Seasonal δ13CDIC sourcing and geochemical flux in telogenetic epikarst of south-central Kentucky

Telogenetic epikarst carbon sourcing and transport processes and their associated hydrogeochemical responses are complex and dynamic. Carbon dioxide (CO₂) transport rates in the epikarst zone are often driven by hydrogeochemical responses, which influence carbonate dissolution and conduit formation. This study examines the influence of land use on carbon sourcing and carbonate dissolution kinetics through a comparative analysis of separate, but similar, epikarst systems in south-central Kentucky. The use of high-resolution hydrogeochemical data from multiple data loggers and isotope analysis from collected water samples reflects the processes within these epikarst aquifers, which are estimated to contribute significantly to bedrock dissolution. Results indicate that, in an agricultural setting, long-term variability and dissolution is governed by seasonal production of CO₂ . In a more urbanized, shallower epikarst system, land cover may affect CO₂ transport between the soil and underlying bedrock. This concentration of CO₂ potentially contributes to ongoing dissolution and conduit development, irrespective of seasonality. The observed responses in telogenetic epikarst systems seem to be more similar to eogenetic settings, which is suggested to be driven by CO₂ transport occurring independent of high matrix porosity. The results of this study indicate site-specific responses with respect to both geochemical and δ¹³C_DIC changes on a seasonal scale, despite regional geologic similarities. The results indicate that further comparative analyses between rural and urban landscapes in other karst settings is needed to delineate the impact of land use and seasonality on dissolution and carbon sourcing during karst formation processes. © 2019 John Wiley & Sons, Ltd.     

海水中大分子有机质对铂族元素的吸附动力学研究

Adsorption kinetics of the interaction between Pt, Pd and Rh(defined here as platinum group elements, PGEs)ions and macromolecular organic compounds(MOCs, 10 kDa), including humic acid, carrageenan and bovine serum albumin, and different cutoff fractions of natural organic matter(1 kDa and 3 kDa) obtained from seawater using centrifugal ultrafiltration devices were investigated. For a given element, all the adsorption kinetics did not reach equilibrium except the interaction between Pt and 1 kDa cutoff, and between Pd and humic acid.For all the tested MOCs, the adsorption kinetics could be divided into two stages, a rapid adsorption process in the first 8 h and the desorption stage after the first 8 h until the equilibrium. The change trend of partition coefficient(log_(10)K_d) values with experiment time was consistent with that of the kinetic curves. However, in the interaction between PGE ions and natural dissolved organic matter(NDOM), an obvious difference in the change trends of log_(10)K_d and kinetic curves was observed. It indicated that the partition behavior of PGE ions interacting with NDOM in seawater was a combined effect of different organic constituents. The adsorption and log_(10)K_d of PGEs in the 1 kDa NDOM fraction were higher and more stable than those in the 3 kDa NDOM fraction. The results also indicated that the 1–3 kDa NDOM may dominate the interaction between PGEs ions and NDOM. Moreover, no kinetic model could perfectly simulate the adsorption process. It indicated that the colloidal struction and morphology of MOCs or NDOM in seawater might be inhomogeneous. Hence, the interaction between PGE ions and organic matter in seawater was a complicated process and needs further research.     

Phase stability and kinetics of methane hydrate formation in presence of calcium and magnesium carbonate

The huge amount of methane hydrate deposits identified in deep marine sediments is considered as the new resource for future energy. Since carbonates are one of the major components of marine sediments, in the present study, an investigation has been made to study methane hydrate stability and kinetics in the presence of CaCO₃ and MgCO₃. Effect of the presence of carbonates on the solubility of methane in the system has also been examined as it directly affects the hydrate formation process. It has been observed that in presence of CaCO₃ and MgCO₃, the hydrate formation is inhibited. Comparative studies have also been done in the presence of artificial seawater to consider the effect of presence of different salts. Mole consumption of methane gas during hydrate formation in different carbonate samples was measured using real gas equation and found to be minimum in CaCO₃ in seawater sample due to the combined effect of the presence of CaCO₃ and different salts of seawater. An increase in nucleation and induction time was also observed demonstrating the inhibition of hydrate formation in the presence of these components. Further, the decrease in hydrate formation rate also confirmed the inhibition effect of CaCO₃ and MgCO₃ on hydrate formation.     

