Rock transformations in spherically converging shock waves: Newly obtained experimental results

The paper presents a concise review of results obtained by studying shock metamorphism of polymineralic rocks with the application of spherical hermetically sealed recovery devices. Such experiments are proved to be able to reproduce principally important features of transformations detected in rocks from natural meteoritic craters (astroblemes). The experimental samples show subspherical concentric zones with different rock transformations, which are generally analogous to zones in natural astroblemes (listed in order from the centers of the spherical samples to their margins): fracturing, diaplectic transformations, selective and then complete melting, and finally, evaporation. However, the laboratory scale of the experiments and the absence of younger overprinted processes, which can obliterate impact transformations of rocks in nature, enable the researcher to reveal distinctive compositional, textural, and phase features of transformations induced in the rocks at increasing isentropic shock wave-induced loading. Data on the mobility of major elements in the course of impact metamorphism show that the type and certain features of the crystal structures of minerals are of paramount importance for the amorphization of the minerals or their shock wave-induced thermal decomposition. The crystal chemical control of mineral transformations was proved to be exerted at a number of levels. High-pressure phases identified in experiments with shock wave loading were determined to crystallize from melt or via a phase transition associated with the migration of elements.     

New experimental evidence on cluster-type vaporization of feldspars

This paper reports experimental data on the investigation of the chemical composition of condensed silicate matter produced during the high-temperature pulse vaporization of feldspars. The experiments simulated the conditions of vaporization accompanying a high-velocity impact. Samples of albite, bytownite, calcic and sodic labradorite, and sanidine were used in the experiments. The investigation of the condensate layers obtained in the experiments included the determination of element distribution and structural characteristics of the materials using layer-by-layer X-ray photoelectron spectroscopy. It was shown that the vaporization of the samples occurred mainly through the release of complex atom–molecule groups referred to as clusters. “Nepheline,” “wollastonite,” and “sillimanite” clusters were identified as characteristic groups. The thermodynamic evaluation of melt composition at temperatures up to 5000 K performed using the Magma program confirmed high activities of these components in feldspar melts.     

Structure of silicate melts: Raman spectroscopic data and thermodynamic simulation results

High-temperature Raman spectroscopy was applied to study model silicate melts in the M₂O-SiO₂ system, where M = K, Na, or Li. Structural units of the melts and equilibrium constants of reactions between them are determined. Thermodynamic calculations were conducted for the dependence of the Q ⁿ distribution on the composition and temperature, and the results of thermodynamic simulations were demonstrated to be consistent with the experimental results.     

New data on the microstructure of silicate Cosmic spherules

Doklady Earth Sciences -     

Hydrogen-alkali exchange between silicate melts and two-phase aqueous mixtures: an experimental investigation

Experiments were performed in the three-phase system high-silica rhyolite melt + low-salinity aqueous vapor + hydrosaline brine, to investigate the exchange equilibria for hydrogen, potassium, and sodium in magmatic-hydrothermal systems at 800 °C and 100 MPa, and 850 °C and 50 MPa. The K ^aqm/melt _H,Na and K ^aqm/melt _H,K for hydrogen-sodium exchange between a vapor + brine mixture and a silicate melt are inversely proportional to the total chloride concentration (ΣCl) in the vapor + brine mixture indicating that HCl/NaCl and HCl/KCl are higher in the low-salinity aqueous vapor relative to high-salinity brine. The equilibrium constants for vapor/melt and brine/melt exchange were extracted from regressions of K ^{a q m / m e l t} _{H , N a} and K ^{a q m / m e l t} _{H , K} versus the proportion of aqueous vapor relative to brine in the aqueous mixture (F^aqv) at P and T, expressed as a function of ΣCl. No significant pressure effect on the empirically determined exchange constants was observed for the range of pressures investigated. Model equilibrium constants are: K ^aqv/melt _H,Na(vapor/melt)=26(±1.3) at 100 MPa (800 °C), and 19( ± 7.0) at 50 MPa (850 °C); K ^aqv/melt _H,K=14(±1.1) at 100 MPa (800 °C), and 24(±12) at 50 MPa (850 °C); K ^aqb/melt _H,b(brine/melt)= 1.6(±0.7) at 100 MPa (800 °C), and 3.9(±2.3) at 50 MPa (850 °C); and K ^aqb/melt _H,K=2.7(±1.2) at 100 MPa (800 °C) and 3.8(±2.3) at 50 MPa (850 °C). Values for K ^aqv/melt _H,K and K ^aqb/melt _H,K were used to calculate KCl/HCl in the aqueous vapor and brine as a function of melt aluminum saturation index (ASI: molar Al₂O₃/(K₂O+Na₂O+CaO) and pressure. The model log KCl/HCl values show that a change in melt ASI from peraluminous (ASI = 1.04) to moderately metaluminous (ASI = 1.01) shifts the cooling pathway (in temperature-log KCl/HCl space) of the aqueous vapor toward the andalusite+muscovite+K-feldspar reaction point. Received: 22 August 1996  / Accepted: 5 February 1997     

