Mangos shale-associated alluvium

Inquiry into the dissolution kinetics of naturally occurring geologic materials, rather than individual mineral species, has been relatively neglected. This is especially true of surface processes, the realm of surface water hydrology and geomorphology. This paper focuses attention at a laboratory study of the rate of such complex reactions. Functions defining the dissolution rates of saline (0.1–20 per cent salt content) Mancos Shale-associated alluvium in distilled water follow varying patterns. Dissolution is characterized by an initial (<5 min) high rate constant, by a following phase (20 min-57 h) where rates are reduced drastically, and by a final period of encroachment to equilibrium. Initial dissolution rates increase with increase in salt content and sediment: water ratio. The time necessary to approach equilibrium is, however, found to be directly proportional to the sediment; water ratio. The concentration of Na⁺, Mg²⁺, Ca²⁺, SC^2?₄ and HCO^?₃, and the relative abundance of Ca²⁺ and HCO^?₃ increase continuously with contact time, indicating that the hydrated sodium and magnesium sulphate minerals provide most of the initial solutes, though not necessarily most of the total solute bulk. The results obtained in this study indicate that the high initial dissolution rate of soluble minerals from alluvium, and particularly from shales in contact with aqueous solutions, is too short-lived to account for most of the solutes occurring in heavily sediment-laden surface flow. Excluding input from slower, usually supersaturated subsurface flow, dissolution from sediment in transport should be a major source of solutes in originally undersaturated and kinetically unequilibrated surface water in semiarid and arid regions.     

Effects of matrix grain size on the kinetics of intergranular diffusion

A linear relationship exists between the mean volume of garnet porphyroblasts and the squared inverse of mean matrix grain diameter for six samples of garnetiferous mica quartzite with identical thermal histories and similar mineralogy and modes. This relationship accords with theoretical predictions of the dependence of intergranular diffusive fluxes on the volume fraction of grain edges that function as diffusional pathways during porphyroblast growth. The impact of matrix grain size is large: compared to a rock with a 1‐mm matrix, a rock with a 10‐μm matrix would experience rates of diffusion‐controlled porphyroblast growth that are 10 000 times faster, and characteristic length scales for chemical equilibration that are 100 times larger. Precursor grain sizes may therefore exert a major influence on crystallization kinetics. If matrix coarsening occurs during prograde reaction, a decrease in the volume fraction of diffusional pathways will tend to counteract the exponential thermal increase in diffusive fluxes. The impact of such matrix grain growth, although difficult to assess without firm knowledge of coarsening rates in polymineralic aggregates, might be significant for matrices finer than c. 100 μm at temperatures above c. 500–600 °C, but is likely negligible for coarser grain sizes and lower temperatures.     

正十八烷的裂解动力学研究（Ⅰ）：气态烃组分及其碳同位素演化特征

本文通过对纯烃类化合物——正十八烷的动力学模拟实验，阐述了正十八烷裂解过程中气态烃组分及其同位素的演化特征，获得了产自正十八烷的甲烷生成动力学参数。运用动力学参数将模拟实验结果外推到地质条件下，表明由烷烃裂解形成的甲烷主要生成于150～200C（Easy％Ro介于1．0％～2．0％）的范围，裂解产生的甲烷、乙烷、丙烷的碳同位素分馏效应与Easy％Ro的关系曲线受升温速率的影响，不能直接应用于地质条件。     

Kinetic research on the sorption of aqueous cadmium on carbonate hydroxyapatite

The sorption of aqueous cadmium on carbonate-hydroxyapatite （CHap） is a complicated non-homogeneous solid/water reaction, From kinetic point of view, it can be described by two stages： at the earlier stage, reaction rate is so fast that its kinetic course is intricate, and at the later stage, the rate of reaction becomes slow and the process of reaction accords with one order reaction kinetic equation. Experimental results show that the relationship between reaction rate constant kl and temperature T accords to Arrhenius Equation, and the activation energy of sorption （Ea） is 6.075 J/mol and frequency factor （A） is 220 s^-1. At the same time, reaction rate constant kl increases with decreasing Cd^2＋ initial concentration, on the contrary, with increasing pH and CHap dosage.     

Methods of metal release assessment in soil water at anoxic sites

Metal mobility at contaminated sites can be assessed by soil water investigations or by leaching tests. Leaching tests are usually carried out in open contact with the atmosphere disregarding possible changes of redox conditions. This can affect the original metal speciation and distribution, particularly when anoxic samples are investigated. In this study, the applicability of common leaching tests (the German S4 test (S4), ammonium nitrate extraction (AmmN), and saturation soil extraction (SSE)) is tested for the assessment of zinc release from sulfide‐bearing flotation residues of a former ore mine. Results are compared to soil solution samples obtained by centrifugation and suction cups. The influence of sample storage on S4 leaching test results is investigated in a long‐term study to assess oxidation kinetics. Within the first 200 days the release of zinc increases with a slope of 0.1 mmol kg^–1 d^–1 or 6.0 mg kg^–1 d^–1, respectively. Since oxidation of the sulfide‐bearing samples leads to a significant overestimation of metal release, a feasible modification for the conduction of leaching tests for anoxic material is proposed where oxidation is prevented efficiently. The modified SSE is found to be the only of the tested leaching procedures, which can be recommended for the assessment of current soil water concentrations at anoxic sites if direct investigation of the soil water is impossible due to technical reasons.     

