The effect of thermal treatment on the 57Fe Mössbauer spectrum of beryl

Mössbauer spectra (MS) of blue, green and yellow beryl (ideally Be₃Al₂Si₆O₁₈) containing approximately 1% of iron were obtained at 295 and 500 K. Room temperature (RT) spectra of both blue and green samples showed the presence of an asymmetric Fe²⁺ doublet (ΔE _Q~2.7 mm/s, δ~1.1 mm/s), with a very broad low-velocity peak. There is no clear evidence for the presence of a ferric component. The MS of the yellow sample at RT consists of an intense central absorption with parameters typical for Fe³⁺ (ΔE _Q~0.4 mm/s, δ~0.29 mm/s), plus an apparently symmetrical Fe²⁺ doublet. This sample acquires a light-blue shade upon heating in air at about 620 K. Thermal treatments at high temperatures caused no significant changes in the MS, but the green and yellow beryl acquire a blue colour. All these results are interpreted in relation to the existence of channel water and the distribution of iron among the available crystallographic sites.     

Synchrotron IR study of hydrous ringwoodite (γ-Mg2SiO4) up to 30 GPa

High-pressure synchrotron infrared (IR) absorption spectra were collected between 650 and 4,000 cm⁻¹ at ambient temperature for hydrous Mg-ringwoodite (γ-Mg₂SiO₄) up to 30 GPa. The main feature in the OH⁻ stretching region is an extremely broad band centred at 3,150 cm⁻¹. The hydrogen bond is strong for most protons and the most probable site for protonation is the tetrahedral edge. With increasing pressure, this band shifts downward while decreasing its integrated intensity until disappearance at a pressure of 25 GPa. Only one band at 2,450 cm⁻¹ and an absorption plateau persist with a maximum wavenumber of 3,800 cm⁻¹. This behaviour is reversible upon pressure release. We interpret this as a second-order phase transition occurring in hydrated Mg-ringwoodite at high pressure (beyond ∼ 25 GPa). This result is compatible with the observation by Kleppe et al. (Phys Chem Miner 29:473–476, 2002a) who suggested the presence of Si–O–Si linkages and/or partial increase in the coordination of Si. Beyond the phase transition, the protons are delocalized and their environment on the ringwoodite structure is probably quite different from that at low pressure. Data obtained in situ at high pressures and temperatures are needed to better understand the effect of protonation on the structure and to better constrain this phase transition.     

大别山及苏鲁地区微粒金刚石分类及其大地构造意义

1992年发现大别山首例微粒金刚石之后，又于2003年和2004年在大别山和苏鲁地区的榴辉岩薄片中和榴辉岩的人工重砂中发现了微粒金刚石。本文报道其中尚未发表的7颗，并对2颗较大的薄片中的微粒金刚石和2颗自由晶体金刚石进行拉曼光谱和红外光谱测试。研究结果表明，本区所有微粒金刚石都为IaA和IaB型金刚石的混合体。缺少Ib型金刚石，表明没有人造金刚石的混入。薄片中的金刚石大部分为石榴子石的包裹体，少数产出于颗粒之间，直径为30-180μm。自由颗粒微粒金刚石直径为400-700μm。在大别山北部，不但又一次找到了微粒金刚石，还在石榴子石中发现有单斜辉石、磷灰石和金红石的出溶。这表明北大剐不但是超高压地质体，而且可能是本区俯冲最深的地质体。     

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.     