Cluster analysis applied to regional geochemical data: Problems and possibilities

Cluster analysis can be used to group samples and to develop ideas about the multivariate geochemistry of the data set at hand. Due to the complex nature of regional geochemical data (neither normal nor log-normal, strongly skewed, often multi-modal data distributions, data closure), cluster analysis results often strongly depend on the preparation of the data (e.g. choice of the transformation) and on the clustering algorithm selected. Different variants of cluster analysis can lead to surprisingly different cluster centroids, cluster sizes and classifications even when using exactly the same input data. Cluster analysis should not be misused as a statistical “proof” of certain relationships in the data. The use of cluster analysis as an exploratory data analysis tool requires a powerful program system to test different data preparation, processing and clustering methods, including the ability to present the results in a number of easy to grasp graphics. Such a tool has been developed as a package for the R statistical software. Two example data sets from geochemistry are used to demonstrate how the results change with different data preparation and clustering methods. A data set from S-Norway with a known number of clusters and cluster membership is used to test the performance of different clustering and data preparation techniques. For a complex data set from the Kola Peninsula, cluster analysis is applied to explore regional data structures.     

Dual speciation of nitrogen in silicate melts at high pressure and temperature: An experimental study

Solubility and speciation of nitrogen in silicate melts have been investigated between 1400 and 1700 °C and at pressures ranging from 10 to 30 kbar for six different binary alkali and alkaline-earth silicate liquids and a Ca-Mg-alumino silicate. Experiments were performed in a piston-cylinder apparatus. The nitrogen source is silver azide, which breaks down to Ag and molecular N₂ below 300 °C. At high pressure and temperature, the nitrogen content may be as high as 0.7 wt% depending on the melt composition, pressure, and temperature. It increases with T, P and the polymerization state of the liquid. Characterization by Raman spectroscopy and ¹⁵N solid state MAS NMR indicates that nitrogen is not only physically dissolved as N₂ within the melt structure like noble gases, but a fraction of nitrogen interacts strongly with the silicate network. The most likely nitrogen-bearing species that can account for Raman and NMR results is nitrosyl group. Solubility data follow an apparent Henry’s law behavior and are in good agreement with previous studies when the nitrosyl content is low. On the other hand, a significant departure from a Henry’s law behavior is observed for highly depolymerized melts, which contain more nitrosyl than polymerized melts. Possible solubility mechanisms are also discussed. Finally, a multi-variant empirical relation is given to predict the relative content of nitrosyl and molecular nitrogen as a function of P, T, and melt composition and structure. This complex speciation of nitrogen in melts under high pressure may have significant implication concerning crystal-melt partitioning of nitrogen as well as for potential elemental and isotopic fractionation of nitrogen in the deep Earth.     

Diffusion in silicate minerals and glasses: A data digest and guide to the literature

The rates of diffusion of cations, oxygen and hydrogen in silicates are of fundamental importance to a wide range of petrological and geochronological problems. In order that the Earth Scientist may readily apply the available experimentally-determined diffusion rates to such problems, a compilation of data for diffusion in silicate minerals and glasses is presented along with a working guide for its use. Published data and experimental conditions are listed in tables, and these are preceded by an outline of diffusion mechanisms, terminology, equations and units, diffusion regimes, factors controlling diffusion rates, measurement techniques, and diffusional behaviour.     

