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.     

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   

Dust production and the release of iron oxides resulting from the aeolian abrasion of natural dune sands

Global dust trajectories indicate that signi?cant quantities of aeolian‐transported iron oxides originate in contemporary dryland areas. One potential source is the iron‐rich clay coatings that characterize many sand‐sized particles in desert dune?elds. This paper uses laboratory experiments to determine the rate at which these coatings can be removed from dune sands by aeolian abrasion. The coatings impart a red colour to the grains to which previous researchers have assigned variable geomorphological signi?cance. The quantities of iron removed during a 120 hour abrasion experiment are small (99 mg kg^?1) and dif?cult to detect by eye; however, high resolution spectroscopy clearly indicates that ferric oxides are released during abrasion and the re?ectance of the particles alters. One of the products of aeolian abrasion is ?ne particles (<10 µm diameter) with the potential for long distance transport. Copyright © 2004 John Wiley & Sons, Ltd.     

Sorption of Eu~(3+) onto nano-size silica-water interfaces

A large amount of nuclear wastes has been pro-duced due to nuclear weapon development and nuclear electricity generation. One possible resolution for the disposal of the nuclear wastes is to seal them in an underground repository, which requires detailed knowledge on the mobility, chemical behavior and immobilization of radionuclides in underground water. In addition, toxic heavy metals are extensively present in ground and underground water, how to immobilize and remedy these toxic heavy meta…     

High-T phase transition of synthetic ANaB(LiMg)CMg5Si8O22(OH)2 amphibole: an X-ray synchrotron powder diffraction and FTIR spectroscopic study

The synthetic amphibole Na_0.95(Li_0.95Mg_1.05)Mg₅Si₈O₂₂(OH)₂ was studied in situ at high-T, using IR OH-stretching spectroscopy and synchrotron X-ray powder diffraction. At room-T the sample has P2₁ /m symmetry, as shown by the FTIR spectrum. It shows in the OH region two well-defined and intense absorptions at 3,748 and 3,712 cm⁻¹, respectively, and two minor bands at 3,667 and 3,687 cm⁻¹. The main bands are assigned to the two independent O–H groups in the primitive structure. The two minor bands evidencing the presence of small amount of vacant A-site (^A□_0.05). With increasing T, these bands shift continuously and merge into a unique absorption at high temperature. A change as a function of increasing T is revealed by the evolution of the refined unit-cell parameters, whose trend shows a transition to C2/m at about 320–330°C. The spontaneous scalar strain, fitted with a tricritical 2–6 Landau potential, gives a T _c of 325(10)°C (β parameter = 0.27). Comparison with the second-order P2₁ /m ⇔ C2/m phase transition at 255°C for synthetic amphibole ^ANa_0.8^B(Na_0.8Mg_1.2)^CMg₅Si₈O₂₂(OH)₂ indicates that the substitution of Na with Li at the B-sites strongly affects the thermodynamic character and the T _c of the phase transition. The comparison of LNMSH amphiboles with cummingtonitic ones shows that the high-T thermodynamic behaviour is affected by A-site occupancy.     

Diamond in metasedimentary crustal rocks from Pohorje,Eastern Alps: a window to deep continental subduction

We report the first finding of diamond and moissanite in metasedimentary crustal rocks of Pohorje Mountains (Slovenia) in the Austroalpine ultrahigh‐pressure (UHP) metamorphic terrane of the Eastern Alps. Microscopic observations and Raman spectroscopy show that diamond occurs in situ as inclusions in garnet, being heterogeneously distributed. Under the optical microscope, diamond‐bearing inclusions are of cuboidal to rounded shape and of pinkish, yellow to brownish colour. The Raman spectra of the investigated diamond show a sharp, first order peak of sp³‐bonded carbon, in most cases centred between 1332 and 1330 cm^?1, with a full width at half maximum between 3 and 5 cm^?1. Several spectra show Raman bands typical for disordered graphitic (sp²‐bonded) carbon. Detailed observations show that diamond occurs either as a monomineralic, single‐crystal inclusion or it is associated with SiC (moissanite), CO₂ and CH₄ in polyphase inclusions_. This rare record of diamond occurring with moissanite as fluid‐inclusion daughter minerals implies the crystallization of diamond and moissanite from a supercritical fluid at reducing conditions. Thermodynamic modelling suggests that diamond‐bearing gneisses attained P–T conditions of ≥3.5 GPa and 800–850 °C, similar to eclogites and garnet peridotites. We argue that diamond formed when carbonaceous sediment underwent UHP metamorphism at mantle depth exceeding 100 km during continental subduction in the Late Cretaceous (c. 95–92 Ma). The finding of diamond confirms UHP metamorphism in the Pohorje Mountains, the most deeply subducted part of Austroalpine units.     

