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. 相似文献
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. 相似文献
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 Na0.5M0.53+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. 相似文献
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. 相似文献
This paper reports on the petrology and geochemistry of a diamondiferous peridotite xenolith from the Premier diamond mine in South Africa.
The xenolith is altered with pervasive serpentinisation of olivine and orthopyroxene. Garnets are in an advanced state of kelyphitisation but partly fresh. Electron microprobe analyses of the garnets are consistent with a lherzolitic paragenesis (8.5 wt.% Cr2O3 and 6.6 wt.% CaO). The garnets show limited variation in trace element composition, with generally low concentrations of most trace elements, e.g. Y (<11 ppm), Zr (<18 ppm) and Sr (<0.5 ppm). Garnet rare earth element concentrations, when normalised against the C1 chondrite of McDonough and Sun (Chem. Geol. 120 (1995) 223), are characterised by a rare earth element pattern similar to garnet from fertile lherzolite.
All diamonds recovered are colourless. Most crystals are sharp-edged octahedra, some with minor development of the dodecahedral form. A number of crystals are twinned octahedral macles, while aggregates of two or more octahedra are also common. Mineral inclusions are rare. Where present they are predominantly small black rosettes believed to consist of sulfide. In one instance a polymineralic (presumably lherzolitic) assemblage of reddish garnet, green clinopyroxene and a colourless mineral is recognised.
Infrared analysis of the xenolith diamonds show nitrogen contents generally lower than 500 ppm and variable nitrogen aggregation state, from 20% to 80% of the ‘B’ form. When plotted on a nitrogen aggregation diagram a well defined trend of increasing nitrogen aggregation state with increasing nitrogen content is observed. Carbon isotopic compositions range from −3.6 ‰ to −1.3 ‰. These are broadly correlated with diamond nitrogen content as determined by infrared spectroscopy, with the most negative C-isotopic compositions correlating with the lowest nitrogen contents.
Xenolith mantle equilibration temperatures, calculated from nitrogen aggregation systematics as well as the Ni in garnet thermometer are on the order of 1100 to 1200 °C.
It is concluded that the xenolith is a fertile lherzolite, and that the lherzolitic character may have resulted from the total metasomatic overprinting of pre-existing harzburgite. Metasomatism occurred prior to, or accompanied, diamond growth. 相似文献
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
