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.     

THERIA_G: a software program to numerically model prograde garnet growth

We present the software program THERIA_G, which allows for numerical simulation of garnet growth in a given volume of rock along any pressure–temperature–time (P–T–t) path. THERIA_G assumes thermodynamic equilibrium between the garnet rim and the rock matrix during growth and accounts for component fractionation associated with garnet formation as well as for intracrystalline diffusion within garnet. In addition, THERIA_G keeps track of changes in the equilibrium phase relations, which occur during garnet growth along the specified P–T–t trajectory. This is accomplished by the combination of two major modules: a Gibbs free energy minimization routine is used to calculate equilibrium phase relations including the volume and composition of successive garnet growth increments as P and T and the effective bulk rock composition change. With the second module intragranular multi-component diffusion is modelled for spherical garnet geometry. THERIA_G allows to simulate the formation of an entire garnet population, the nucleation and growth history of which is specified via the garnet crystal size frequency distribution. Garnet growth simulations with THERIA_G produce compositional profiles for the garnet porphyroblasts of each size class of a population and full information on equilibrium phase assemblages for any point along the specified P–T–t trajectory. The results of garnet growth simulation can be used to infer the P–T–t path of metamorphism from the chemical zoning of garnet porphyroblasts. With a hypothetical example of garnet growth in a pelitic rock we demonstrate that it is essential for the interpretation of the chemical zoning of garnet to account for the combined effects of the thermodynamic conditions of garnet growth, the nucleation history and intracrystalline diffusion. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.

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.     

低硼氢氧化镁的制备及热分解动力学参数

本文以水合氯化镁、工业氨水为原料制备出了低硼含量的纯度 >99%的氢氧化镁和氧化镁。利用差热 -热重 (DTA- TG)、X-射线衍射 (XRD)、透射电子显微镜 (TEM)等手段 ,对氢氧化镁的热稳定性、相结构、表观状态以及脱水动力学参数进行了分析。结果为 :氢氧化镁以束状纤维和片状粉末共存 ,在 6 2 3K基本完成脱水反应生成氧化镁 ,其脱水反应的表观活化能 E为135 .4 k J· mol-1,指前因子 A为 5 .15× 10 10 ,反应级数 n为 1.10     

Kinetics of redox cycling of iron coupled with fulvic acid

The kinetics of conversion of iron(III) (hydr)oxides to ferrous iron mediated by fulvic acid have been investigated in order to improve the understanding of the redox cycling of iron at the oxic-anoxic boundary in natural waters. Under the conditions similar to natural waters, fulvic acid is able to reduce the iron(III) (hydr)oxide. The kinetics of the reaction depend on the reactivity of iron(III) (hydr)oxides and the reducing power of the fulvic acid. The rate of reaction is 60 nm/h obtained under following conditions: total concentration of Fe(III) 1.0 × 10^–4 M, pH 7.5, fulvic acid 5 mg/L. The rate is considered as a net result of reduction and oxidation in the > Fe^III-OH/Fe(II) wheel coupled with fulvic acid. In a real natural water system, reductants other than fulvic acid may be of importance. The results obtained in the laboratory, however, provide evidence that the Fe(OH)₃(s)/Fe(II) redox couple is able to act as an electron-transfer mediator for the oxidation of natural organic substances, such as fulvic acid by molecular oxygen either in the absence of microorganisms or as a supplement to microbial activity.     

MODELING THE FATE AND TRANSPORT OF HYDROPHOBIC ORGANIC COMPOUNDS IN AN UNSTEADY RIVER-ESTUARINE SYSTEM

1 INTRODUCTION Extensive literature (Brown et al., 1985; Sawhney et al., 1981; Bierman and Swain, 1982; Connolly, 1980; Lopez-Avila and Hites, 1980; O扖onnor, 1988) described lots of sorbed pollutants or toxic substances in bed sediments of rivers, even after the effluent was halted for a long time. This is particularly true for hydrophobic organic compounds that can be sorbed on the particles and accumulated in the river bed sediments (Karickhoff et al., 1979). Pollution events of…     

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.     

Oxygen Isotope Exchange Kinetics Between Coexisting Minerals and Water in the Aral Granite Pluton of the Altay Mountains, Northern Xinjiang

Coexisting quartz, feldspar and biotite vary widely in their δ18O values and display a remarkable 18O/16O disequilibrium relation; especially, a quartz-feldspar reversal (△ 18OQUartz_feldspar< 0) exsists in the Aral granite pluton of the Altay Mountains, northern Xinjiang. The 18O / 16O exchange reaction definitely occurred between granite and water. Initial δ18O values of the granite and exotic fluid are evaluated by the mass balance consideration. The conventional method of discrimination between various magma derivations simply with δ18O values of either whole rock or separate minerals is misleading and unreliable. Experiments carried out by the authors show that the 18O / 16O exchange reaction is not accompanied by what geologists describe as petrological and mineralogical alteration effect. This decoupling relation implies that exchange reaction occurs at a relatively high temperature during subsolidus-postmagmatic cooling of magmas. The exchange mechanism is mainly diffusion-controlled. It is