The redox state of cerium in basaltic magmas: an experimental study of iron-cerium interactions in silicate melts

Ce(IV)-Ce(III) and Fe(III)-Fe(II) redox equilibria in Ca-Mg-Al-silicate melts have been individually measured with respect to the base composition, melt temperature, imposed oxygen fugacity, and multivalent element concentration (up to about 1.5 wt%). The mutual interaction of these two redox couples has been studied in analogous glasses which simultaneously contained iron and cerium. Analyses of Fe(III) concentrations in iron-cerium glasses by electron paramagnetic resonance and optical absorption spectroscopy indicate that Ce(IV) is stoichiometrically reduced by Fe(II) in the melt to produce Fe(III) and Ce(III) and that Ce(III)-O-Fe(III) complexes are formed in the melt. Consequently, it is concluded that cerium exists only as Ce(III) in basaltic magmas; cerium anomalies cannot be ascribed to the stabilization of Ce(IV) in magmas.     

Predicting phosphate saturation in silicate magmas: An experimental study of the effects of melt composition and temperature

A series of 1 atm experiments has been performed to test the influence of iron content and oxidation state on the saturation of phosphate minerals in magmatic systems. Four bulk compositions of different iron content have been studied. The experiments cover a range of temperature from 1030 to 1070 °C and oxygen fugacity from 1.5 log units below to 1.5 log units above the Fayalite-Magnetite-Quartz buffer. The results demonstrate that neither iron content of the liquid nor oxidation state play a significant role on phosphate saturation. On the other hand, SiO₂ and CaO contents of the liquid strongly influence the appearance of a crystalline phosphate. Our results are combined with data from the literature to define an equation which predicts the P₂O₅ content of silicate liquids saturated in either whitlockite or fluorapatite:

     

The effect of titanium and phosphorus on ferric/ferrous ratio in silicate melts: an experimental study

The effect of TiO₂ and P₂O₅ on the ferric/ferrous ratio in silicate melts was investigated in model silicate melts at air conditions in the temperature range 1,400–1,550 °C at 1-atm total pressure. The base composition of the anorthite–diopside eutectic composition was modified with 10 wt % Fe₂O₃ and variable amounts of TiO₂ (up to 30 wt %) or P₂O₅ (up to 20 wt %). Some compositions also contained higher SiO₂ concentrations to compare the role of SiO₂, TiO₂, and P₂O₅ on the Fe³⁺/Fe²⁺ ratio. The ferric/ferrous ratio in experimental glasses was analyzed using a wet chemical technique with colorimetric detection of ferrous iron. It is shown that at constant temperature, an increase in SiO₂, TiO₂, and P₂O₅ content results in a decrease in the ferric/ferrous ratio. The effects of TiO₂ and SiO₂ on the Fe³⁺/Fe²⁺ ratio was found to be almost identical. In contrast, adding P₂O₅ was found to decrease ferric/ferrous ratio much more effectively than adding silica. The results were compared with the predictions from the published empirical equations forecasting Fe³⁺/Fe²⁺ ratio. It was demonstrated that the effects of TiO₂ are minor but that the effects of P₂O₅ should be included in models to better describe ferric/ferrous ratio in phosphorus-bearing silicate melts. Based on our observations, the determination of the prevailing fO₂ in magmas from the Fe³⁺/Fe²⁺ ratio in natural glasses using empirical equations published so far is discussed critically.     

Strain localization in sand: an overview of the experimental results obtained in Grenoble using stereophotogrammetry

Experimental results are presented from the extensive program of drained plane strain compression tests on sand carried out in Grenoble over the last two decades. Systematic analysis of photographs of the deforming specimen allowed for measuring deformations and determining strain fields throughout the test, that is: prior to, at, and after the onset of strain localization. The principles, details and accuracy of the procedure are described, as well as its suitability to properly depict the patterns of deformation. Findings concerning the occurrence and progression of strain localization are discussed. The issues of shear band orientation and thickness are addressed, as well as temporary and persistent complex localization patterns, and the volumetric behaviour inside a band after its formation. The influence of such variables as initial state of the sand (effective stress and relative density), specimen size and slenderness, as well as grain size, is discussed. Copyright © 2004 John Wiley & Sons, Ltd     

Formation of epigenetic graphite inclusions in diamond crystals: experimental data