Combining two filter paper‐based analytical methods to monitor temporal variations in the geochemical properties of fluvial suspended particulate matter

Many of the commonly used analytical techniques for assessing the properties of fluvial suspended particulate matter (SPM) are neither cost effective nor time efficient, making them prohibitive to long‐term high‐resolution monitoring. We present an in‐depth methodology utilizing two types of spectroscopy which, when combined with automatic water samplers, can generate accurate, high‐temporal resolution SPM geochemistry data, inexpensively and semi‐destructively, directly from sediment covered filter papers. A combined X‐ray fluorescence spectroscopy and diffuse reflectance infrared Fourier transform spectroscopy approach is developed to estimate concentrations for a range of elements (Al, Ca, Ce, Fe, K, Mg, Mn, Na, P, Si, Ti) and compounds (organic carbon, Al_dithionate, Al_oxalate, Fe_dithionate, and Fe_oxalate) within SPM trapped on quartz fibre filters at masses as low as 3 mg. Calibration models with small prediction errors are derived, along with mass correction factor models to account for variations in retained SPM mass. Spectral pre‐processing methods are shown to enhance the reproducibility of results for some compounds, and the importance of filter paper selection and homogeneous sample preparation in minimizing spectral interference is emphasized. The geochemical signal from sediment covered filter papers is demonstrated to be time stable enabling samples to be stored for several weeks prior to analysis. Example results obtained during a heavy precipitation event in October 2012 demonstrate the methodology presented here has considerable potential to be utilized for high‐resolution monitoring of SPM geochemistry under a range of in‐stream hydrological conditions. Copyright © 2013 John Wiley & Sons, Ltd.     

Iron isotopic systematics of UHP eclogites respond to oxidizing fluid during exhumation

The iron stable isotope compositions (δ⁵⁶Fe) and iron valence states of ultrahigh‐pressure eclogites from Bixiling in the Dabie orogen belt, China, were measured to trace the changes of geochemical conditions during vertical transportation of earth materials, for example, oxygen fugacity. The bulk Fe³⁺/ΣFe ratios of retrograde eclogites, determined by Mössbauer spectroscopy, are consistently higher than those of fresh eclogites, suggesting oxidation during retrograde metamorphism and fluid infiltration. The studied eclogites (five samples) display limited mid‐ocean ridge basalts (MORB)‐like (~0.10‰) δ⁵⁶Fe values, which are indistinguishable from their protoliths, that is, gabbro cumulates formed through differentiation of mantle‐derived basaltic magma. This suggests that Fe isotope fractionation during continental subduction is limited. Garnet separates display limited δ⁵⁶Fe variation ranging from ?0.08 ± 0.07 ‰ to 0.02 ± 0.07‰, whereas coexisting omphacite displays a large variation of δ⁵⁶Fe values from 0.15 ± 0.07‰ to 0.47 ± 0.07‰. Omphacite also has highly variable Fe³⁺/ΣFe ratios from 0.367 ± 0.025 to 0.598 ± 0.024, indicating modification after peak metamorphism. Omphacite from retrograde eclogites has elevated Fe³⁺/ΣFe ratios (0.54–0.60) compared to that from fresh eclogites (~0.37), whereas garnet displays a narrow range of ferric iron content with Fe³⁺/ΣFe ratios from 0.039 ± 0.013 to 0.065 ± 0.022. The homogenous δ⁵⁶Fe values and Fe³⁺/ΣFe ratios of garnet suggest that it survived the retrograde metamorphism and preserved its Fe‐isotopic features and ferric contents of peak metamorphism. Because of similar diffusion rates of Fe and Mg in garnet and omphacite, and constant Δ²⁶Mg_{omphacite‐garnet} values (1.14 ± 0.04‰), equilibrium iron isotope fractionation between garnet and omphacite was probably achieved during peak metamorphism. Elevated Fe³⁺/ΣFe ratios of omphacite from retrograde eclogites and variant Δ⁵⁶Fe_{omphacite‐garnet} values of the studied eclogites (0.13 ± 0.10‰ to 0.48 ± 0.10‰) indicate that oxidized geofluid infiltration resulted in the elevation of δ⁵⁶Fe values of omphacite during retrograde metamorphism.