Interaction between sulphide and H₂O in silicate melts     

Jan Stelling  Harald Behrens  Jörg Göttlicher 《Geochimica et cosmochimica acta》2011,75(12):3542-3557

Reaction between dissolved water and sulphide was experimentally investigated in soda-lime-silicate (NCS) and sodium trisilicate (NS3) melts at temperatures from 1000 to 1200 °C and pressures of 100 or 200 MPa in internally heated gas pressure vessels. Diffusion couple experiments were conducted at water-undersaturated conditions with one half of the couple being doped with sulphide (added as FeS or Na₂S; 1500-2000 ppm S by weight) and the other with H₂O (∼3.0 wt.%). Additionally, two experiments were performed using a dry NCS glass cylinder and a free H₂O fluid. Here, the melt was water-saturated at least at the melt/fluid interface. Profiling by electron microprobe (sulphur) and infrared microscopy (H₂O) demonstrate that H₂O diffusion in the melts is faster by 1.5-2.3 orders of magnitude than sulphur diffusion and, hence, H₂O can be considered as a rapidly diffusing oxidant while sulphur is quasi immobile in these experiments.In Raman spectra a band at 2576 cm⁻¹ appears in the sulphide - H₂O transition zone which is attributed to fundamental S-H stretching vibrations. Formation of new IR absorption bands at 5025 cm⁻¹ (on expense of the combination band of molecular H₂O at 5225 cm⁻¹) and at 3400 cm⁻¹ was observed at the front of the in-diffusing water in the sulphide bearing melt. The appearance and intensity of these two IR bands is correlated with systematic changes in S K-edge XANES spectra. A pre-edge excitation at 2466.5 eV grows with increasing H₂O concentration while the sulphide peak at 2474.0 eV decreases in intensity relative to the peak at 2477.0 eV and the feature at 2472.3 eV becomes more pronounced (all energies are relative to the sulphate excitation, calibrated to 2482.5 eV). The observations by Raman, IR and XANES spectroscopy indicate a well coordinated S²⁻ - H₂O complex which was probably formed in the glasses during cooling at the glass transition. No oxidation of sulphide was observed in any of the diffusion couple experiments. On the contrary, XANES spectra from experiments conducted with a free H₂O fluid show complete transformation of sulphide to sulphate near the melt surface and coexistence of sulphate and sulphide in the center of the melt. This can be explained by a lower H₂O activity in the diffusion couple experiments or by the need of a sink for hydrogen (e.g., a fluid which can dissolve high concentration of hydrogen) to promote oxidation of sulphide by H₂O via the reaction S²⁻ + 4H₂O = SO₄²⁻ + 4H₂. Sulphite could not be detected in any of the XANES spectra implying that this species, if it exists in the melt, it is a subordinate or transient species only.  相似文献   

Stability of pyrochlores in alkaline matrices: Solubility of calcium antimonate   总被引：1，自引：0，他引：1  

Geert Cornelis  Tom Van Gerven  Ruben Snellings  Bram Verbinnen  Jan Elsen  Carlo Vandecasteele 《Applied Geochemistry》2011,26(5):809-817

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Fe–Mg interdiffusion rates in clinopyroxene: experimental data and implications for Fe–Mg exchange geothermometers     

T. Müller  R. Dohmen  H. W. Becker  Jan H. ter Heege  S. Chakraborty 《Contributions to Mineralogy and Petrology》2013,166(6):1563-1576