To elucidate the conditions of formation of epigenetic graphite inclusions in natural diamond, we carried out experiments on high-temperature treatment of natural and synthetic diamond crystals containing microinclusions. The crystal annealing was performed in the CO–CO₂ atmosphere at 700–1100 °C and ambient pressure for 15 min to 4 h. The starting and annealed diamond crystals were examined by optical microscopy and Raman spectroscopy. It has been established that the microinclusions begin to change at 900 °C. A temperature increase to 1000 °C induces microcracks around the microinclusions and strong stress in the diamond matrix. The microinclusions turn black and opaque as a result of the formation of amorphous carbon at the diamond–inclusion interface. At 1100 °C, ordered graphite in the form of hexagonal and rounded plates is produced in the microcracks. A hypothesis is put forward that graphitization in natural diamond proceeds by the catalytic mechanism, whereas in synthetic diamond it is the result of pyrolysis of microinclusion hydrocarbons. The obtained data on the genesis of graphite microinclusions in diamond are used to evaluate the temperature of kimberlitic melt at the final stage of formation of diamond deposits.     

An experimental study of Ca-(Fe,Mg) interdiffusion in silicate garnets

Ca-(Fe,Mg) interdiffusion experiments between natural single crystals of grossular (Ca_2.74Mg_0.15 Fe_0.23Al_1.76Cr_0.04Si_3.05O₁₂) and almandine (Ca_0.21Mg_0.40 Fe_2.23Mn_0.13Al_2.00Cr_0.08Si_2.99O₁₂ or Ca_0.43Mg_0.36Fe_2.11 Al_1.95Si_3.04O₁₂), were undertaken at 900–1100 °C and 30 kbar, and pressures of 15.0–32.5 kbar at 1000 °C. Samples were buffered by Fe/FeO in most cases. Diffusion profiles were determined by electron microprobe. Across the experimental couples the interdiffusion coefficients (D˜) were almost independent of composition. The diffusion rates in an unbuffered sample were significantly faster than in buffered samples. The temperature dependence of the D˜ (Ca-Fe,Mg) interdiffusion coefficients may be described by

Isoseismal map of the 1755 Lisbon earthquake obtained from Spanish data

The Royal Academy of History (RAH) of Spain collected very detailed information about the effects on the Spanish territory of the Lisbon, 1755 earthquake, reporting such information within a year after the shock. The data provided by the RAH has been thoroughly analyzed, deriving an M S K intensity value for each one of the localities (more than 1000) included in the report, and an isoseismal map has been obtained from such values. Observations reported, such as tsunami, surface effects, duration of shaking and effects on the population are also discussed. Finally, a comparison is made of the data with the results of recent investigations on the tectonics of the region.     

The hungarian magnetic network and the processing of the obtained data

In 1994–1995 a geomagnetic survey was carried out on the territory of Hungary and the neighbouring regions on 195 stations. Magnetic declination, inclination and total field were directly observed. Some of the stations were measured jointly with Istituto Nazionale di Geofisica (ING), Roma. The results were reduced to the epoch of 1995.0. Normal fields for the magnetic components were determined as second order functions of the geographic coordinates. The polynomial coefficients have been computed in three different ways: by means of simple and weighted least squares procedure and using the adjustment according to the “most frequent value”. In the present paper the mathematical foundation of these methods and the comparison between the obtained results will be presented.     

Ni partitioning between diopside and silicate melt: A redetermination by ion microprobe and recognition of an experimental complication

The ion probe is uniquely suited for measurement of element partitioning between phases in experimental and natural systems. A redetermination of the partitioning of Ni between diopside and quenched silicate melt using samples previously measured by β-track mapping gives 1.87 (weight ratio of ⁶²Ni in diopside/melt), slightly lower than the β-track value of 2.05. Critical to the accurate determination of distribution coefficients are: (1) a secondary ion signal that is linear with concentration in the range measured, and (2) a calibration using known concentrations to correct for differential secondary ion yields from different phases. In the present case the secondary ion signal is linear with Ni concentrations below ~ 1 wt% in both diopside and glass, but nonlinear above. Differential yields were corrected by calibrating the secondary ion signal against compositions determined by electron microprobe.Partition coefficients measured using ⁵⁸Ni and ⁶⁰Ni, in contrast to ⁶²Ni, are not constant with concentration in these samples probably due to Ni migration during crystallization. Measurements using these isotopes (or bulk Ni) show a change of partition coefficient with Ni concentration.