Thermodynamic and Kinetic Properties of Natural Brines

The physical chemistry of natural brines made up of mostly NaCl has been studied over the years. In this article, the work on the thermodynamics and kinetics of processes in NaCl brines will be examined. The importance of ionic interactions of the processes will be stressed. This will include the pressure–volume–temperature and physical–chemical properties of NaCl and other brine salts from 0 to 6 m, 0 to 200°C, and 0 to 1,000 bar applied pressures. Acid–base, gas–liquid, solid–liquid, and ion–complex formation processes in NaCl are examined. Equations that can be used to estimate the equilibria in NaCl are given. Pitzer models are discussed that can be used to estimate ionic equilibria in brines. The oxidation of Fe(II) and Cu(I) with O₂ and H₂O₂ and the reduction of Cu(II) with H₂O₂ in NaCl are examined in terms of ionic complexes of metals with OH^? and CO₃ ^2?. The oxidation of H₂S with O₂ and H₂O₂ is also examined in NaCl media. Equations are given that can be used to estimate the effect of ionic interactions on kinetic processes in NaCl.     

粘土矿物的掺杂对沉积物吸持Cu、Zn能力的影响

通过考察粘土矿物及掺杂粘土矿物前后沉积物的吸附/解吸特性,分析了伊利石与蒙脱石对重金属污染沉积物中Cu与Zn稳定固定化的可行性。结果表明：伊利石与蒙脱石的掺杂均降低了沉积物吸持Cu的能力（最大下降量分别为5.4%和3.8%）,伊利石的掺杂同样降低了沉积物吸持Zn的能力（最大下降量为4.4%）,但蒙脱石掺杂后沉积物吸持Zn的能力明显增强,最高增加5.7%。因此,蒙脱石具有固定污染沉积物中Zn的能力,但不能提高污染沉积物中Cu的稳定性。     

粘土矿物转化的化学动力学模型与应用

本文讨论了粘土矿物转化的化学动力学模型及其应用。对于某一地区，粘土矿物蒙皂石向伊利石的转化主要受温度和时间的影响，可以用化学动力学一级反应的模型描述，这一模型可用于:（１）反演古大地热流；（２）模拟成岩史；（３）在盆地内没有钻井的区域预测地层的成岩阶段。     

Sorption of Trace Elements on Mineral Surfaces: Modern Perspectives from Spectroscopic Studies,and Comments on Sorption in the Marine Environment

The partitioning (or sorption) of trace elements from aqueous solutions onto mineral surfaces and natural organic matter (NOM) has played a major role in determining the trace element content of natural waters. This review examines sorption processes on mineral surfaces for nine trace elements (Cr, Co, Ni, Cu, Zn, Sr, Cd, Hg, Pb), focusing on the results of modern x-ray spectroscopic studies. Such studies provide unique information on the structure and composition of sorption products, including their mode of attachment to mineral surfaces or functional groups in NOM under in situ conditions (i.e., with aqueous solution present at 25°C). The types of chemical reactions (acid-base, ligand exchange, redox, dissolution/reprecipitation) that can occur at mineral-aqueous solution interfaces are also reviewed, and some of the factors that affect the reactivity of mineral surfaces are discussed, including changes in the geometric and electronic structures of mineral surfaces when they first react with aqueous solutions and constraints on the bonding of adions to surface functional groups imposed by Pauling bond valence sums. A summary of electrical double layer (EDL) theory is presented, including the results of several recent x-ray spectroscopic and parameter regression studies of the EDL for metal-(oxyhydr) oxide-aqueous solution interfaces. The effects of common inorganic and organic complexants on the sorption of trace metal cations at mineral-solution interfaces are considered, in the context of spectroscopic studies where possible. The results of sorption studies of trace metal cations on NOM, common bacteria, and marine biomass are reviewed, and the effects of coatings of NOM and microbial biofilms on cation uptake on mineral surfaces are discussed, based on macroscopic and spectroscopic data. The objective here is to assess the relative importance of inorganic versus organic sorption processes in aquatic systems. The paper concludes with a discussion of the effects of water composition on trace element removal mechanisms, with the aim of providing an understanding of the effects of the high salinity of seawater on trace element sorption processes. The information presented in this review indicates that sorption processes on mineral, NOM, and microbial and algal surfaces, including true adsorption and precipitation, are highly effective at removing trace elements from natural waters and generally supports Krauskopf's (1956) conclusion that such processes are likely responsible for the present trace element concentrations in seawater.     