花岗岩酸岩作用反应动力学研究

化学刺激能够改善增强型地热系统(EGS)热储层裂隙连通情况、提高裂隙渗透率。本文以EGS热储化学刺激为出发点,开展土酸体系 花岗岩作用实验,总结实验规律,明确了酸岩作用机理,建立多矿物耦合反应动力学模型并获取重要参数。得出以下结论：土酸中HF浓度越高,对花岗岩的溶蚀率和溶蚀速率就越大,但更易产生二次沉淀;酸液中离子的浓度与不同矿物溶蚀存在对应关系,Na+和K+分别来自于钠长石和伊利石,Al3+和硅来自长石类和黏土类矿物,Ca2+前期来自方解石,后期受钙长石和氟石影响;土酸 花岗岩反应为双重机制控制下的动力学反应;HF机制下的矿物溶解反应速率常数数量级约为10-4～10-5,比中性机制下的矿物的溶解速率提高了约9个数量级。研究结果可以为EGS储层化学刺激工作提供理论支持。     

沉积盆地超压系统内油气的生成与保存

沉积盆地内的超压系统是一个相对独立的封闭-半封闭体系,与油气生成、保存关系密切.超压系统内矿物介质、有机质、水相互作用过程以及有效应力对有机质演化的作用机理研究揭示了超压对有机质演化具有显著的阶段性和差异性,具体表现在:(1)压力的影响程度是有机质演化程度的函数;(2)超压/压力效应对有机质演化发生显著影响需要达到某一最小值,即门限值;(3)在有机质演化不同阶段发育的超压对生烃的影响不同;(4)同一超压系统内,不同类型有机质对超压的响应具有差异性.迄今,已经建立了超压/压力对有机质演化影响程度的定量化模型,包括化学动力学模型和热力学模型两类.化学动力学模型仍有许多需要改进的地方,如压力影响的阀值、指前因子和活化能随反应时间的变化规律等,相对而言,热力学模型似乎更简单、易用,但其可靠性和普适性还有待时间的检验.由于异常高压对超压系统储层内原油的热裂解反应具有抑制效应,有利于深部高温高压储层内液态烃的保存,因此,含油气盆地深部高温高压地层已成为一个较为有利的石油勘探领域.     

二甲基硫光化学氧化反应的动力学研究

实验研究水溶液中二甲基硫（ＤＭＳ）的光化学氧化反应的动力学。结果表明，在入射光频率与强度一定条件下，ＤＭＳ进行光化学氧化反应的速率会受到介质、ｐＨ、重金属离子的影响。Ｈｇ２＋能显著加快人工海水介质中ＤＭＳ的光氧化速率。ＤＭＳ进行光氧化的一级速率常数为４．４６×１０－５～３０．４×１０－５ｓ－１，其在光照下的人工海水介质中的半寿期为３．６ｈ。这说明光化学过程对于影响和控制ＤＭＳ在海洋中的浓度和分布起着十分重要的作用     

Organotin accumulation in an estuarine food chain: comparing field measurements with model estimations

The bioaccumulation model OMEGA (optimal modelling for ecotoxicological applications) is used to explore accumulation of organotins in the Western Scheldt food chain, consisting of herbi-detritivores, primary and secondary carnivorous fish and a piscivorous bird. Organotins studied are tributyltin (TBT) and triphenyltin (TPT) and the respective di- and mono-organotin metabolites. Empirical elimination rate constants are compared to model predictions for organic substances and metals. It is found that field bioaccumulation ratios are higher than predicted based on elimination kinetics relevant for organic compounds. The results indicate that uptake of organotins mainly occurs via hydrophobic mechanisms, whereas elimination may occur via metal-like kinetics. This results in very low elimination rates, which are comparable to model predictions for metals.     