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     

Premelting and calcium mobility in gehlenite (Ca2Al2SiO7) and pseudowollastonite (CaSiO3)

 Premelting effects in gehlenite (Ca₂Al₂SiO₇) have been studied by Raman spectroscopy and calorimetry, and in gehlenite and pseudowollastonite (CaSiO₃) by electrical conductivity. The enthalpy of premelting of gehlenite is 17.3 kJ mol⁻¹ and represents 9% of the reported enthalpy of fusion, which is in the range of the reported fraction of other minerals. The Raman and electrical conductivity experiments at high temperatures, for gehlenite and pseudowollastonite, show that the premelting effects of both compositions are associated with enhanced dynamics of calcium atoms near the melting point. This conclusion agrees with the results obtained for other minerals like diopside, but contrasts with those found for sodium metasilicate in which the weaker bonding of sodium allows the silicate framework to distort near the melting temperature and deform in such a way to prefigure the silicate entities present in the melt. Received: 30 April 2002 / Accepted: 7 August 2002 Acknowledgements We thank Y. Linard for help with DSC measurements and two anonymous reviewers for their constructive comments. This work has been partly supported by the EU Marie-Curie fellowship contract no. HPMF-CT-1999-00329, the CNRS-Carnegie Institution of Washington program PICS no.192, and the NSF grants EAR-9614432 and EAR-9901886 to B.O.M.     

Column Amounts of ClONO2, HCl, HNO3, and HF from Ground-Based FTIR Measurements Made Near Kiruna, Sweden, in Late Winter 1994

During SESAME phase I ground-based FTIR measurements were performed atEsrange near Kiruna, Sweden, from 28 January to 26 March 1994. Zenith columnamounts of ClONO₂, HCl, HF, HNO₃,O₃, N₂O, CH₄, and CFC-12 werederived from solar absorption spectra. Time series of ClONO₂and HCl indicate a chlorine activation at the end of January and around 1March. On 1 March a very low amount of HCl of 2.09times; 10¹⁵molec. cm^-2 was detected, probably caused by a second chlorineactivation phase starting from an already decreased amount of HCl. The ratioof column amounts of HCl to ClONO₂ decreased inside the vortexfrom about 1 in January to 0.4 in late March compared to values of about 2outside the vortex. Although the Arctic stratosphere was rather warm in winter1993/94 and PSCs occurred seldom, chlorine partitioning into its reservoirspecies HCl and ClONO₂ changed during that winter andClONO₂ is the major chlorine reservoir at the end of thewinter as in cold winters like 1991/92 and 1994/95.     

伊利石层间钾释放的远红外光谱研究

本文介绍了新近研究层间交换的远红外方法，并用该方法研究了金砂伊早石层间交换的性质，随着温度的升高，伊利石的远红外谱段从１０８ｃｍ＾－１向低波数方向偏移，３００Ｃ时为１０７ｃｍ＾－１，５００℃时为１０００ｃｍ＾－１，７００℃时为９８ｃｍ＾－１，同时，伊利石的释钾程度也伴随着增加，远红外谱同释放钾的能力有一清楚对比，因此可以用远红外方法预言伊利石释钾的能力，最后，利用量子化学计算的ＰＭ３方法首次从理论     

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.     

Thermal decomposition of NH4-analcime

The thermal decomposition of ammonium-exchanged natural analcime is characterized by gas chromatography, IR spectroscopy and X-ray diffraction. The de-ammoniation and dehydroxylation proceed in parallel throughout the decomposition, which evidences the instability of the protonated analcime framework. The mechanism of degassing of NH₄-analcime changes throughout its decomposition. At the initial step, the mechanism of de-ammoniation consists in thermal dissociation of NH₄⁺ molecule onto NH₃ and proton (framework OH group) and diffusion of NH₃ out of the structure. Subsequent decomposition and removal of the OH groups lead to a progressive loss of crystallinity. At this step, an apparent activation energy for NH₃ desorption is estimated to be 145(±13) kJ mol^–1. This value is within the upper limit of the activation energy characteristic for the NH₃ desorption from proton centres in large-pore zeolites. At the final step, the adsorption of NH₃ and protons onto the defect centres in the amorphosed aluminosilicate framework results in a significant increase of an apparent activation energy for the de-ammoniation and dehydroxylation up to 270(±20) kJ mol^–1.