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11.
Polarized single crystal absorption spectra, in the spectral range 40 000–5 000 cm-1, were obtained on Co2+ in trigonally distorted octahedral oxygen fields of buetschliite-type K2Co(SeO3)2 (I), K2Co2(SeO3)3 (II) and zemannite-type K2Co2(SeO3)3 · 2H2O (III). Site symmetries of Co2+ are m (D3d) in I, 3m (C3v) in II, and 3 (C3) in III. The spectra can be interpreted on the basis of an electric dipole mechanism, wherein transitions of Co2+ in the centrosymmetric site in I gain intensity from dynamic removal of the inversion centre by vibronic coupling. In accordance with the elongation of the CoO6 octahedra along the trigonal axis, the split component E(g) of the ground state 4T1g in octahedral fields is the ground state in all three compounds. Trigonal field parameters Dq(trig), D, D and the Racah parameters B have been fitted to the energies of spin allowed transitions (293 K) as follows: I: 744, 94, -16, and 838 cm-1, resp.; II: 647, 227, 42, and 798 cm-1, resp.; III: 667, 181, 21, and 809 cm-1, respectively. Racah parameters C were estimated from the energy of some observed spin-forbidden transitions to be 3770 (I), 3280 (II), and 3465 cm-1 (III). Values of Dq and of the Racah parameters B and C indicate slight differences of Co2+-O bonding in I as compared to II and III, with somewhat higher covalency in compounds II and III which contain face-sharing CoO6 octahedra with short Co-Co contacts. Also, in II and III the observed D values do not agree with theoretical D values, predicted from the magnitude of the mean octahedral distortions.  相似文献   
12.
The effect of raising temperature on spin-allowed dd-transitions of octahedral Cr3+ was studied for various point symmetries of the Cr3+-bearing structural sites, i.e. 3 m and 3 with inversion center in spinel and garnets, respectively, or 32, 3, 2 and 1, lacking the inversion centre, in beryl, corundum, diopside and topaz, respectively. For this purpose, crystals of Cr3+-bearing spinel, pyrope, andradite, grossular, uvarovite, emerald, ruby, diopside and topaz were analyzed by microprobe, oriented, and measured in polarized radiation (except for the cubic minerals) in the spectral range 30 000 to 11 100 cm-1 and at temperatures between 77 and 797 K. The evaluation of the intensities, half widths, and energy positions of bands due to Cr3+-transitions derived from 4 A 2g 4 T 2g (F) and 4 T 1g (F) as well as of Dq- and B-values derived, had the following results:In all cases, red shift of the above bands and, hence, independent on the site symmetry of Cr3+, decreases in the Dq-values were obtained. The dependcies of Dq on T are nearly linear above room temperature and amount between -1.6% in topaz and -5.1% in pyrope in the temperature range studied. From this, values for the local thermal expansion of the Cr3+-centered octahedra, loc, were derived on the basis of the R M-0 -5 -proportionality of 10Dq. Such values are consistently higher than those obtained from X-ray refinements, a method averaging rm-o for all the respective octahedral positions.  相似文献   
13.
14.
Summary Soil temperature is often inadequately based upon relatively few measurements at widely dispersed locations. Within arid regions, such as the desert southwestern United States, soils, microclimates, and thus soil temperature may be markedly heterogeneous. Because extensive measurement of soil temperature is often not feasible, models are needed that simulate soil temperature based on readily available soil survey and above-ground weather information. This paper describes a simple energy-budget based model for simulating daily mean temperatures within a bare arid land soil. The model requires basic information on soil physical properties, and daily weather data including air temperature, windspeed, rainfall, and solar radiation to calculate daily surface energy budget components and surface temperature. One of two alternative numerical methods is then used to calculated subsurface temperatures. Tests of the model using 1987 daily temperature data from an arid site at Yuma, Arizona resulted in root mean square deviations within 1.4°C between daily modeled and measured temperatures at both 0.05 and 0.10 m depths. Sensitivity analysis showed modeled temperatures at 0.05 m depth to be most sensitive to parameters affecting the surface energy balance such as air temperature and solar radiation. Modeled temperatures at 1.0m depth were relatively more sensitive to initial temperature conditions and to parameters affecting distribution of energy within the profile such as thermal conductivity.With 3 Figures  相似文献   
15.
