Characterisation of tobelite (NH4)Al2[AlSi3O10](OH)2 and ND4-tobelite (ND4)Al2[AlSi3O10](OD)2 using IR spectroscopy and Rietveld refinement of XRD spectra

Tobelite (NH₄) Al₂ [AlSi₃O₁₀] (OH)₂, the ammonium analogue of muscovite, and its deuterated form ND₄-tobelite (ND₄) Al₂ [AlSi₃O₁₀] (OD)₂ have been synthesised at 600?°C and 200 and 500 Mpa using a well homogenised, stoichiometric SiO₂-Al₂O₃ oxide mix with Al₂O₃ in excess of 5 mol% and a 25% NH₃ solution whose relative abundance was such that the amount of NH₄ ⁺ stoichiometrically available was in excess of 50%. Characterisation of both tobelite and ND₄-tobelite using IR-spectroscopy, Rietveld refinement of X-ray powder diffraction data, and electron microprobe analysis indicate that, similar to K⁺ in muscovite, the NH₄ ⁺ or ND₄ ⁺ molecule occupies the interlayer site. IR absorption bands caused by NH₄ ⁺ and ND₄ ⁺ can be explained, to a very good approximation, on the basis of T_d symmetry. Nevertheless, substantial line broadening and the occurrence of shoulders indicate a deviation from ideal T_d symmetry. However, even at 77?K, no discrete splitting of the degenerate states could be confirmed. The OH stretching frequencies observed for synthetic tobelite are quite similar to those for muscovite, indicating that the replacement of K⁺ by NH₄ ⁺ has no effect. The low FWHH of the OH bands indicate that the hydroxyl groups are well ordered within the structure. Rietveld refinement of tobelite and ND₄-tobelite indicates that all samples synthesised consist of the 3 different mica polytypes which are typical of muscovite – namely 1M (C2/m), 2M ₁ (C2/c) and 2M ₂ (C2/c). Tobelite and ND₄-tobelite synthesised at 500 Mpa principally contain the 1M polytype, whereas the principle polytype for ND₄-tobelite synthesised at 200 Mpa, is 2M ₂. Rietveld refinement of X-ray diffraction spectra for tobelite synthesised at 200 Mpa was problematic due to the very broad FWHH of the X-ray peaks indicating poor crystallinity. In comparision to synthetic muscovite, the cell dimensions observed for tobelite and its deuterated analogue are quite similar except for the lattice constant c. Due to the larger radius of NH₄ ⁺ or ND₄ ⁺ compared to K⁺ cation, the c-direction is expanded form 10.275 Å in muscovite to approximately 10.540 Å in tobelite and ND₄-tobelite.     

Application of short-wave infrared spectroscopy to define alteration zones associated with the Elura zinc–lead–silver deposit, NSW, Australia

Short-wave infrared reflectance spectra obtained from a Portable Infrared Mineral Analyser (PIMA) have been used to define alteration zones adjacent to base metal sulfide ore bodies at the Elura Mine, Cobar, Australia. The spectroscopic work identified white mica (sericite), chlorite and carbonates of hydrothermal origin in the alteration zones associated with the ore bodies. Weathering, alteration and ore zones can be discriminated by variations in the intensity and wavelength of relevant absorption features. Hydrothermal alteration is classified into four principal types, namely sericitic, silicic, chloritic and carbonate alteration. The first three types comprise overprinting hydrothermal assemblages of quartz, sericite, chlorite, ankerite, siderite, calcite and sulfides developed in strongly altered metasiltstone and slate of Early Devonian age, adjacent to the zinc–lead–silver mineralisation. An extensive zone of carbonate alteration, manifested as porphyroblasts of siderite in the host metasediments, is recognised beyond the zones of strong alteration. Spectral analysis is consistent with the mineralogical data obtained from XRD and XRF analyses and defines the limits of the alteration zones to distances of about 80 m around the ore bodies. The study demonstrates the potential for spectral analysis to assist with drill hole logging and the identification of alteration zones as part of mineral exploration and development programs.     

