Dissolution and depletion of ferromagnesian minerals from Holocene tephra layers in an acid bog,New Zealand,and implications for tephra correlation

This study examines the depletion of ferromagnesian silicate minerals from a sequence of thin, distal, mainly rhyolitic tephra layers of Holocene age preserved in an acid peat bog (Kopouatai), North Island, New Zealand. The rate of such depletion has been fast, as indicated by the complete loss of biotite from one tephra layer (Kaharoa Tephra), in which it is normally dominant, in only ca. 770 yr. Chemical dissolution is advocated as the likely cause for the depletion, with amphiboles and other mineral grains commonly showing etch pits, microcaves, and other characteristic surface solution features. Theoretical thermodynamic and kinetic models show a marked increase in the rate of dissolution of all ferromagnesian minerals under conditions of low pH (< 4), but that where silica concentrations in solution are high the relative proportions of minerals remaining are unaffected. However, where concentrations of dissolved silica are low, as in most bog environments, the relative proportions of ferromagnesian minerals are affected as well as absolute amounts being decreased. Amphiboles are depleted relative to pyroxenes, consistent with kinetic studies. The results show that the identification and correlation of tephras on the basis of relative abundances of ferromagnesian minerals alone may be unreliable, and emphasise the need to use multiple criteria in such studies.     

Controls on porphyroblast size along a regional metamorphic field gradient

Garnet-bearing schists from the Waterville Formation of south-central Maine provide an opportunity to examine the factors governing porphyroblast size over a range of metamorphic grade. Three-dimensional sizes and locations for all garnet porphyroblasts were determined for three samples along the metamorphic field gradient spanning lowest garnet through sillimanite grade, using high-resolution X-ray computed tomography. Comparison of crystal size distributions to previous data sets obtained by stereological methods for the same samples reveals significant differences in mode, mean, and shape of the distributions. Quantitative textural analysis shows that the garnets in each rock crystallized in a diffusion-controlled nucleation and growth regime. In contrast to the typical observation of a correlation between porphyroblast size and position along a metamorphic field gradient, porphyroblast size of the lowest-grade specimen is intermediate between the high- and middle-grade specimens’ sizes. Mean porphyroblast size does not correlate with peak temperatures from garnet-biotite Fe-Mg exchange thermometry, nor is post-crystallization annealing (Ostwald Ripening) required to produce the observed textures, as was previously proposed for these rocks. Robust pseudosection calculations fail to reproduce the observed garnet core compositions for two specimens, suggesting that these calc-pelites experienced metasomatism. For each of these two specimens, Monte Carlo calculations suggest potential pre-metasomatism bulk compositions that replicate garnet core compositions. Pseudosection analyses allow the estimation of the critical temperatures for garnet growth: ∼481, ∼477, and ∼485°C for the lowest-garnet-zone, middle-garnet-zone, and sillimanite-zone specimens, respectively. Porphyroblast size appears to be determined in this case by a combination of the heating rate during garnet crystallization, the critical temperature for the garnet-forming reaction and the kinetics of nucleation. Numerical simulations of thermally accelerated, diffusion-controlled nucleation, and growth for the three samples closely match measured crystal size distributions. These observations and simulations suggest that previous hypotheses linking the garnet size primarily to the temperature at the onset of porphyroblast nucleation can only partially explain the observed textures. Also important in determining porphyroblast size are the heating rate and the distribution of favorable nucleation sites.     

In situ methods for studying adsorbed phases at the solid/liquid interface: microcalorimetry and ellipsometryLes méthodes d'étude in situ des phases adsorbées : microcalorimétrie et ellipsométrie

The applications of calorimetric and ellipsometric methods to the understanding of adsorption phenomena occurring at the solid–liquid interface are presented with examples in the field of surfactant adsorption. The various experimental approaches are presented and compared, i.e., immersion calorimetry, titration calorimetry and liquid flow calorimetry. It is shown how they can be used to follow, in situ, the building steps of the surfactant adsorbed layer. On the other hand, ellipsometry allows the adsorption isotherm, the adsorption kinetics as well as the thickness of the adsorbed layer to be determined on well-defined flat surfaces. To cite this article: R. Denoyel, C. R. Geoscience 334 (2002) 689–702.     

Kinetic study of the dehydroxylation of chrysotile asbestos with temperature by in situ XRPD

 The kinetics of the dehydroxylation of chrysotile was followed in situ at high temperature using real-time conventional and synchrotron powder diffraction (XRPD). This is the first time kinetics parameters have been calculated for the dehydroxylation of chrysotile. The value of the order of the reaction mechanism calculated using the Avrami model indicates that the rate-limiting step of the reaction is a one-dimensional diffusion with an instantaneous nucleation or a deceleratory rate of nucleation of the reaction product. Hence, the rate-limiting step is the one-dimensional diffusion of the water molecules formed in the interlayer region by direct condensation of two hydrogen atoms and an oxygen atom. The calculated apparent activation energy of the reaction in the temperature range 620–750 °C is 184 kJ mol⁻¹. The diffusion path is along the axis of the fibrils forming the fibers. The amorphous or short-range ordered dehydroxylate of chrysotile is extremely unstable because forsterite readily nucleates in the Mg-rich regions. Moreover, it is less stable than the dehydroxylate of kaolinite, the so-called metakaolinite, which forms mullite at about 950 °C. This difference is interpreted in terms of the different nature of the two ions Mg²⁺ and Al³⁺ and their function as glass modifier and glass-forming ion, respectively. Received: 10 April 2002 / Accepted: 7 January 2003 Acknowledgements This work is part of a COFIN project (04 Scienze della Terra, NR 17, 2000) supported by MURST. Dr Dapiaggi is kindly acknowledged for help during the data collection at the Dipartimento di Scienze della Terra, University of Milan.     

