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.     

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。     

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.     

Iron oxidation state in lower mantle mineral assemblages: II. Inclusions in diamonds from Kankan, Guinea

Inclusions of ferropericlase and former (Mg,Fe)(Si,Al)O₃ perovskite in diamonds from Kankan, Guinea believed to originate in the lower mantle were studied using Mössbauer spectroscopy to determine Fe³⁺/ΣFe. Fe³⁺ concentration in the (Mg,Fe)(Si,Al)O₃ inclusion is consistent with empirical relations relating Fe³⁺/ΣFe to Al concentration, supporting the inference that it crystallised in the perovskite structure at lower mantle conditions. In ferropericlase there is a nearly linear variation of trivalent cation abundance with monovalent cation abundance, suggesting a substitution of the form Na_0.5M_0.5³⁺O (M=Fe³⁺, Cr³⁺, Al³⁺). Excess positive charge is likely balanced by cation vacancies, where their abundance is observed to increase with increasing iron concentration, consistent with high-pressure experiments. The abundance of cation vacancies is related to oxygen fugacity, where ferropericlase inclusions from Kankan and São Luiz (Brazil) are inferred to have formed at conditions more oxidising than Fe-(Mg,Fe)O equilibrium, but more reducing than Re-ReO₂ equilibrium. Fe²⁺/Mg partition coefficients between (Mg,Fe)(Si,Al)O₃ and ferropericlase were calculated for inclusions co-existing in the same diamond using Mössbauer data and empirical relations based on high-pressure experimental work. Most values are consistent with high-pressure experiments, suggesting that these inclusions equilibrated at lower mantle conditions. The measured ferropericlase Fe³⁺ concentrations are consistent with diamond formation in a region of redox gradients, possibly arising from the subduction of oxidised material into reduced lower mantle. Reduction of carbonate to form ferropericlase and diamond is consistent with a slight shift of Kankan δ¹³C values to isotopically heavy compositions compared to the worldwide dataset, and could supply the oxygen necessary to satisfy the high Fe³⁺ concentration in (Mg,Fe)(Si,Al)O₃ perovskite, as well as account for the high proportion of ferropericlase in the lower mantle paragenesis. The heterogeneity of lower mantle diamond sources indicates that the composition of lower mantle diamonds do not necessarily reflect those of the bulk mantle.     

近红外反射光谱学在岩石矿物研究中的应用Ⅱ.快速测定地质样品中有机质

利用偏最小二乘法回归的多变量校正方式,建立了应用近红外反射光谱学方法无损快速测定各种地质样品中有机质的模型.设计了多重散射光校正、标准正常变量转换及导数光谱,扣除额外基线和重叠信号的影响,分离出与有机质含量有关的光谱信息.大多数地质样品的有机质近红外反射光谱估算结果与化学法符合.     

大兴安岭地区浅覆盖层对地面伽马能谱测量的影响

讨论在大兴安岭地区进行地质填图中浅覆盖层对伽马能谱测量的影响问题。通过放射性元素的取样分析、岩石—土壤的矿物分析以及实测剖面分析,得知了伽马能谱测量的影响因素,从而为应用伽马能谱测量解决地质填图中的问题提供了依据。     

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.     

Mudstones of the Tanqua Basin, South Africa: an analysis of lateral and stratigraphic variations within mudstones, and a comparison of mudstones within and between turbidite fans

Permian deep‐water mudstones in the Tanqua Basin, South Africa, have been studied using geochemical and spectral gamma ray techniques. The mudstones occur as thick sequences between sand‐rich submarine fans, but also occur as thinner mud‐rich units within each fan. The interfan mudstones are interpreted to have accumulated during transgression and the consequent period of relatively high sea‐level, while the submarine fans and their intrafan mudstones were deposited during regression and relatively low sea‐level. Geochemical analyses revealed systematic differences between interfan and intrafan mudstones because the two types of mudstones have slightly different source lithologies. Differences between the two types of mudstone suggest that changes in relative sea‐level played a role in controlling exposure of sediment source areas. There are geochemical signals that display systematic stratigraphic trends within both interfan and intrafan mudstones. These are best explained by gradual denudation, exposure and weathering of different lithologies within a single sediment source area. Both interfan and intrafan mudstones have uniform geochemical signals along the flow direction except for the relative amount of uranium. It is most likely that the basinward increase in uranium in the mudstones is the result of reduced clastic dilution of uranium‐bearing pelagic fallout.