High Resolution Stepped-Combustion Mass Spectrometry: Application to the Detection and Analysis of Fine-Grained Diamond in Meteorites and Rocks

An analytical system and operating protocol are described for high resolution, stepped-combustion mass spectrometry, designed for the extraction, purification, quantification and isotopic analysis of light elements (e.g. C and N) in fine-grained reduced components (e.g. diamond) which have been chemically extracted from natural samples (e.g. meteorites). Specifically, a simple model has been developed for the extraction of diamond from meteorite and its analysis by high resolution stepped heating under an atmosphere of oxygen. Changes in the pressure of oxygen within the range 1.3 to 12kPa (10 to 90 torr) were not found to have any detectable effect on the combustion. Results obtained by this procedure were compared with those predicted by a model and excellent agreement was found, taking into account the limitations of this approach. Results of a preliminary attempt to find fine-grained diamond in a lamproite are outlined.     

镜质体成烃反应动力学模型的标定及其在热史恢复中的应用

镜质体反射率（Ｒｏ）与其生烃率有关，因此，由Ｒｏ应可求取其生烃率；同时，在求取了镜质体成烃反应动力学参数之后，若已知其受热史，则可计算出镜质体的生烃率；反过来，若已知镜质体的生烃率，应可反推其受热史。基于这一基本原理，本文在建立和标定镜质体成烃反应动力学模型的基础上推导了可将其应用于存在着抬升、剥蚀和古地温非线性变化等复杂地质条件下热史恢复的原理模型，结合海拉尔盆地海参７井的实测Ｒｏ值，有效地恢复了其古热史     

不同粒径泥沙共存吸附动力学模式研究

天然水体中泥沙组成具有非恒定性和非均匀性,而不同粒径泥沙的吸附能力差异很大.因此.讨论天然水体中泥沙对重金属污染物的自净能力,必须研究不同粒径泥沙共存(即非均匀沙)的吸附模式.通过系统室内静态试验,研究了不同粒径泥沙共存吸附的吸附动力学模式.它表明,不同粒径泥沙共存吸附体系各粒径之间不存在竞争和干扰,共存体系单位重量泥沙的吸附量等于各粒径泥沙单独存在,在相同条件下单位重量泥沙的吸附量乘以其在共存体系中所占份额的和.这在一定程度上解决了天然河流水体泥沙吸附量的计算问题.     

A crystal-chemical basis for Pb retention and fission-track annealing systematics in U-bearing minerals, with implications for geochronology

This study develops an empirical crystal-chemical framework for systematizing the kinetics of Pb loss and fission-track annealing in U-bearing minerals. Ionic porosity, Z (the fraction of a mineral's unit-cell volume not occupied by ions) potentially accounts for kinetic behavior by monitoring mean metal-oxygen bond length/strength. Various tests of a general kinetics-porosity relationship are presented, based upon diverse mineral data including: (1) Pb diffusion parameters; (2) measured closure temperatures (T_C) for fission-track annealing and (3) retentivities of both Pb and fission tracks, from apparent-age data. Every kinetic parameter (including T_C and mineral age for both the U/Pb and fission-track systems) is inversely correlated with Z within the sub-assemblage: zircon (Z ≈ 29%), titanite ( 34%) and apatite ( 38%). Assuming a diffusional closure model, Pb isotopic transport phenomena are described by a T_C-Z scale “calibrated” with field-based T_C data for titanite (≥ 680 ± 20°C) and apatite ( 500°C). Extrapolation of this scale yields T_C estimates for the following minerals: staurolite (T_C ≥ 1060°C, Z ≈ 25%); garnet (≥ 1010°C, 26.5%); zircon (≥900°C); monazite, xenotime, and epidote (≥ 750°C, 32%); and Ca-clinopyroxene (≥ 670 ± 30°C, 34 ± 1%, depending on composition). These empirical results imply that a (U/)Pb/Pb date for staurolite or garnet records the time of mineral growth, not post-growth isotopic closure, as also concluded in recent field studies. Because Z systematizes fission-track annealing, this recrystallization process, like volume-diffusion, must also be rate-limited by the strength of chemical bonds. The extent to which other recrystallization processes are likewise rate-limited is important to U/Pb geochronology because they potentially compete with diffusion as mechanisms for Pb-isotopic resetting in nature.     

Kinetics of the aromatisation of rearranged ring-C monoaromatic steroid hydrocarbons

The kinetics of the aromatisation of both rearranged and non-rearranged monoaromatics have been investigated in the laboratory under free radical conditions. These studies have indicated that the aromatisation rate constant for the non-rearranged is greater than that for the rearranged isomers at any one particular temperature. Since the members of the rearranged series coelute with their non-rearranged counterparts when both series are present in geological extracts, these results suggest that care needs to be exercised when assessing extents of maturation using monoaromatic and triaromatic steroid hydrocarbons.