Surface Charge Concentrations on Silica in Different 1.0 M Metal-Chloride Background Electrolytes and Implications for Dissolution Rates     

Magnus Karlsson  Colin Craven  Patricia M. Dove  William H. Casey 《Aquatic Geochemistry》2001,7(1):13-32

The empirical rate laws formulated to describe the dissolution rates of oxide minerals include the surface charge concentration that results from the protonation and deprotonation of surface functional groups. Previous experiments on quartz and silica have shown that dissolution rates vary as a function of different background electrolyte solutions, however, such experiments are often conducted at elevated temperatures where it is difficult to estimate surface charge along with the dissolution rates. In the present study we measuresurface charge concentrations for silica in different electrolyte solutions at 298 K in order to quantify the extent to which the different counterions could affect the dissolution rates through their influence on the surface charge concentrations. The experimental solutions in the electrolyte series: LiCl, NaCl, KCl, RbCl, CaCl₂, SrCl₂ and BaCl₂ were prepared to maintain a constant metal concentration of 1.0 M. For the alkali-metal chlorides, the surface charge concentrations correlate with the size of the hydrated alkali metal, consistent with the idea that these counterions affect charge via outer-sphere coordination that shield proton surface complexes from one another. The reactivity trend for alkaline-earth cations is less clear, but the data demonstrate distinct differences in the acid-base propertiesof the silica surface in these different electrolytes. We then discuss how these trends are manifested in the rate equations used to interpret dissolution experiments.  相似文献   

An application of least-squares inverse analysis in kinetic interpretations of hydrous pyrolysis experiments     

S?ren B. Nielsen  Tanja Barth 《Mathematical Geology》1991,23(4):565-582

A least-squares inverse method is applied to the estimation of optimum kinetic parameters with statistical error bounds from concentration data obtained in isothermal hydrous pyrolysis experiments. The inverse method requires the specification of a data-parameter relationship (e.g., classical kinetic theory), the prior covariance matrices of data and parameter errors, as well as the prior central estimates of data and parameters. The reaction scheme considered is the common case of kerogen breakdown by Gaussian-weighted independent parallel first-order reactions and bitumen cracking by a single first-order reaction. The nonlinearity of the problem is reduced by a logarithmic transformation, which suggests a parameterization in terms of logarithmic concentrations, activation energies, and logarithmic Arrhenius factors. The linearized variance analysis is valid for the case studied, and the posterior covariance matrix reveals which parameters are constrained by the data. We find that the statistical errors in the average activation energy and the associated Arrhenius factor are strongly correlated. Hence, the parameters which determine the temperature dependence of the reaction rate have not been resolved independently. Furthermore, the kinetic results are very sensitive to the presence of a distribution of activation energies in kerogen breakdown. This distribution is not constrained by the data. As a consequence, neglecting the consideration of distributions of activation energies results in activation parameter values which are much too low. This is the major reason for the commonly encountered discrepancy between kinetic parameter values obtained from hydrous pyrolysis and micropyrolysis experiments, respectively.  相似文献   

陕西丹凤秦岭群石榴子石变质结晶动力学研究     

王河锦 《矿物学报》1991,11(3):258-266

本文运用晶体大小分布理论对陕西丹凤秦岭群石榴子石进行了变质结晶动力学的研究,通过对石榴子石在岩石中出现的频率及其大小值的系统测定,有关变质结晶动力学的分析计算,最终得出了丹凤秦岭群石榴子石的变质结晶初始成核密度、成核速度、晶体生长速度、生长时间及冷却过程中体积转移量等诸动力学要素,并从晶体大小分布研究中获得了多期复杂变质这一与地质事实一致的重要地质信息。  相似文献   

New aspects on the chemistry of aluminum in soils   总被引：2，自引：0，他引：2  

Gerhard Furrer 《Aquatic Sciences - Research Across Boundaries》1993,55(4):281-290

Dissolution kinetics of minerals can be significantly inhibited by re-adsorbed aluminum. As a consequence of neutralization, polynuclear Al species may be formed in soil solutions. While re-acidification leads to decomposition of the polymers, further neutralization induces the formation of aggregates. The complexation of heavy metal ions with dissolved and aggregated Al polymers is illustrated as a potential factor influencing the chemical speciation of heavy metals in soils.  相似文献   

Comparative study of adsorption behavior of copper, lead, and zinc onto goethite in aqueous systems   总被引：2，自引：1，他引：2  

Z. S. Kooner 《Environmental Geology》1993,21(4):242-250

  相似文献   

The Role of Particulate Matter in the Mobilization of Trace Metals during Anaerobic Digestion of Solid Waste Material Die Bedeutung der partikulären Substanz für die Mobilisierung von Spurenmetallen beim anaeroben Abbau fester Abfallstoffe     