Heave Studies on Fly Ash-Stabilised Expansive Clay Liners

Clay liners or compacted earthen barriers are important barrier materials used for preventing contaminant transport through soils. A low hydraulic conductivity (k) is a significant parameter that governs the design and construction of clay liners. Compacted expansive clays, which are montmorillonite clays, also have a very low hydraulic conductivity (k). When expansive clays are blended with fly ash, an industrial waste, the hydraulic conductivity (k) further reduces as the ash-clay blends result in increased dry densities at increased fly ash contents. Hence, fly ash-stabilised expansive clay can also be proposed as a unique clay liner material. As expansive clays undergo heave when they come into contact with water, it is necessary to study the heave behaviour of fly ash-stabilised expansive clay liners. This paper presents heave studies on fly ash-stabilised expansive clay liners. Fly ash in different contents by dry weight of the expansive clay was added to the clay, and the ash-clay blend was compacted as a liner overlying a natural field soil layer. Compacted lateritic clay was used for simulating the natural field soil into which contaminants migrate. Calcium chloride (CaCl₂) solution of varying concentration (5, 10, 20, 50, 100 and 500 mM) was used as the permeating fluid in the heave studies. The rate of heave and the amount of heave of the fly ash-stabilised expansive clay liners were monitored. Deionised water (DIW) was also used as inundating fluid for comparative study. Heave (mm) decreased with increase in solute concentration for all fly ash contents. For a given solute concentration, heave decreased up to a fly ash content of 20 % and thereafter it increased when the fly ash content was increased to 30 %. Heave of the fly ash-stabilised expansive clay liners was correlated with their permeability, liquid limit (LL) and free swell index (FSI) pertaining to the respective fly ash content and CaCl₂ concentration.     

Effects of Local Dispersion and Kinetic Sorption on Evolution of Concentration Variance in a Heterogeneous Aquifer

A Eulerian stochastic method is applied to develop a theory of concentration variance for solute transport in a heterogeneous medium. The study focuses on the effects of kinetic sorption and local dispersion on solute dissipation. Spatial distribution of the concentration variance is obtained by scaling the zero local dispersion form of σ_c ². The scaling function resulting from the local dispersion and kinetic sorption is derived in a closed integral form. It satisfies the measurement of total concentration variance resulting from the Eulerian mass balance using spatially integrated concentration moments. The spatially integrated moments bypass the need for classical closures applied to joint moments between concentration and velocity fields. The study results indicate that kinetic sorption reduces the total development of concentration variance in comparison with non-reactive solute transport. Kinetic sorption acts as a reduction mechanism, but not as a dissipating mechanism like the local dispersion. Kinetic sorption and local dispersion are not additive processes and their effects on the concentration variance depend on the stage of transport time.     

超压背景下粘土矿物转化的化学动力学模型及应用

在目前的粘土矿物转化化学动力学模型中,人们仅考虑了温度、时间和流体介质的影响。然而新近的一些研究表明,超压可以抑制粘土矿物的转化,增加反应活化能。通过超压调节反应活化能,建立超压背景下粘土矿物转化的化学动力学模型,并根据渤海湾盆地板桥凹陷、歧北凹陷超压发育井和歧南凹陷超压不发育井的粘土矿物实测资料,确定了相关参数。模拟结果表明,在超压井中,伊/蒙混层中蒙皂石层含量S%的计算值与实测数据吻合较好,但与Pytter和Reynolds(1989)模型的预测结果相差甚远,在压力系数为1.2~1.7的地层中,超压对S%的抑制最大可达15%~20%。由于在蒙皂石向伊利石转化的过程中,释放出大量S i4+、Ca2+、Mg2+、Fe3+、Na+等阳离子,所以超压对粘土矿物转化的抑制,导致了泥岩中这些阳离子生成量的减少和相邻砂岩中许多胶结作用的延迟,这非常有利于深层(埋深>3 500 m)优质储层的发育和油气藏的形成。     