岩石化探样中微量铀 钍的XRFA法测定

本文提出以粉末样品直接压饼法测定岩石化探样品中的微量U,Th,其方法简便、快速,适用于各类地质样品,尤其是岩石化探样品测量。     

Prediction method of sand-movement direction in water by geochemical elements

The analysis of sand samples by x-ray fluorescent spectroscopy (XRF) gives the ratio of the geochemical elements to construct the sand samples. The x-ray analysis therefore shows the geochemical characteristics of sand in the sampled area. In this study, sand is sampled on coasts and rivers of the Noto Peninsula to determine the geochemical elements and to show the geological characteristics that occur, especially iron and calcium. The experiments show the effect of rivers and Kotogahama beach on iron and calcium, respectively. Applying the method of ratio matching to the measured data of the geochemical elements, the direction of movement of sand on the coast is determined by considering the correlation matrix and the ratio of geochemical elements between sand samples at two locations. The predominant longshore direction movement of sand offshore in the study area is from south to north. Sand in rivers is not directly transported to adjacent beaches; however, offshore sand is transported to beaches. The estimated direction of movement of sand longshore near coastal structures agrees with observations. The proposed method to predict the direction of movement of sand gives the correct one in comparison with the observed data in rivers.     

Intracrystalline fractionation of Fe in synthetic (Fe, Mg, Zn) - bearing staurolite: a Mössbauer spectroscopic study

⁵⁷Fe-Mössbauer spectra of eleven Fe-Mg-bearing staurolite samples, synthesized at 5, 20 and 25 kbar and 680°C, ranging in composition from x_Fe?=1.00 to x_Fe?=0.15, and of two Zn-Fe-bearing staurolite samples, synthesized at 20 kbar and 700°C with x_Fe?=0.10 and x_Fe?=0.32 were collected at room temperature. The spectra reveal that about 80% of Fe_tot (in case of Fe-Mg-bearing staurolite) and about 70% of Fe_tot (in case of Fe-Zn-bearing staurolite) are located as Fe²⁺ at the three subsites Fe1, Fe2 and Fe3 of the tetrahedral T2-site. The refinement of the spectra results in almost identical values for the isomer shift (IS) (±1.0 mm/s) but significantly different values for the quadropole splitting (QS) for the three subsites which is in accordance with the different distortions of these sites. About 8% of Fe_tot (in case of Fe-Mg-bearing staurolite) and 13% of Fe_tot (in case of Fe-Zn-bearing staurolite) are located as Fe²⁺ at the octahedral M4 site, while the remainder percents of Fe_tot indistinguishably occur as Fe²⁺ at the octahedral M1 and M2 sites of the kyanite-like part of the structure. Within the whole Fe-Mg-staurolite solid solution series the Mössbauer parameters QS of the sites M4 and (M1, M2) vary systematically with composition whereas IS remains constant. There is a high negative correlation of the total Mg-content with Fe-occupation of all the Fe-bearing sites indicating a continuous substitution of Fe²⁺ by Mg on all these sites. Synthetic Fe-staurolites show no increasing occupation of the octahedral sites by two-valent cations with pressure, as was assumed by several authors.     

Crystal chemistry of tremolite–tschermakite solid solutions

Tremolite–tschermakite solid solutions have been synthesized between 700 and 850 °C and 200 and 2000 MPa. The starting materials were oxide–hydroxide mixtures and an additional 0.1–1.8 molal CaBr₂ solution. The run products were characterized using SEM, HRTEM, EMP, XRD and FTIR. The synthesized Al tremolites formed needles and lath-shaped crystals of up to 300 × 20 μm. HRTEM investigations showed that the majority of the amphiboles were well ordered. The EMP analysis revealed that the Al tremolites were solid solutions in the ternary tremolite–tschermakite–cummingtonite. The highest observed Al content was close to the composition of magnesiohornblende (X_ts=0.54). Different cummingtonite concentrations (X_cum=0.00–0.18) were observed, which generally increased with Al content. Rietveld refinements of the lattice constants showed a linear decrease of the cell parameters a and b with increasing Al content, whereas c and β increased. Small deviations from the linear behaviour were caused by variable amounts of the cummingtonite component. For pure tschermakite lattice parameters of a=9.7438(11) Å, b=17.936(14) Å, c=5.2995(3) Å, β=105.68(9)° and V=891.7 ± 1.4 ų were extrapolated by least-squares regression. Using the a and β lattice parameters for tremolite, tschermakite and cummingtonite, it was possible to derive amphibole compositions using powder XRD. IR spectra of the Al tremolites showed a total of 12 individual bands. The FWHMs of all bands increased with increasing Al content. According to their FWHMs, these bands were grouped into three band systems at 3664–3676 cm^?1 (I), 3633–3664 cm^?1 (II) and 3526–3633 cm^?1 (III). Assuming ^[6]Al substitution at M2 and/or M3 and ^[4]Al at T1, three principal different configurational groups could be assigned as local environments for the proton. I: only Si⁴⁺ at T1 and one or two Al³⁺ at M2 and/or M3_far, II: one Al³⁺ at T1 and one to three Al³⁺ at M2 and/or at M3_far, III: either Al³⁺ on M3_near and/or two Al³⁺ on T1 and additional one to four Al³⁺ at M2. It is assumed that these three configurational groups correspond to the three groups of observed bands. This was quantitativly supported by Monte-Carlo simulations. A model with random distribution at M2 and M3 including Al avoidance at tetrahedral and octahedral sites yielded the best agreement with the spectroscopical results.     