In 2005 Geostandards and Geoanalytical Research embarked upon a new initiative for its readers. Key researchers in various fields of geoanalytical technique development and their application were identified and invited to provide reviews pertinent to their expertise. As noted in the first of these publications "…instead of revisiting the historical context or decades of development in each analytical technique, the goal here has been to capture a snapshot of "hot topics" across a range of fields as represented in the… literature" (Hergt et al . 2005). Rather than prepare an annual review, a decision was taken earlier this year to provide a biennial summary of progress and accomplishments, in this case for the years 2004–2005. The principal techniques employed in Earth and environmental sciences are covered here, and include laser ablation and multicollector ICP-MS, ICP-AES, thermal ionisation and secondary ion mass spectrometry, as well as neutron activation analysis, X-ray fluorescence and atomic absorption spectrometry. A comprehensive review of the development of reference materials, often essential to these techniques, is also provided. The contributions assembled serve both to keep readers informed of advances they may be unfamiliar with, but also as a means of showcasing examples of the breadth and depth of work being conducted in these fields.  相似文献   
16.
This review gives an overview of the use and development of reference materials of geochemical and environmental interest in the literature of the years 2004 and 2005. In these years the performance of existing methods has been improved and new geochemical applications using new techniques have been developed. Accordingly, there was an increasing need for new reference materials, especially for in situ microanalysis and for precise stable isotope measurements. In addition, there was a notable trend for further characterisation of existing reference materials, mainly for the platinum-group elements. This review focuses on five topics: reference materials for platinum-group elements, reference glasses for in situ microanalysis, zircon reference materials, isotopic reference materials, and the development and certification of reference materials.  相似文献   
17.
The evaluation of seismic site response in the urban area of Catania was tackled by selecting test areas having peculiar lithological and structural features, potentially favourable to large local amplifications of ground motion. The two selected areas are located in the historical downtown and in the northern part of Catania where the presence of a fault is evident. Site response was evaluated using spectral ratio technique taking the horizontal- to-vertical component ratio of ambient noise. Inferences from microtremor measurements are compared with results from synthetic accelerograms and response spectra computed at all drillings available for this area. Such method is particularly suitable in urban areas where the nature of the outcropping geological units is masked by city growth and anthropic intervention on the surface geology. The microtremor H/V spectral ratios evaluated at soft sites located within the downtown profile tend to be smaller than that usually reported in the literature for such soils. A tendency for amplifications to peaks near 2 Hz is observed only in some sites located on recent alluvial deposits. Evidences for amplifications of site effects (frequency range 4–8 Hz) were observed in the sampling sites located on the fault, with a rapid decrease of spectral amplitude just a few tenths of metres away from the discontinuity. Numerical simulations evidenced the importance of geolithological features at depth levels even greater than 20–30 m. Besides this, the results strongly confirm the importance of the subsurface geological conditions, in the estimate of seismic hazard at urban scale.  相似文献   
18.
Regular aerosol extinction and backscatter measurements using a UV Raman Lidar have been performed for almost 3 years in Hamburg in the frame of the German Lidar Network. A set of 92 aerosol extinction and 164 aerosol backscatter profiles has been used for statistical investigations. Mean values and variances of the aerosol extinction and backscatter in the boundary layer have been calculated. Large fluctuations during the whole year have been found. The measured aerosol extinction over Hamburg shows a seasonal cycle with highest values in early fall and a second less prominent peak in spring.An analysis of the data using back trajectories showed a dependence of the aerosol extinction on the origin of the air mass. The residence time of the air mass over industrialized areas was found to be an important parameter for the measured aerosol extinction at Hamburg. However, only a small part of the total variability could be explained by the air mass origin.For 75 cases of aerosol extinction measurements under cloud-free conditions, the aerosol backscatter profile and therefore, the lidar ratio as a function of altitude could be determined. Winter measurements of the lidar ratio are often close to model results for maritime aerosol, the summer measurements are close to the model results for urban or continental aerosols.The high quality of the data has been proven by intercomparisons with other lidar systems and with star photometer measurements of the aerosol optical depth during the Lindenberg Aerosol Characterization Experiment (LACE'98) field campaign.  相似文献   
19.