Chemical interdiffusion of Fe–Mg along the c-axis [001] in natural diopside crystals (X _Di = 0.93) was experimentally studied at ambient pressure, at temperatures ranging from 800 to 1,200 °C and oxygen fugacities from 10^?11 to 10^?17 bar. Diffusion couples were prepared by ablating an olivine (X _Fo = 0.3) target to deposit a thin film (20–100 nm) onto a polished surface of a natural, oriented diopside crystal using the pulsed laser deposition technique. After diffusion anneals, compositional depth profiles at the near surface region (~400 nm) were measured using Rutherford backscattering spectroscopy. In the experimental temperature and compositional range, no strong dependence of D ^Fe–Mg on composition of clinopyroxene (Fe/Mg ratio between Di₉₃–Di₆₅) or oxygen fugacity could be detected within the resolution of the study. The lack of fO₂-dependence may be related to the relatively high Al content of the crystals used in this study. Diffusion coefficients, D ^Fe–Mg, can be described by a single Arrhenius relation with $$D^{{{\text{Fe}} - {\text{Mg}}}} = 2. 7 7\pm 4. 2 7\times 10^{ - 7} {\text{exp(}}-3 20. 7\pm 1 6.0{\text{ kJ}}/{\text{mol}}/{\text{RT)m}}^{ 2} /{\text{s}}.$$ D ^Fe–Mg in clinopyroxene appears to be faster than diffusion involving Ca-species (e.g., D ^Ca–Mg) while it is slower than D ^Fe–Mg in other common mafic minerals (spinel, olivine, garnet, and orthopyroxene). As a consequence, diffusion in clinopyroxene may be the rate-limiting process for the freezing of many geothermometers, and compositional zoning in clinopyroxene may preserve records of a higher (compared to that preserved in other coexisting mafic minerals) temperature segment of the thermal history of a rock. In the absence of pervasive recrystallization, clinopyroxene grains will retain compositions from peak temperatures at their cores in most geological and planetary settings where peak temperatures did not exceed ~1,100 °C (e.g., resetting may be expected in slowly cooled mantle rocks, many plutonic mafic rocks, or ultra-high temperature metamorphic rocks).  相似文献   

Thermodynamic properties and phase stability of wadsleyite II     

Kamil Tokár  Paweł T. Jochym  Przemysław Piekarz  Jan Łażewski  Małgorzata Sternik  Krzysztof Parlinski 《Physics and Chemistry of Minerals》2013,40(3):251-257

The thermodynamical stability of a newly observed wadsleyite II phase in the Mg₂SiO₄ system is studied by the density functional theory. The wadsleyite II equation of state has been derived. The phase boundaries of Mg₂SiO₄ polymorphs: wadsleyite, wadsleyite II and ringwoodite are studied using the quasi-harmonic approximation at high external pressures. Clapeyron slopes determined for wadsleyite II–ringwoodite and wadsleyite–wadsleyite II boundaries are 0.0047 and 0.0058 GPa/K, respectively. It is shown that the wadsleyite II phase is not thermodynamically preferred in the pure Mg₂SiO₄ system and will probably not occur between wadsleyite and ringwoodite phases.  相似文献   

Relation entre fabriques de la sanidine et mise en place des magmas trachytiques (exemple de massif de Hradiště, Bohême du nord)     

Jančušková Zita  Schulmann Karel  Melka Radek 《Geodinamica Acta》2013,26(4):235-244

Résumén

La distribution des fabriques dans un dôme trachytique a été analysée sur la base des orientations préférentielles des cristaux de sanidine. L’orientation préférentielle des plans (010) des cristaux de sanidine a été quantifiée par le calcul du tenseur d’orientation. Le sens de cisaillement a été déterminé à l’aide de relations entre les plans S et C.

Les plans (010) des cristaux de sanidine montrent une fabrique résultant d’un aplatissement dans la partie centrale du dôme et d’un cisaillement simple dans les parties marginales. Les critères de cisaillement montrent le mouvement uni forme de magma trachytique à l’échelle de tout le massif. Nous interprétons la disposition des plans S-C et la répartition des fabriques dans le massif à la superposition de lames successives de magma les unes sur les autres. L’acquisition des fabriques dans le massif est comparée aux expériences en compression uniaxiale le Tullis (1976) et la mise en place des magmas trachytiques est assimilée au mouvement d’un piston dans des conditions de basse pression de confinement et de haute vitesse de déformation pendant le stade d’intrusion précuce. Le gonflement faible a modifié tardivement les fabriques initiales surtout dans la partie de déversement et sommitale.  相似文献   

Maris Gullying: canonical analysis of erosion and sedimentation sequences (Baronnies - France)     

Michel Lecompte  Jan Chodzko  René Lhénaff  Alain Marre 《Geodinamica Acta》2013,26(3):115-124

Abstract

The gullying action on Jurassic and Cretaceous marls in the Baronnies is observed, warm season after cold season, thanks to a network of measuring stakes arranged in 12 gullies. The climate, characterized by summer heath, rather cold but luminous winters, and quite heavy rain, can be classified as mountainous-mediterranean. Seasonal ablation/sedimentation measures have been carried out upon 119 stakes five times within two years (768 days): two in automn, two in early spring (april), and one at end-of-spring.

