矿物热力学数据的获取

简介矿物热力学数据获取方法发展现状,重点评述量热法和相平衡法的近期发展状况。     

First-order asymptotic theory of the polar phase shift of Rayleigh waves

The precision of measurement of surface-wave phase velocities at very long periods has reached a point where the exact, rather than asymptotic, form of the spherical harmonics must be considered in order to compute theoretical phase velocities or phase delays. The zeroth-order (i.e. constant) polar phase shift afterBrune et al. (1961) applies only between stations antipodal to each other. Everywhere else a correction for incomplete polar phase shift must be applied even if the waves do not cross a pole between the stations. The correction can exceed one percent of the total phase delay and thus be of the same order as the expected regional anomalies. It depends on the epicentral distance on the signal period and on the focal mechanism; the latter dependence can make the practical application cumbersome. We derive first-order asymptotic formulae for the correction of local phase velocities and total phase travel times of Rayleigh waves.Contribution No. 247 of the Institute of Geophysics, Swiss Federal Institute of Technology, Zürich.     

Peristerite compositions in quartzofeldspathic schists, Franz Josef-Fox Glacier Area, New Zealand

Plagioclase compositions vary from An_0.1–2.5 to An₃₂ with increasing grade in chlorite zone to oligoclase zone quartzofeldspathic schists, Franz Josef-Fox Glacier area, Southern Alps, New Zealand. This change is interrupted by the peristerite composition gap in rocks transitional between greenschist and amphibolite facies grade. Oligoclase (An_20-24) and albite (An_0.1–0.5) are found in biotite zone schists below the garnet isograd. With increasing grade, the plagioclase compositions outline the peristerite gap, which is asymmetric and narrows to compositions of An₁₂ and An₆ near the top of the garnet zone. In any one sample, oligoclase is the stable mineral in mica-rich layers above the garnet isograd, whereas albite and oligoclase exist in apparent textural equilibrium in adjacent quartz-plagioclase layers. The initial appearance of oligoclase in both layers results from the breakdown of epidote and possibly sphene. Carbonate is restricted to the quartz-plagioclase rich layers and probably accounts for the more sodic composition of oligoclase in these layers. The formation of more Ca-rich albite and more Na-rich oligoclase near the upper limit of the garnet zone coincides with the disappearance of carbonate and closure of the peristerite gap. Garnet appears to have only a localized effect on Ca-enrichment of plagioclase in mica-rich layers within the garnet zone. The Na-content of white mica increases sympathetically with increasing Ca-content of oligoclase and metamorphic grade. Comparison of the peristerite gap in the Franz Josef-Fox Glacier schists and schists of the same bulk composition in the Haast River area, 80 km to the S, indicates that oligoclase appears and epidote disappears at lower temperatures, and that the composition gap between coexisting albite and oligoclase is narrower in the Franz Josef-Fox Glacier area. It is suggested that a higher thermal gradient (38-40°C/km) and variations in Si/Al ordering during growth of the plagioclases between the two areas may account for these differences. In the Alpine schists the peristerite gap exists over a temperature and pressure interval of about 370-515°C and 5.5-7 kbar (550-700 MPa) P_H2O.     

TDR detection of nonaqueous phase liquids in sandy soils using the eigendecomposition method

In this study, the presence of nonaqueous phase liquids (NAPL) in sandy soils are detected using a TDR probe system and the eigendecomposition method of analysis. As a demonstration, five NAPLs with different physicochemical properties (acetone, benzene, heptane, trichloroethylene, and xylene; Table 1) were used. Samples were prepared in such a way that the soil pore fluid has different contents of deionized water and NAPLs. For each experiment, a pulse signal with known characteristics was used and reflected signals were captured by an oscilloscope and analyzed using the eigendecomposition method. Autoregressive modeling and singular value decomposition were used to calculate the eigenvalues. The most significant eigenvalues were identified based on their power spectrum. The relative eigenvalue of the first mode (Eow), which is a measure of the power carried by the signal, was calculated and correlated to NAPL type and content, and octanol water partition coefficient (log Kow). The results indicated that for the same NAPL content, as log Kow increases, Eow decreases due to increase of hydrophobicity. For the same log Kow, as the organic content in soil pore fluid increases, Eow increases due to decrease of dielectric properties of the pore fluids.     