Studies on Hydraulic Conductivity of Fly Ash-Stabilised Expansive Clay Liners

Earthen barriers or clay liners are a major concern in geo-environmental engineering. They are designed to preclude or reduce leachate migration. Hence, a low hydraulic conductivity (k) is an important parameter in the design of clay liners. Materials such as bentonite and lateritic clays, which have a low hydraulic conductivity at high dry densities, are used in the construction of clay liners. Compacted expansive clays which are high in montmorillonite content also have a very low hydraulic conductivity. When expansive clays are blended with fly ash, an industrial waste, the hydraulic conductivity further reduces as the ash-clay blends result in increased dry densities at increased fly ash contents. Hence, fly ash-stabilised expansive clay can also be proposed as an innovative clay liner material. It is, therefore, required to study various physical and engineering properties of this new clay liner material. Liquid limit (LL) and free swell index (FSI) are important index properties to be studied in the case of this clay liner material. The hydraulic conductivity of this new clay liner material depends on the fly ash content in the blend. Further, parameters such as solute concentration and kinematic viscosity also influence hydraulic conductivity of clay liners. This paper presents experimental results obtained on hydraulic conductivity (k) of fly ash-stabilised expansive clay liner at varying fly ash content and solute concentration. The tests were performed with deionised water (DIW), CaCl₂, NaCl and KCl as permeating fluids. Fly ash content in the blend was varied as 0, 10, 20 and 30 % by weight of the expansive clay, and the solute concentration was varied as 5 mM (milli molar), 10, 20, 50, 100 and 500. It was found that hydraulic conductivity (k) decreased with increasing fly ash content, solute concentration and kinematic viscosity. Further, hydraulic conductivity (k) was correlated with LL and FSI of the clay liner material for different fly ash contents and solute concentrations. Useful correlations were obtained.     

Reduction of Manganese Oxides: Thermodynamic,Kinetic and Mechanistic Considerations for One- Versus Two-Electron Transfer Steps

Manganese oxides, typically similar to δ-MnO₂, form in the aquatic environment at near neutral pH via bacterially promoted oxidation of Mn(II) species by O₂, as the reaction of [Mn(H₂O)₆]²⁺ with O₂ alone is not thermodynamically favorable below pH of ~?9. As manganese oxide species are reduced by the triphenylmethane compound leucoberbelein blue (LBB) to form the colored oxidized form of LBB (λ_max?=?623 nm), their concentration in the aquatic environment can be determined in aqueous environmental samples (e.g., across the oxic–anoxic interface of the Chesapeake Bay, the hemipelagic St. Lawrence Estuary and the Broadkill River estuary surrounded by salt marsh wetlands), and their reaction progress can be followed in kinetic studies. The LBB reaction with oxidized Mn solids can occur via a hydrogen atom transfer (HAT) reaction, which is a one-electron transfer process, but is unfavorable with oxidized Fe solids. HAT thermodynamics are also favorable for nitrite with LBB and MnO₂ with ammonia (NH₃). Reactions are unfavorable for NH₄⁺ and sulfide with oxidized Fe and Mn solids, and NH₃ with oxidized Fe solids. In laboratory studies and aquatic environments, the reduction of manganese oxides leads to the formation of Mn(III)-ligand complexes [Mn(III)L] at significant concentrations even when two-electron reductants react with MnO₂. Key reductants are hydrogen sulfide, Fe(II) and organic ligands, including the siderophore desferioxamine-B. We present laboratory data on the reaction of colloidal MnO₂ solutions (λ_max?~?370 nm) with these reductants. In marine waters, colloidal forms of Mn oxides (<?0.2 µm) have not been detected as Mn oxides are quantitatively trapped on 0.2-µm filters. Thus, the reactivity of Mn oxides with reductants depends on surface reactions and possible surface defects. In the case of MnO₂, Mn(IV) is an inert cation in octahedral coordination; thus, an inner-sphere process is likely for electrons to go into the empty e _g ^* conduction band of its orbitals. Using frontier molecular orbital theory and band theory, we discuss aspects of these surface reactions and possible surface defects that may promote MnO₂ reduction using laboratory and field data for the reaction of MnO₂ with hydrogen sulfide and other reductants.     