Mechanodestruction of minerals at the crack tip (<Emphasis Type="Italic">Overview</Emphasis>): 1. Experiment

The kinetics of the amount of volatiles emitted from synthetic and natural calcite single crystals while cleaving and grinding are determined using time-of-flight mass spectrometry. It is revealed that the CO₂ emission is a product of mechano destruction rather than the release of impurities trapped in the crystal. Irradiation of calcite increases the CO₂ emission. A diffusion–desorption model is suggested to explain the kinetics of volatile emission from cleaved surfaces and experimental results on the emission of volatile products during the mechano destruction of various single crystals are summarized. The effects of several sources of systematic errors are discussed. The yield of volatiles is correlated with the speed of the brittle crack propagation and the physicochemical properties of minerals.     

Changes of acoustic emission and strain in hard coal during gas sorption–desorption cycles

The cylindrical coal samples were subjected to three successive cycles of sorption–desorption processes of a single gas (CO₂, CH₄). Acoustic emission (AE) and strains were simultaneously recorded during the sorption and desorption processes.Tests were conducted on medium-rank coal from the Upper Silesia Basin, Poland. Follow-up tests for gas sorption–desorption consistently showed significant changes of AE characteristics for re-runs on the same sample. The AE level decreased in each successive test. The most spectacular differences were observed between AE generated during the first cycle of gas sorption and the subsequent cycle. This phenomenon could be due to structural changes in the coal taking place substantially on its first exposure to the sorbate. The AE results indicate, that each cycle of gas sorption–desorption was run on the same coal though with a somewhat different structure.In those tests, the swelling of coal by CO₂ or/and CH₄ was anisotropic (greater in the direction perpendicular to the bedding plane than parallel) in each cycle of the gas sorption–desorption process.     

Heterogeneous growth of cordierite in low P/T Tsukuba metamorphic rocks from central Japan

This paper examines the spatial statistics of matrix minerals and complex patterned cordierite porphyroblasts in the low‐pressure, high‐temperature (low P/T) Tsukuba metamorphic rocks from central Japan, using a density correlation function. The cordierite‐producing reaction is sillimanite + biotite + quartz = K‐feldspar + cordierite + water. The density correlation function shows that quartz is distributed randomly. However, the density correlation functions of biotite, plagioclase and K‐feldspar show that their spatial distributions are clearly affected by the formation of cordierite porphyroblasts. These observations suggest that cordierite growth occurred through a selective growth mechanism: quartz adjacent to cordierite has a tendency to prevent the growth of cordierite, whereas other matrix minerals adjacent to cordierite have a tendency to enhance the growth of cordierite. The density correlation functions of complex patterned cordierite porphyroblasts show power‐law behaviour. A selective growth mechanism alone cannot explain the origin of the power‐law behaviour. Comparison of the morphology and fractal dimension of cordierite with two‐dimensional sections from a three‐dimensional diffusion‐limited aggregation (DLA) suggests that the formation of cordierite porphyroblasts can be modelled as a DLA process. DLA is the simple statistical model for the universal fractal pattern developed in a macroscopic diffusion field. Diffusion‐controlled growth interacting with a random field is essential to the formation of a DLA‐like pattern. The selective growth mechanism will provide a random noise for the growth of cordierite due to random distribution of quartz. Therefore, a selective growth mechanism coupled with diffusion‐controlled growth is proposed to explain the power‐law behaviour of the density correlation function of complex patterned cordierite. The results in this paper suggest that not only the growth kinetics but also the spatial distribution of matrix minerals affect the progress of the metamorphic reaction and pattern formation of metamorphic rocks.