Ablation and sedimentation sequences are described among the stakes population by Correspondance Factor Analysis (CFA), and their covariations in space and time are explained by Canonical Correspondance Analysis (CCA) according to biophysical environment variables.

Axis 1 of the CFA opposes ground level variations according to their amplitude, high or moderate, regardless of the direction of variation and of measurement date. Axis 2 presents a temporal variation, opposing, on one side, sedimentation sequences at post-winter terms and ablation sequences at postsummer terms, to their converse on the other side.

The CCA indicates that talwegs in their medium and lower parts are more likely to undergo hard gullying or strong accumulation, especially on steep, or conversely flat, vegetationfree slopes of oxfordian marls; on the contrary, interfluve ridges and Gonson moderate gentle to moderate slopes on cenomanian marls, possibly with some vegetation are less dynamic (canonical axis 1). This result allows to extend former observations on rythmic, contrasted variations of gullies bottoms, well different of interfluves and gonson, progressive, regular, ones.

Owing to their varied reactions to seasonal erosive agents (cryoclasty, concentrated run-off), upper parts of talwegs and lower parts of gully slopes and interfluves (canonical axis 2) originate seasonal contrasts revealed by CFA’s axis 2. However, to insure this point of view, more sampling is needed.  相似文献   

Back-arc basin assemblages in Kohistan,Northern Pakistan     

Tahseenullah Khan  M. Asif Khan  M. Qasim Jan  M. Naseem 《Geodinamica Acta》2013,26(1):30-40

Abstract

The east central part of the Kohistan magmatic arc is made up principally of the Jaglot Group. From bottom to top it consists of I) paragneisses and schists intercalated with amphibolites and calc-silicates (Gilgit Formation), II) Gashu-Confluence Volcanics (GCV) and III) the Thelichi Formation comprising a volcanic base (Majne volcanics) and turbidites, marble, volcanoclastic sediments and lava flows. Metamorphic grade varies up to the sillimanite zone. The GCV are correlated with the Chalt volcanics and the Thelichi Formation with the Yasin Group. Other lithologies include the Chilas Complex, the Kohistan Batholith and part of the Kamila Amphibolite. Metavolcanics show a broad range in chemical composition. Geochemical parameters used to specify the tecto-nomagmatic regime suggest affinities of both island arc and MORB-like back-arc basin basalts. Kohistan can be divided into three tectonic zones, I) the southern (Kamila) zone comprises amphibolitized basalts, and mafic and ultramafic rocks, II) the central Chilas Complex, and III) the northern (Gilgit) zone i.e., the Jaglot Group. Previous tectonic models considered the southern two zones as the crust of a Cretaceous island arc. This investigation concludes that only the southern zone represents a true island arc. The Jaglot Group derives from back-arc basin assemblages and the Chilas Complex is a magmatic diapir emplaced in the back-arc basin.  相似文献   

柴北缘锡铁山榴辉岩退变质成因角闪石⁴⁰Ar/³⁹Ar年代学研究   总被引：2，自引：2，他引：0  

胡荣国  王敏  Jan R WIJBRANS  Fraukje M BROUWER  邱华宁 《岩石学报》2013,29(9):3031-3038

采用激光阶段加热⁴⁰Ar/³⁹Ar技术,对柴达木盆地北缘锡铁山榴辉岩退变质作用形成的榴闪岩和斜长角闪岩之角闪石进行了定年分析。09NQ44Amp来自榴闪岩,各阶段表观年龄(以现代空气氩⁴⁰Ar/³⁶Ar比值295.5扣除非放射性成因⁴⁰Ar)构成了单调下降的阶梯状年龄谱。在反等时线图解上,2~4阶段数据点和5~18阶段数据点分别构成了两条等时线,等时年龄分别为427.6±10Ma和425.1±2.6Ma,对应的初始⁴⁰Ar/³⁶Ar比值则分别为435.2±6.1和705.3±13。角闪石09NQ43Amp来自榴辉岩强烈退变质作用形成的斜长角闪岩,⁴⁰Ar/³⁹Ar阶段加热分析也获得单调下降的年龄谱,在反等时线图解上其数据点3~6阶段和7~16阶段分别构成了两条等时线,等时年龄分别为418.9±2.9Ma和418.1±2.1Ma,对应的初始⁴⁰Ar/³⁶Ar比值则分别为493.7±2.8和685.8±34.3。等时线截距值高于现代大气⁴⁰Ar/³⁶Ar比值,表明角闪石中含过剩⁴⁰Ar。同时,由低温和中-高温阶段加热数据点分别构成两条等时年龄基本一致,截距值却明显不同的等时线,表明在角闪石热力学性质不同的源区,存在两期明显不同且未混合的初始捕获Ar组分。等时年龄425~418Ma代表的是锡铁山榴辉岩角闪岩相退变质作用发生的时间。等时线图解法虽然有效的校正了角闪石中的过剩⁴⁰Ar,但仅根据表观年龄图谱和等时线图谱还无法清晰判断过剩⁴⁰Ar在角闪石中的赋存状态,有待进一步探讨。  相似文献   