原油族组分成气的化学动力学模型及其标定

利用等温密封热解实验技术及恒速升温热解实验与PY—GC分析技术的结合,本文分别建立并标定了原油中各族组分,即饱和烃、芳烃、非烃和沥青质成气的化学动力学模型。结果表明,原油中不同族组分成气的过程均可用平行一级反应描述,但不同组分在平均活化能及活化能分布上有明显的差异。各族组分在地史过程中成气的过程可由各自的化学动力学模型来描述。这将使原油成气过程的定量、动态描述成为可能。     

Rice Husk Ash as a Low Cost Adsorbent for the Removal of Methylene Blue and Congo Red in Aqueous Phases

Adsorption is of significant importance for effluent treatment, especially for the treatment of colored effluent generated from the dyeing and bleaching industries. Low cost adsorbents have gained attention over the decades as a means of achieving very high removal efficiencies to meet effluent discharge standards. The present article reports on batch investigations for color removal from aqueous solutions of Methylene Blue (MB) and Congo Red (CR) using Rice Husk Ash (RHA) as an alternative low cost adsorbent. The performance analysis was carried out as a function of various operating parameters, such as initial concentration of dye, adsorbent dose, contact time, shaker speed, interruption of shaking and ionic concentration. Performance studies revealed that a very high percentage removal of color was achievable for both dyes. The maximum percentage removal of MB was 99.939%, while 98.835% removal was observed for CR. These percentage removals were better than existing systems. Detailed data analysis indicated that adsorption of MB followed the Temkin isotherm, while CR followed the Freundlich isotherm. These isotherms were feasible within the framework of experimentation. Batch kinetic data, on the other hand, indicated that pseudo second order kinetics governed adsorption in both cases. Sensitivity analysis further indicated that the effects of initial dye concentration, shaker speed, pH and ionic strength had no noticeable effect on the percentage dye removal at equilibrium. Batch desorption studies revealed that 50% acetone solution was optimum for CR, while desorption of MB varied directly with acetone concentration.     

The Metastable Phase Equilibria of the MeX-MgCl_2-H_2O Systems

正1 Introduction The Pingluoba brine,which characterized as high concentration with sodium,potassium,boron,lithium,and rubidium,possess great development value.The main composition of the brine can be summarized to the     

Lacustrine basin unconventional resource plays: Key differences

There has been a revival in hydrocarbon source rock characterization and development associated with growing interest in unconventional resources, where these fine-grained organic-rich rocks act as both source and reservoir. To-date, the exploration focus on shale reservoirs has been largely on marine systems. Lacustrine source rocks for conventional resources are geographically important, dominating regions such as China, Indonesia, and Brazil's resource-base. However, they have been generally untested for unconventional resources.There are a number of key differences in the nature of these hydrocarbon systems that should be considered when assessing whether lacustrine systems may represent future unconventional opportunities in areas where the conventional resource-base is dominated by lacustrine-sourced oil. Among the key differences between these depositional systems is the greater sensitivity to high frequency climatic variability within lacustrine systems. Lacustrine systems are highly sensitive to changes in the balance between precipitation and evaporation, which may lead to rapid changes in lake level, potentially exceeding 600 m. These changes in depositional conditions are geologically rapid and may occur over periods of thousands of years. Such changes can reduce the areal extent of potentially thick source rock intervals to only those portions of a basin where a permanent deep lake was present. Thus the core unconventional target area may be geographically limited compared with their marine counterpart. Although potentially areally limited, a review of many lacustrine source rocks suggests that their thicknesses are often significantly greater than marine source rocks. An examination of the more distal portions of lacustrine systems, where better source rock potential is present reveals that there is generally limited connectivity between source and conventional reservoir. In these settings, such as the Wind River basin (Waltman Shale), the hydrocarbons remain trapped within the shales, potentially leading to over-pressured hydrocarbon charged systems. Such conditions suggest that although areally limited, viable unconventional targets may exist, if suitable reservoir conditions are present. Finally, the character of the oils produced is different in these settings, with lacustrine oils being waxy and displaying different hydrocarbon generation and cracking kinetics. High wax oils display distinct flow characteristics, being more viscous, and may offer different production challenges than their non-waxy marine equivalents. Additionally, differences in their cracking kinetics may indicate that the timing of gas generation for shale gas plays may differ significantly from marine systems.