Namibia's passive continental margin records a long history of tectonic activity since the Proterozoic. The orogenic belt produced during the collision of the Congo and Kalahari Cratons in the Early Proterozoic led to a zone of crustal weakness, which became the preferred location for tectonism during the Phanerozoic. The Pan-African Damara mobile belt forms this intraplate boundary in Namibia and its tectonostratigraphic zones are defined by ductile shear zones, where the most prominent is described as the Omaruru Lineament–Waterberg Thrust (OML–WT). The prominance of the continental margin escarpment is diminished in the area of the Central and Northern Zone of the Damara belt where the shear zones are located. This area has been targeted with a set of 66 outcrop samples over a 550-km-long, 60-km-broad coast-parallel transect from the top of the escarpment in the south across the Damara sector to the Kamanjab Inlier in the north. Apatite fission track age and length data from all samples reveal a regionally consistent cooling event. Thermal histories derived by forward modelling bracket this phase of accelerated cooling in the Late Cretaceous. Maximum palaeotemperatures immediately prior to the onset of cooling range from ca. 120 to ca. 60 °C with the maximum occurring directly south of the Omaruru Lineament. Because different palaeotemperatures indicate different burial depth at a given time, the amount of denudation can be estimated and used to constrain vertical displacements of the continental crust. We interpret this cooling pattern as the geomorphic response to reactivation of basement structures caused by a change in spreading geometry in the South Atlantic and South West Indian Oceans.  相似文献   
20.
The Quaternary Eifel volcanic fields, situated on the Rhenish Massif in Germany, are the focus of a major interdisciplinary project. The aim is a detailed study of the crustal and mantle structure of the intraplate volcanic fields and their deep origin. Recent results from a teleseismic P-wave tomography study reveal a deep low-velocity structure which we infer to be a plume in the upper mantle underneath the volcanic area [J.R.R. Ritter et al., Earth Planet. Sci. Lett. 186 (2001) 7-14]. Here we present a travel-time investigation of 5038 teleseismic shear-wave arrivals in the same region. First, the transverse (T) and radial (R) component travel-time residuals are treated separately to identify possible effects of seismic anisotropy. A comparison of 2044 T- and 2994 R-component residuals demonstrates that anisotropy does not cause any first-order travel-time effects. The data sets reveal a deep-seated low-velocity anomaly beneath the volcanic region, causing a delay for teleseismic shear waves of about 3 s. Using 3773 combined R- and T-component residuals, an isotropic non-linear inversion is calculated. The tomographic images reveal a prominent S-wave velocity reduction in the upper mantle underneath the Eifel region. The anomaly extends down to at least 400 km depth. The velocity contrast to the surrounding mantle is depth-dependent (from −5% at 31-100 km depth to at least −1% at 400 km depth). At about 170-240 km depth the anomaly is nearly absent. The resolution of the data is sufficient to recover the described features, however the anomaly in the lower asthenosphere is underestimated due to smearing and damping. The main anomaly is similar to the P-wave model except the latter lacks the ‘hole’ near 200 km depth, and both are consistent with an upper mantle plume structure. For plausible anhydrous plume material in the uppermost 100 km of the mantle, an excess temperature as great as 200-300 K is estimated from the seismic anomaly. However, 1% partial melt reduces the required temperature anomaly to about 100 K. The temperature anomaly associated with the deeper part of the plume (250 to about 450 km depth) is at least 70 K. However, this estimate is quite uncertain, because the amplitude of the shear-wave anomaly may be larger than the modelled one. Another possibility is water in the upwelling material. The gap at 170-240 km depth could arise from an increase of the shear modulus caused by dehydration processes which would not affect P-wave velocities as much. An interaction of temperature and compositional variations, including melt and possibly water, makes it difficult to differentiate quantitatively between the causes of the deep-seated low-velocity anomaly.  相似文献   
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