Site-specific multipath characteristics of global IGS and CORS GPS sites

The site-specific multipath characteristics of 217 Global Positioning System (GPS) sites worldwide were analyzed using the variability of the post-fit phase residuals. Because the GPS satellite constellation returns to the same configuration in a sidereal day (23 h 56 min 4 s), the multipath repeats on that period. However, daily GPS position estimates are usually based on the solar day. When several days of GPS data are processed, this steady change in the orientation of the satellite constellation with respect to the station manifests itself in the form of patterns in the post-fit phase residuals which shift by 3 min 56 s per day. It was found that the mean root mean square of the time-shifted post-fit phase residuals is highly dependent on the GPS antenna type. The conclusions derived from the analysis of the time-shifted post-fit residuals were verified by performing a cross-correlation of the post-fit residuals across many days for selected sites.     

High-pressure Partial Melting of Mafic Lithologies in the Mantle

We review experimental phase equilibria associated with partialmelting of mafic lithologies (pyroxenites) at high pressuresto reveal systematic relationships between bulk compositionsof pyroxenite and their melting relations. An important aspectof pyroxenite phase equilibria is the existence of the garnet–pyroxenethermal divide, defined by the enstatite–Ca-Tschermakspyroxene–diopside plane in CaO–MgO–Al₂O₃–SiO₂projections. This divide appears at pressures above 2 GPa inthe natural system where garnet and pyroxenes are the principalresidual phases in pyroxenites. Bulk compositions that resideon either side of the divide have distinct phase assemblagesfrom subsolidus to liquidus and produce distinct types of partialmelt ranging from strongly nepheline-normative to quartz-normativecompositions. Solidus and liquidus locations are little affectedby the location of natural pyroxenite compositions relativeto the thermal divide and are instead controlled chiefly bybulk alkali contents and Mg-numbers. Changes in phase volumesof residual minerals also influence partial melt compositions.If olivine is absent during partial melting, expansion of thephase volume of garnet relative to clinopyroxene with increasingpressure produces liquids with high Ca/Al and low MgO comparedwith garnet peridotite-derived partial melts. KEY WORDS: experimental petrology; mantle heterogeneity; partial melting; phase equilibrium; pyroxenite     

Estimation of elevation-dependent satellite antenna phase center variations of GPS satellites

A method for the estimation of the phase center variations of GPS satellite antennas using global GPS data is presented. First estimations have shown an encouraging repeatability from day to day and between satellites of the same block. Thus, two different satellite antenna patterns for Block II/IIA and for Block IIR with a range of about 4 cm and an accuracy of less than 1 mm could be found. The present approach allows the creation of a consistent set of receiver and satellite antenna patterns and phase center offsets. Thereby, it is possible to switch from relative to absolute phase center variations without a scale problem in global networks. This changeover has an influence on troposphere parameters, reduces systematic effects due to uncorrect antenna modeling and should diminish the elevation dependence of GPS results. AcknowledgmentsThe authors thank Prof. G. Seeber (University of Hannover) and Dr. G. Wübbena (Geo++ GmbH) and their groups for their kindness in making available the absolute field calibration results derived from robot measurements.     

基于不规则网络下网络流算法的相位解缠方法

相位解缠作为SAR干涉测量数据处理中的一个关键步骤,受到越来越广泛的关注,出现了各种各样的算法。但现有的相位解缠算法仍无法解决高噪声问题,由此导致噪声区域的误差传递到其它区域,产生全程误差,从而影响相位解缠精度。针对这种情况,我们根据网络优化原理,提出了一种基于不规则网络下网络流算法的解缠方法,以干涉相干作为评价相位质量的标准,从含有大量噪声的干涉纹图中剔除低质量的相位,只对高质量相位进行处理,最终获取有用信息。该方法可以避免低质量区域的误差对高质量区域解缠的影响,保证高质量区域的相位解缠,从而获得较理想的解缠结果。     

Inhibition of the S(IV) Autoxidation in the Atmosphere by Secondary Terpenic Compounds

To better understand the role of terpenic compounds in atmospheric chemistry the influence of sobrerol, a water-soluble product of photochemical autoxidation or ozonolysis of -pinene, on the rate of S(IV) autoxidation was studied. Laboratory experiments were performed under heterogeneous conditions, at constant supply with S(IV) by dissolution of CaSO₃.1/2 H₂O fine particles and with air oxygen by diffusion through a planar gas-liquid interface. The progress of S(IV) autoxidation, uncatalysed or catalysed by Fe₂(SO₄)₃ or CoSO₄, was followed conductometrically. The inhibiting effect of sobrerol was discussed in terms of the chain reaction terminated in a step linear with respect to sulphoxy radicals. A method was proposed for quantification of the inhibiting effect and the rate constant (2.0–3.8)10⁸ M^–1s^–1 was given for the step eliminating sulphate radicals. Further consequences of the inhibition: shifting the reaction locus from the gas-liquid (droplet) interface to the liquid (droplet) bulk and strong oscillations in the rate of S(IV) autoxidation resulting of the activity of sobrerol-derived radicals were also shown.