白云石形成过程中的热力学与动力学基础及自云岩形成环境划分

CaMg(CO3)2在现代海水中是过饱和的,但是前人的研究发现在实验室标准状态下(25℃.1atm)无法从海水中直接沉淀出白云石,所以,白云石的形成不是一个单纯的热力学问题,而是一个动力学问题.依据白云石形成的热力学和动力学特征,将白云岩的形成环境划分为表生成岩环境与埋藏成岩环境.表生成岩环境按白云岩发育位置又分为:潮坪一漏湖蒸发环境、环礁潜流面与深海沉积环境.埋藏成岩根据流体进入体系的方式又分为:与裂缝相关的埋藏成岩、与缝合线相关的埋藏成岩、与岩溶相关的埋藏成岩和与渗透回流相关的浅埋藏成岩.分别对所划分的各成岩环境进行了详细的岩石学与地球化学特征分析与讨论.     

白云石形成过程中的热力学与动力学基础及白云岩形成环境划分

CaMg(CO3)2在现代海水中是过饱和的,但是前人的研究发现在实验室标准状态下(25℃,1atm)无法从海水中直接沉淀出白云石,所以,白云石的形成不是一个单纯的热力学问题,而是一个动力学问题。依据白云石形成的热力学和动力学特征,将白云岩的形成环境划分为表生成岩环境与埋藏成岩环境。表生成岩环境按白云岩发育位置又分为:潮坪-澙湖蒸发环境、环礁潜流面与深?粱肪场B癫爻裳腋萘魈褰胩逑?的方式又分为:与裂缝相关的埋藏成岩、与缝合线相关的埋藏成岩、与岩溶相关的埋藏成岩和与渗透回流相关的浅埋藏成岩。分别对所划分的各成岩环境进行了详细的岩石学与地球化学特征分析与讨论。     

Kinetics and Equilibrium Sorption Studies of 4-Nitrophenol on pyrolyzed and activated oil shale residue

Sorption of the organic pollutant 4-nitrophenol (4-NP) by pyrolyzed and activated Jordanian oil-shale was studied. Pyrolyzed oil shale was prepared using a fluidized bed reactor at 520 °C in the presence of nitrogen. Physical activation was carried out by treating the pyrolyzed oil shale with CO₂ at 830 °C, while chemical activation was achieved by using KOH and ZnCl₂ as impregnating agents. Batch kinetics and isotherm studies were conducted to evaluate the sorption process. Effects of contact time, initial sorbate concentration, sorbent concentration, temperature, pH and inorganic salts (NaCl and KCl) on the sorption process by the different sorbents were considered. Chemically activated oil shale, pretreated with ZnCl₂, gave the highest uptake of 4-NP. The isotherm experimental data fit reasonably well to Langmuir, Freundlich and Redlich-Paterson models. Three kinetic models, namely the Morris-Weber, Lagergren, and Pseudo-Second-Order model (PSOM), were applied to represent the experimental results for both pyrolyzed and ZnCl₂-oil shale sorbents.     