Fault zone signatures from ambient vibration measurements: a case study in the region of Visp (Valais, Switzerland)     

Cyrill Baumann  Jan Burjánek  Clotaire Michel  Donat Fäh  Luis A. Dalguer 《Swiss Journal of Geoscience》2013,106(3):529-541

Investigations of tectonic features, such as faults, are important challenges for geologists and engineers. Although direct investigational methods, such as boreholes and trenches, have the potential to provide accurate data, these direct methods are usually expensive and time consuming, and give only punctual insights into subsurface structures. Geophysical methods, for example electric surveys and ground penetrating radar, are less expensive and faster to implement. However, these geophysical methods may be difficult or sometimes even impossible to apply in regions with rough topography or regions which are highly urbanized. In this study, we propose an easy-to-use and affordable method to detect fault zones based on ambient vibration observations. We apply this method in the region between Visp and Unterstalden (canton Valais, Switzerland) on a small fault branch, which has no explicit surface expression, and which is linked to a major fault zone, the Simplon Fault Zone. The assumption is that the fault of interest is surrounded by damage zone consisting of fractured rock, and that this results in lateral changes of both seismic velocity and attenuation. The objective was, first, to identify such lateral changes in the observed seismic wave-field, and second, to map any anomalies and combine them with the available geological information. In this way, we were able to follow the fault trace even without a clear surface expression of the fault. Our observations showed the existence of a signature in the power spectra of the seismic noise that may correspond to a damage zone. Such signature is observed along the trace of the expected fault.  相似文献   

Delineation of fluvial sediment architecture of subalpine riverine systems using noninvasive hydrogeophysical methods   总被引：2，自引：2，他引：0  

Daniel Altdorff  Jannis Epting  Jan van der Kruk  Peter Dietrich  Peter Huggenberger 《Environmental Earth Sciences》2013,69(2):633-644

River management and restoration measures are of increasing importance for integrated water resources management (IWRM) as well as for ecosystem services. However, often river management mainly considers engineering and construction aspects only and the hydrogeological settings as the properties and functions of ancient fluvial systems are neglected which often do not lead to the desired outcome. Knowledge of the distribution of sediment units could contribute to a more efficient restoration. In this study, we present two noninvasive approaches for delineation of fluvial sediment architecture that can form a basis for the restoration, particularly in areas where site disturbance is not permitted. We investigate the floodplain of a heavily modified low-mountain river in Switzerland using different hydrogeophysical methods. In the first approach, we use data from electromagnetic induction (EMI) with four different integral depths (0.75–6 m) and gamma-spectrometry as well as the elevation data as input for a K-means cluster algorithm. The generated cluster map of the surface combines the main characteristics from multilayered input data and delineates areas of varying soil properties. The resulting map provides an indication of areas with different sedimentary units. In the second approach, we develop a new iterative method for the generation of a geological structure model (GSM) by means of various EMI forward models. We vary the geological input parameters based on the measured data until the predicted EMI maps match the measured EMI values. Subsequently, we use the best matched input data for the GSM generation. The derived GSM provides a 3D delineation of possible ancient stream courses. A comparison with an independent ground penetrating radar (GPR) profile confirmed the delineations on the cluster map as well as the vertical changes of the GSM qualitatively. Thus, each of the approaches had the capacity for detecting sedimentary units with distinct hydraulic properties as an indication of former stream courses. The developed methodology presents a promising tool for the characterization of test sites with no additional subsurface information.  相似文献