共查询到20条相似文献，搜索用时 215 毫秒
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石英、高岭石、伊利石、蒙脱石和铁氧化物对五氯苯酚(PCP)吸附的pH关系等温线和浓度关系等温线已用批量平衡技术进行研究。所有矿物的pH关系等温线都表现出典型的峰形曲线特征,峰位在pH=5~6之间,依矿物不同而不同。基于矿物表面羟基位化合态和PCP的化合态考虑,研究提出一种包含表面络合反应和表面静电吸附反应的模式,对pH关系等温线计算拟合发现有很好的相关性。模式计算还表明,石英和层硅酸盐矿物对PCP吸附以表面络合反应为主,而氧化铁矿物则既包含表面络合反应,又包含表面静电吸附反应,但以后者占主导,其反应平衡常数比前者大1~3个… 相似文献
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五氯苯酚在矿物表面吸附——实验、表面反应模式及其环境意义 总被引：4，自引：0，他引：4
利用批量平衡技术研究了石英、高岭石、伊利石、蒙脱石和铁氧化物对五氯苯酚(PCP)吸附的pH关系等温线和浓度关系等温线,发现所有矿物的pH关系等温线都表现出典型的峰形曲线特征,峰位在pH=5～6之间,依矿物不同而不同。基于矿物表面羟基位化合态和PCP的化合态考虑,提出一种包含表面络合反应和表面静电吸附反应的模式,对pH关系等温线计算拟合发现有很好的相关性。模式计算还表明,石英和层状硅酸盐矿物对PCP吸附以表面络合反应为主,而氧化铁矿物则包含表面络合反应和表面静电吸附反应,但以后者占主导,其反应平衡常数比前者大1～3个数量级。高岭石和氧化铁矿物的浓度吸附等温线可用Langmuir方程很好拟合,最大吸附量的大小顺序是赤铁矿>纤铁矿>针铁矿>高岭石>石英>蒙脱石≈伊利石,并可以用矿物表面羟基位浓度和反应机制加以解释。PCP在矿物表面可观的吸附量说明矿物表面吸附对憎水性可离解有机化合物(HIOCs)在天然水相体系和沉积中的迁移转化过程起着相当重要的作用。 相似文献
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氧化铁矿物对重金属离子的吸附及其表面特征 总被引：5，自引：0，他引：5
杂质和复杂的微形貌导致铁（氢）氧化矿物表面的能量和结构高度不均一。能量高、配位数低的位置吸附力强。电荷和离子半径决定了重金属离子的吸附能力。由于表生地球化学过程中的吸附过程几乎都与流体有关,流体的ｐＨ值主要通过对铁氧化物的影响吸附过程,ｐＨ值的变化改变了铁氧化物表面羟基的分布,即改变表面吸附位置的结构,进而影响氧化物的吸附能力,铁（氢）氧化物的表面结构其复杂,现有的吸附理论从不同的角度出发,在一定程度上解释了铁（氢）氧化物的吸附行为,但也存在许多问题。 相似文献
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矿物—氨基酸水溶液的表面离子化及溶解作用研究 总被引：1，自引：1，他引：1
在矿物－氨基酸－水组成的多相体系中，矿物在氨基酸中的溶解作用是一个复杂的过程，其矿物的成分、结构和表面离子化是影响矿物溶解和络合的重要因素。水镁石、纤蛇纹石、硅灰石由于表面羟基化，在氨基酸水溶液中有较高的溶解度，溶解以配合作用为主；坡缕石、海泡石层状硅酸盐矿物表面羟基化作用较弱，与氨基酸的作用为配合作用和吸附作用并存，以后者为主；沸石矿物则以吸附作用为主。在中性氨基酸水溶液中，矿物的溶解度大小为：水镁石＞纤蛇纹石＞硅灰石＞海泡石＞坡缕石＞斜发沸石。 相似文献
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阳离子粘土即通常所指的粘土。阳离子粘土主要由层状结构的铝硅酸盐粘土矿物组成。粘土矿物的结构层板带负电荷 ,层间充填有可交换性阳离子。阴离子粘土是与阳离子粘土相对而言的。阴离子粘土又称水滑石型化合物或层状双金属氢氧化物 (简写为LDHs) ,天然产出少 ,以人工合成为主 ,具类似于水镁石的层状结构。阴离子粘土层板带正电荷 ,层间充填有平衡电荷的阴离子。阴离子粘土由于具有独特的阴离子交换性、层板组成的可设计性、结构的可恢复性而在近年受到极大的重视 ,是一类极具发展潜力的新型无机材料。由于阴阳离子两类粘土在成分、结构… 相似文献
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膨润土是以蒙脱石为主要成分(一般大于50%)的粘土矿物.蒙脱石属二八面体含水的层状铝硅酸盐类矿物.由于蒙脱石结构单元层中的硅和铝离子,分别被铝和镁离子置换因而层间出现电荷有吸附阳离子的作用.根据层间阳离子的不同,可分为钠基膨润土、钙基膨润土、镁基膨润土以及钙 相似文献
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矿物表面活性是矿物表界面反应中一个重要的指标性参数。如矿物溶解和晶体生长、矿物表面吸附和表面络合反应、矿物表面氧化还原和催化反应,都与矿物表面活性相关。甚至生物矿物界面作用过程中,常用到矿物表面反应性氧基(ROS),其释放能力也与矿物表面活性密切相 相似文献
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富钴结壳是一种重要的海底矿产资源,具有独特的经济价值和科学意义,其不仅富含Mn、Co、Ni、Cu、PGE和REY等金属,而且在反演新生代以来古海洋环境记录等方面扮演着独特的角色。锰氧化物(MnO2·xH2O)和铁羟基氧化物(FeOOH)是构成富钴结壳的主要矿物,矿物颗粒十分微小(纳米级)。水羟锰矿和水钠锰矿具有层状结构且层电荷为负,通过吸附阳离子来补偿。前人通过连续浸出实验、元素相关性统计分析、吸附实验和拓展X射线吸收精细结构(EXAFS)光谱广泛研究了微量元素在矿物中的赋存状态,确定了微量元素在锰氧化物矿物中主要存在三种类型络合物:共六边(edge-sharing)、共双角(double-corner sharing)和共三角(triple-corner sharing)。综合研究表明,在最低含氧带之下铁锰氧化物(氢氧化物)从海水沉淀到周围海山坚硬基岩上形成富钴结壳的机制主要是无机胶体化学反应和矿物表面反应。最后针对已有的相关研究现状以及富钴结壳研究面临的挑战,富钴结壳的成矿物质来源及演化、微量元素富集机制、蕴含的古海洋信息等问题仍需要进一... 相似文献