低成熟石油烃源岩的动力学研究

本文介绍了对东营凹陷下第三系沙河街组沙四段上部具有不同自然熟化程度的低成熟石油烃源岩进行动力学研究的结果。结果表明，浅埋藏、低成熟、低有机丰度且与碳酸盐岩相关的源岩具相对较高的烃产率和平均活化能；平均活化能可能会掩盖低熟成烃特征。依据研究结果，指出当前进入门限埋深以下且具有低活化能生烃母质存在的牛１１样品可能在浅埋藏、低成熟时曾为该区（八面河低熟油田）低成熟石油的形成提供了油源。另外，笔者通过对样品可溶有机质抽提前后活化能分布对比研究，指出了低活化能分布范围内的生烃母质主要为可溶有机质。并且进而提出本区低成熟石油的成油下限埋深划分至２８００ｍ为宜，其对应的下限反应活化能不超过１７７ＫＪ/ｍｏｌ。     

岩溶水系统对大气CO2的潜在影响——基于热力学的研究

认识不同条件下岩溶水释放或吸收CO2的反应过程是研究碳酸盐岩对碳循环响应的前提和基础。本文从吉布斯自由能的热力学原理出发,对全球不同岩溶地区162组岩溶水(河水、溪水、湖水等)进行了热力学研究,结果显示:1)河水、溪水、湖水和洞穴滴水等岩溶水所处的环境因方解石矿物沉积而释放CO2成为大气CO2一个潜在的源;2)地下水在所处的环境下由于方解石的溶解而吸收CO2,成为大气CO2一个潜在的汇;3)少数出露点的泉水所处的环境既可发生方解石的溶解而吸收CO2,成为大气CO2的潜在汇,也可发生方解石的沉积而释放CO2,成为大气CO2的潜在源;4)在洪水期,泉水的水化学特征变化并未导致对大气CO2潜在贡献在源汇之间的跨跃性转变。162组岩溶水数据中,所有河水与溪水皆无一例外地在释放CO2。结果表明,从吉布斯自由能的热力学原理出发,研究岩溶水系统对大气CO2潜在源汇的贡献,没有条件约束,是一种较好的途径。     

Available Clay and Feldspar Reference Samples As Standards for Archaeological Pottery Studies

The available clay and feldspar reference samples, rather than the frequently used rock reference samples, are suggested as standards for archaeological pottery studies because their trace-element contents are more like those of the artefacts. Such samples may provide a basis for correlating archaeological studies throughout the world. The assumption that bottles of such reference samples should have homogeneous trace-element contents because of the nature of the materials has been confirmed by the analysis of variance of trace -element data by instrumental neutron activation analysis.     

广西百色盆地干酪根的研究──兼探干酪根的演化与粘土矿物的关系

本文用Ｘ射线、微区分析等方法对广西百色盆地那读三段泥岩中的干酪根进行了详细研究。该盆地干酪根的芳香度（Ｆａ）为０.２８至０.３７，芳香核厚度（Ｌｅ）为１６.６０Ａ到２０.７６Ａ，芳香片层数（ｎ）为５到６层，证明属Ⅱ型干酪根。在同一剖面，Ｆａ随深度增加而变大，表明了干酪根向成熟方向转化。在干酪根中碳元素的分布是不均匀的，一般中间含量高，向边部则含量变低，铁及硅元素也向中间聚集，多数情况下形成ＦｅＳ２核，在核的周围分布有粘土矿物。干酪根成熟程度的变化趋势与粘土矿物的演化趋势在宏观上是一致的，即与蒙脱石转化为伊/蒙混层粘土矿物的趋势一致。并从化学健和能量方面对这种过程进行了一些探讨。     

广西百色盆地干酪根的研究--兼探干酪根的演化与粘土矿物的关系

本文用X射线、微区分析等方法对广西百色盆地那读三段泥岩中的干酪根进行了详细研究,该盆地干酪根的芳香度（Fa）为0.28至0.37,芳香核厚度（Le）为16.60A到20.76A,芳香片层数（n）为5到6层,证明属Ⅱ型干酪根,在同一剖面,fa随深度增加而变大,表明了干酪根向成熟方向转化。在干酪根中碳元素的分布是不均匀的,一般中间含量高,向边部则含量变低,铁及硅元素也向中间聚集,多数情况下形成FeS₂核,在核的周围分布有粘土矿物。干酪根成熟程度的变化趋势与粘土矿物的演化趋势在宏观上是一致的,即与蒙脱石转化为伊/蒙混层粘土矿物的趋势一致。并从化学健和能量方面对这种过程进行了一些探讨。     

