 和Fe^3 的相对含量分别为4.1%～29.4%和76.6%～95.9%,Fe^2 /Fe^3 值的变化为0.043～0.42。3个月龄的Fe^2 /Fe^3 值大于10个月龄，从10个月龄到22个月龄的Fe^2 /Fe^3 值呈增加的趋势，这可能反映了不同生长期合浦珠母贝对不同价态的铁的需求。     

碱性玄武岩中的某些巨晶单斜辉石──Ⅱ:穆斯堡尔谱──兼论单斜辉石的异常穆斯堡尔谱和铁结构态的测定

本文对辽宁宽甸碱性玄武岩中巨晶单斜辉石进行穆斯堡尔谱研究。应用晶体结构研究结果较合理地解释了单斜辉石的异常穆斯堡尔谱。结合XRD讨论了单斜辉石中Fe结构态的测定以及穆斯堡尔谱的可应用性。巨晶应结晶于相当氧化的环境。     

Dehydration experiments on natural omphacites: qualitative and quantitative characterization by various spectroscopic methods

A series of natural omphacites from a wide range of P, T occurrences were investigated by electron microprobe (EMP), infrared (IR)-, Mössbauer (MS)- and optical spectroscopy in the UV/VIS spectral range (UV/VIS), secondary ion mass spectrometry (SIMS) and single crystal structure refinement by X-ray diffraction (XRD) to study the influence of hydrogen loss on valence state and site occupancies of iron. In accordance with literature data we found Fe²⁺ at M1 as well as at M2, and in a first approach assigned Fe³⁺ to M1, as indicated by MS and XRD results. Hydrogen content of three of our omphacite samples were measured by SIMS. In combination with IR spectroscopy we determined an absorption coefficient: ε _i,tot = 65,000 ± 3,000 lmol_H2O ^?1 cm^?2. Using this new ε _i,tot value, we obtained water concentrations ranging from 60 to 700 ppm H₂O (by weight). Hydrogen loss was simulated by stepwise heating the most water rich samples in air up to 800°C. After heat treatment the samples were analyzed again by IR, MS, UV/VIS, and XRD. Depending on the type of the OH defect, the grade of dehydration with increasing temperature is significantly different. In samples relatively poor in Fe³⁺ (<0.1 Fe³⁺ pfu), hydrogen associated with vacancies at M2 (OH bands around 3,450 cm^?1) starts to leave the structure at about 550°C and is completely gone at 780°C. Hydrogen associated with Al³⁺ at the tetrahedral site (OH bands around 3,525 cm^?1, Koch-Müller et al., Am Mineral, 89:921–931, 2004) remains completely unaffected by heat treatment up to 700°C. But all hydrogen vanished at about 775°C. However, this is different for a more Fe³⁺-rich sample (0.2 Fe³⁺ pfu). Its IR spectrum is characterized by a very intense OH band at 3,515 cm^?1 plus shoulder at 3,450 cm^?1. We assign this intense high-energy band to vibrations of an OH dipole associated with Fe³⁺ at M1 and a vacancy either at M1 or M2. OH release during heating is positively correlated with decrease in Fe²⁺ and combined with increase in Fe³⁺. That dehydration is correlated with oxidation of Fe²⁺ is indirectly confirmed by annealing of one sample in a gas mixing furnace at 700°C under reducing conditions keeping almost constant OH^? content and giving no indication of Fe²⁺-oxidation. Obtained data indicate that in samples with a relatively high concentration of Fe²⁺ at M2 and low-water concentrations, i.e., at a ratio of Fe^{2+ M2}/H > 10 dehydration occurs by iron oxidation of Fe²⁺ exclusively at the M2 site following the reaction: \( {\left[ {{\text{Fe}}^{{{\text{2 + [ M2]}}}}{\text{OH}}^{ - } } \right]} = {\left[ {{\text{Fe}}^{{{\text{3 + [ M2]}}}} {\text{O}}^{{{\text{2}} - }} } \right]} + {\text{1/2}}\;{\text{H}}_{{\text{2}}} \uparrow . \) In samples having relatively low concentration of Fe²⁺ at M2 but high-water concentrations, i.e., ratio of Fe^{2+ M2}/H < 5.0 dehydration occurs through oxidation of Fe²⁺ at M1.     

Optical and X-Ray Observations of the Symbiotic System Ag Draconis During Quiescence and Outburst

We review the main characteristics of the symbiotic system AG Draconis, with special emphasis on its optical and X-ray variations. We also discuss the X-ray to visual energy distribution during quiescence and outburst and describe our spectroscopic and X-ray observations during the 2003 outburst. Based on X-ray observations collected with the XMM–Newton Observatory, on INES data from the IUE satellite, and on optical spectra collected with the Asiago–Cima Ekar, Bologna–Loiano and La Palma–Galileo Italian telescopes.