傅立叶变换红外光谱联用技术在化石燃料分析中的应用

对傅立叶变换红外光谱联用技术在化石燃料分析中的应用进行了较全面的总结评述,重点介绍了气相色谱／红外光谱联机、高压液相色谱／红外光谱联机、薄层色谱／红外光谱联机、超临界流体色谱／红外光谱联机、裂解色谱／红外光谱联机、热重分析／红外光谱联机、气相色谱／红外光谱／质谱三机联用技术等在化石燃料的结构组分分析、成因机理研究及其勘探等诸方面的重要应用,尤其是在芳香族化合物和几何异构体的分离鉴定方面发挥出的突出功效。引用文献５９篇。     

Upper Limit of Iodine Oxide in the Lower Stratosphere

It has been suggested that iodine oxides, IOx, could play a significant role in the ozone destruction in the lower stratosphere. To investigate this suggestion, spectra from nine SAOZ uv-visible spectrometer balloon flights were examined for the IO absorption signature between 405 and 450 nm. IO was not detected, either at mid- or high latitude, in the morning or the evening, in summer or winter. An upper limit of 0.2 parts per trillion by volume (pptv) at 20 km and 0.1 pptv at 15 km at the 95% confidence level (2), was derived from the best measurements at 90° SZA at sunset and sunrise. Since a photochemical model shows that 70% of inorganic iodine should be in the form IO at that time, it is concluded that unless iodine chemistry is different from that assumed at the moment, the role of iodine in stratospheric ozone depletion is small.     

Intercomparison of Tropospheric OH Measurements by Different Laser Techniques during the POPCORN Campaign 1994

In-situ OH measurements by laser-induced fluorescence (LIF) spectroscopy and folded long-path differential optical absorption spectroscopy (DOAS) were carried out in a rural environment in North-East Germany as part of the field experiment POPCORN in August 1994. The large set of OH data obtained allowed an intercomparison of both techniques based on relative diurnal profiles and simultaneously measured absolute concentrations. Most of the time the two OH instruments encountered the same air and agreed well in the measured relative diurnal variations. Only on a few occasions the measurements significantly disagreed due to a perturbation of the DOAS measurements by a local OH source in the north-western wind sector. Excluding data from this wind direction, the statistical analysis of 137 data pairs yields a correlation coefficient of r = 0.90 and a weighted linear fit with a slope of 1.09 ± 0.12. The correlations are carefully analyzed. The comparison of both instruments is discussed in the light of newly published effective absorption cross-sections for H2O and O2 that affect the calibration of LIF.     

Intrinsic spectra of the AXPs

Using direct measurements of photo-electric absorption edges, I derive the intrinsic spectra for the Anomalous X-ray Pulsars. In the past, the hydrogen column density, N _H had been found by fitting the X-ray spectra with a variety of simple continuum models. Since different models fit equally well, with different values of N _H, little is learned about the true column density or intrinsic spectra. Here, I measure the column densities in a model-independent way, and thus derive intrinsic spectra without first assuming what those spectra ought to look like. Particularly for the brightest source, 4U 0142+61, the column density can be determined accurately, and is a factor of 1.4 smaller that the typically N _H quoted. With this new value, the new intrinsic spectrum can be investigated anew, and shows a slight hint of a feature around 13 Å. To be emphasised, this is an empirical method with the minimum of assumptions, as is appropriate for these beguiling sources, the behaviour of which has mystifies astronomers for over a decade. This paper summarises the methods and conclusions to be published in the Astrophysical Journal by Durant and Van Kerkwijk (2006; see astro-ph/0606604).