Adsorption of Fe~(3+) Ions from Aqueous Solution by Natural and Synthetic Apatites: Kinetic,Equilibrium and Thermodynamic Study

In this study, the adsorption kinetics, equilibrium and thermodynamics of Fe3+ ions on natural (NAP) and synthetic (HAP) apaties were examined. The adsorption efficiency of Fe3+ onto the NAP and HAP was increased with increasing temperature. The kinetics of adsorption of Fe3+ ions was discussed using three kinetic models, the pseudo-first-order, the pseudo-second-order and the intra-particle diffusion model. The experimental data fitted very well the pseudo-second-order kinetic model. The initial sorption rate and the activation energy were also calculated. The activation energy of the sorption was calculated as 37.15 and 49.84 kJ·mol 1 for NAP and HAP, respectively. Experimental results were also analysed by the Langmuir, Freundlich and Dubinin–Redushkevich (D–R) isotherm equations at different temperatures. RL separation factor for Langmuir and the n value for Freundlich isotherm show that Fe3+ ions are favorably adsorbed by NAP and HAP. Various thermodynamic parameters such as enthalpy (ΔH), Gibbs free energy (ΔG) and entropy (ΔS) changes were computed and the results showed that the adsorption of Fe3+ ions onto NAP and HAP were spontaneous and endothermic in nature.     

Sorption of lead on Iranian bentonite and zeolite: kinetics and isotherms

This study deals with the use of the natural, low-cost sorbents bentonite and zeolite for the removal of lead from aqueous solutions. The mineral material is from large deposits of bentonite and zeolite that have been discovered recently in Iran. Experimental and modeling data from our kinetic and equilibrium investigations reveal that (1) the pseudo-second-order kinetic model gave the best fit, and (2) the Koble–Corrigan sorption model describes the interaction between Pb(II) and the two mineral materials better than the Freundlich and Langmuir models. However, the sorption of Pb(II) ions by zeolite and bentonite is complex and probably involves several mechanisms. The experimental data show that natural zeolite and bentonite used in this study exhibited a reasonable sorption capacity for Pb(II), and thus may be useful for the immobilization of Pb(II) from polluted sites.     

Sorption of lanthanides on smectite and kaolinite

Experiments were carried out to investigate the sorption of the complete lanthanide series (Ln or rare earth elements, REE) on a kaolinite and an a Na-montmorillonite at 22°C over a wide range of pH (3-9). Experiments were conducted at two ionic strengths, 0.025 and 0.5 M, using two different background electrolytes (NaNO₃ or NaClO₄) under atmospheric conditions or N₂ flow (glove box). The REE sorption does not depend on the background electrolyte or the presence of dissolved CO₂, but is controlled by the nature of the clay minerals, the pH and the ionic strength. At 0.5 M, both clay minerals exhibit the same pH dependence for the Ln sorption edge, with a large increase in the sorption coefficient (K_D) above pH 5.5. At 0.025 M, the measured K_D is influenced by the Cation Exchange Capacity (CEC) of the minerals. Two different behaviours are observed for smectite: between pH 3 and 6, the K_D is weakly pH-dependent, while above pH 6, there is a slight decrease in log K_D. This can be explained by a particular arrangement of the particles. For kaolinite, the sorption coefficient exhibits a linear increase with increasing pH over the studied pH range. A fractionation is observed that due to the selective sorption between the HREEs and the LREEs at high ionic strength, the heavy REE is being more sorbed than the light REE. These results can be interpreted in terms of the surface chemistry of clay minerals, where two types of surface charge are able to coexist: the permanent structural charge and the variable pH-dependent charge. The fractionation due to sorption observed at high ionic strength can be interpreted either because of a competition with sodium or because of the formation of inner-sphere complexes. Both processes could favour the sorption of HREEs according to the lanthanide contraction.