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131.
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+, SC2?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.  相似文献   
132.
Effects of matrix grain size on the kinetics of intergranular diffusion   总被引:1,自引:0,他引:1  
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.  相似文献   
133.
我国下古生界碳酸盐岩烃源岩评价研究现状   总被引:6,自引:0,他引:6  
碳酸盐岩烃源岩评价对我国油气资源评价与勘探至关重要。本文从有机质成熟度、有机质丰度下限、有机质丰度及生烃潜力的恢复、碳酸盐岩生烃机制与生烃模式等几个方面,介绍了我国碳酸盐岩烃源岩的研究现状,提出了运用生烃动力学对碳酸盐岩烃源岩进行研究的新方法,展望了需要继续关注的问题。  相似文献   
134.
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。  相似文献   
135.
Layered double hydroxides (LDHs) are a class of synthetic anionic clays whose structure can be described as containing brucite-like layers in which some of the divalent cations have been replaced by trivalent ions, giving rise to positively charged sheets. This charge is balanced by intercalation of anions in the hydrated interlayer regions. LDHs act as sorbents of anionic species through two types of reactions, namely, anion exchange and reconstruction, which further adds the possibility of recycling and reuse. The sorption of anions from aqueous solutions by structural reconstruction of a calcined LDHs is based on a very interesting property of these materials, the so-called memory effect: Calcination of LDHs produces intermediate non-stoichiometric oxides (CLDH) which undergo rehydration in aqueous medium and give back the hydroxide structure with different anions in the interlayers. Perchlorate's (ClO4^-) strong oxidizing capabilities make it ideally suited for use as a propellant in solid rocket fuel. However, this use in rocket fuel has led to the ClO4^- contamination of considerable amounts of water throughout the United States. ClO4^- has been shown to inhibit iodide uptake by the thyroid gland; and in large doses, it has been linked to anemia and fetal brain damage. This is especially a problem in China. With the recent emergence of perchlorate contamination as an important drinking water quality issue, adsorption by calcined LDHs was studied for ClO4^- removal. In this work, the effect of various factors such as (a) CLDH structure, (b) conditions for removal of ClO4^- ion, such as dosage of adsorbent, initial concentration of ClO4^-, and temperature and (c) co-existing anions in perchlorate contamination on the removal of ClO4^-, have been investigated, respectively.  相似文献   
136.
Ilmenite separated from beach sands of Bangladesh was oxidized for 1 h at 950 °C and then reduced in charcoal for 4 h at 1050 °C. This was followed by leaching in 5% to 15% hydrochloric acid solution in temperature range of 30 to 75 °C for periods of up to 2 h. The results were compared with those obtained by leaching of ilmenite reduced without oxidizing. Oxidation prior to reduction of the ilmenite was found to increase both the extent and the rate of leaching. The residual iron contents after leaching were also found to be lower than that obtained for non-oxidized samples. The kinetic data of leaching of ilmenite reduced after oxidation was found to follow first order reaction model, i.e., G(α) = − ln(1 − α) up to an α value of 0.5 (i.e. up to 50% reduction) and then changed to spherical model, i.e., G(α) = [1 − (1 − α)]3. On the other hand, leaching of ilmenite reduced without oxidizing was found to follow the Ginstling-Brounshtein reaction, i.e., G(α) = 1 − (2/3)α − (1 − α)2/3 throughout the leaching process. Oxidation of ilmenite prior to reduction was also found to have decreased the activation energy of leaching from 43 kJ/mol, found for samples leached after reduction without oxidizing, to 30 kJ/mol.  相似文献   
137.
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.  相似文献   
138.
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.  相似文献   
139.
利用广泛应用的高压釜和Rock Eval热解实验技术,对松辽盆地3个有机质样品同时进行了密闭条件下的加水恒温热解实验和开放条件下的恒速升温热解实验。利用后一实验数据所标定得到的化学动力学模型计算了与高压釜相同实验条件下的有机质产油、产气率。结果表明,在线计量的恒速升温Rock Eval实验方法由于不损失C6—C13的轻质烃组分,在计量液态油的产量方面较需要抽提、恒重的高压釜实验方法更为准确。因此为解决热模拟实验中难以计量、但对成烃评价有重要意义的C6—C13组分的计量问题提供了一条有效的途经。这可能也表明,先由实验数据建立有关的化学动力学模型,之后由它来进一步计算有机质的成烃率,不仅是可行的,而且应该更为准确。  相似文献   
140.
To systematically explain relations between light hydrocarbons, CO, and CO2 concentrations/emissions of biomassburning, we measured concentrations/emissions of carbon gases – CO,CO2, light hydrocarbons (CH4, C2H6,C2H4, C2H2, C3H8, C3H6,n-C4H10, i-C4H10, n-C5H12,i-C5H12), and THC (total hydrocarbon) – in the burning of dead plant material, mainly Imperata grass, byclosed-chamber experiments and by time-series analyses of gas concentrations in combustion plumes in relatively efficient and inefficient combustion situations. Concentrations of hydrocarbons measured were well correlated to [CO] although [C2H2] was exceptionally well correlated to[CO2]. The phase diagrams (relation between [CO]/ [CO2] and [hydrocarbon]/ [CO2]) obtained by the time-seriesexperiments well illustrated the variation in the overall emission rates of the closed-chamber experiments. The higher rates of decrease in hydrocarbon concentration with increasing carbon number in the efficient case compared with the inefficient case probably reflected the rate of oxidation and the amount of radicals. The overall concentrations (or emissions) of C2H4 and C3H6 were higher thanthose of C2H6 and C3H8, suggesting a linkage to mechanisms in whichthe predominant path of hydrocarbon oxidation is through the degradation of alkyl radicals, which can be immediately converted into or formed from alkenes. For C3 and C4 species, normal-chain species hadhigher emissions than iso-chain species under lower combustion efficiency. This may be attributable to the presence of tertiary C–H bonds in iso-species,which show more reactivity in the abstraction of H than secondary C–H bonds unless the carbon number is large.  相似文献   
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