St. Peiffer  U. Becker  R. Herrmann 《洁净——土壤、空气、水》1994,22(3):130-137

Metal ions bound to particulate matter represent the greatest portion (i.e. > 95%) of the total metal content found in leachate from reactor experiments where solid waste material was anaerobically digested. This seems true even though strong complexing agents are in solution which increase the solubility of Pb and Cu by a factor up to 10⁴… 10⁵ over that theoretically predicted according to the solubility of the corresponding sulfide mineral. A titrimetric characterization of the metal ion binding sites of the particulate matter suggests that the metal binding properties of the particulate matter are mainly due to organic, aminoacid-type compounds (amines. thio groups, carboxylic groups) probably of bacterial origin. The change of the concentration of the binding sites with time, together with the change of the composition of the particulate matter indicates that bacterial flocs are suspended in the leachate during the switch from acidogenic to methanogenic conditions — either due to the detachment of bacterial films from the solid material by the intensive gas production or due to the formation of syntrophic methanogenic bacterial associations or a combination of both. A combination of the two factors, strong affinity of bacterial mass to metal ions on the one hand, and suspending of the bacterial mass in the leachate on the other hand, will therefore imply a great mobilizing potential for trace metals. Consequently, the highest concentrations of particulate bound Cd were found in reactor experiments where sewage sludge contaminated with Cd was added to the waste material. An increase of the concentration of dissolved cadmium over the solubility of cadmium sulfide, however, could not be observed.  相似文献   

Eine mathematische Methode zur Durchführung von Adsorptionsanalysen A Mathematical Method for Evaluation of Adsorption Analysis     

K. Johannsen  E. Worch 《洁净——土壤、空气、水》1994,22(5):225-230

Adsorption analysis is a method for describing an overall isotherm of a mixture of unknown composition such as natural organic substances or chemical industries wastewater by dividing into fictive components of different adsorbability. The adsorption behaviour of the fictive components is characterized by using the Freundlich isotherm. The competitive adsorption between these components is described by the Ideal Adsorbed Solution Theory (IAST). Usually, at given Freundlich parameters K and n, the initial concentrations of the fictive components must be adjusted in order to obtain a good fit between calculated and measured isotherm data points. The results of this adjustment depend to some extent on the minimization criteria. Previously, the modeling was done with empirical or numerical methods which required a lot of computation time and sometimes caused numerical problems which made the interpretation of the results difficult. This paper describes a mathematical method for the evaluation of isotherms by adsorption analysis.  相似文献   

集安岩群石榴石成分特征及其动力学意义     

Hu Daqian  Xu Xuechun 《吉林大学学报(地球科学版)》1994,(4)

集安岩群石榴石以富铁为特征，均属铁铝榴石。形成于高角闪岩相的石榴石成分比较稳定，＜ＦｅＯ＞平均含量３２．２０％，ＭｇＯ５．１７％，Ｘ＿（Ｍｇ）平均值０．２３；结晶于低角闪岩相的石榴石（ＦｅＯ＋ＭｇＯ）含量３３．５０％，（ＭｎＯ＋ＣａＯ）６．９１％。石榴石微区成分不均匀，晶体内具有一些微区成分环带，这种环带不是各进变质作用阶段ｐ－Ｔ条件平衡或近平衡的产物。石榴石边缘存在着明显的扩散环带，表现为晶体边缘相对晶体核部，Ｃａ含量和＜ＦｃＯ＞含量增高，ＭｇＯ含量降低，Ｘ＿（Ｍｇ）值变小，反映本区变质峰期后经历的是一个近等压冷却的地质动力学过程。  相似文献   

生油岩热解生烃潜力及生烃动力学研究     

查明  赵永军  毛超林  周绍强 《地质论评》1994,40(7):63-69

利用岩石评价仪(R0cK EVAL I)对某凹陷30块生油岩进行了热解生烃和生烃动力学研究。在热解实验中，用类型指数、生烃潜量、最大热解峰温Tmax、等指标对上侏罗统3个层位的生油岩进行了母质类型、成熟度和生烃能力评价，结果表明，母质类型好、有机质丰富的未成熟生油岩的热解生烃量要比相同的已成熟生油岩高得多，说明选择未成熟生油岩热解对评价其生油能力的重要性。在对另2个未成熟生油岩的热解模拟实验中，得到了生烃率与温度之间的关系，并由此计算了生油岩的表观活化能、频率因子等动力学参数。  相似文献   

Probabilistic modeling of aerated lagoons: A comparison of methodologies     

R. Leduc  S. Ouldali 《Stochastic Environmental Research and Risk Assessment (SERRA)》1990,4(1):65-81

Two stochastic models are developed to describe the BOD output (i.e. effluent) variation of facultative aerated lagoons in series. One of the models uses the uncertainty analysis (UA) technique and the other is based on the moment equation solution methodology of stochastic differential equations (SDE's). The former considers a second-order approximation of the expectation (SOAE) and a first-order approximation of the variance (FOAV). The SDE model considers that output variability is accounted for by random variations in the rate coefficient. Comparisons are provided. Calibration and verification of the two models are aciieved by using field observations from two different lagoon systems in series. The predictive performances of the two models are compared with each other and with another SDE model, presented in a previous paper, that considers input randomness. The three methods show similar predictive performances and provide good predictions of the mean and standard deviation of the lagoon effluent BOD concentrations and thus are considered as appropriate methodologies.  相似文献