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稀土开采本质上是利用离子交换作用将稀土元素从矿物(黏土矿物、铁(氢)氧化物)表面解吸下来的过程,厘清不同类型矿物对稀土元素浸出的影响,对于提高开采效率至关重要。(NH4)2SO4溶液是稀土元素浸矿时的常用提取剂,SO42-可以通过与稀土元素络合、改变矿物表面电荷性质以及键桥作用等影响稀土元素在矿物表面的吸附/解吸行为,进而影响浸出效率。本研究以高岭石和水铁矿分别作为黏土矿物和铁(氢)氧化物的代表,通过向离子吸附型稀土原矿中添加不同含量(0、5%和10%)的高岭石或水铁矿,结合批量实验、X射线衍射分析(XRD)、电感耦合等离子体发射光谱仪(ICP-OES)及原位红外光谱(in situ ATR-FTIR)等分析表征手段,模拟不同浸取剂体系(NH4Cl和(NH4)2SO4)下,矿物类型对稀土元素浸取的影响。结果表明,在空白对照组中(未添加高岭石和水铁矿),NH4Cl浸出稀土... 相似文献
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Modeling the binding of fulvic acid by goethite: the speciation of adsorbed FA molecules 总被引：1，自引：0，他引：1
Jeroen D. Filius David G. Lumsdon Willem H. van Riemsdijk 《Geochimica et cosmochimica acta》2003,67(8):1463-1474
Under natural conditions, the adsorption of ions at the solid-water interface may be strongly influenced by the adsorption of organic matter. In this paper, we describe the adsorption of fulvic acid (FA) by metal(hydr)oxide surfaces with a heterogeneous surface complexation model, the ligand and charge distribution (LCD) model. The model is a self-consistent combination of the nonideal competitive adsorption (NICA) equation and the CD-MUSIC model. The LCD model can describe simultaneously the concentration, pH, and salt dependency of the adsorption with a minimum of only three adjustable parameters. Furthermore, the model predicts the coadsorption of protons accurately for an extended range of conditions. Surface speciation calculations show that almost all hydroxyl groups of the adsorbed FA molecules are involved in outer sphere complexation reactions. The carboxylic groups of the adsorbed FA molecule form inner and outer sphere complexes. Furthermore, part of the carboxylate groups remain noncoordinated and deprotonated. 相似文献
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WU Daqing DIAO Guiyi YUAN Peng PENG Jinlian 《《地质学报》英文版》2006,80(2):192-199
The adsorption of pentachlorophenol （PCP） onto quartz, kaolinite, illite, montmorillonite and iron oxides has been investigated by batch equilibrium techniques. The pH-dependent isotherms are curves with peak values, the position of which is at about pH = 5-6 depending on the mineral species. Based on distribution of both speciation of surface hydroxyls on minerals and PCP in solution a surface reaction model involving surface complexation and surface electrostatic attraction is presented to fit the pH-dependent isotherms, and both reaction constants are calculated. The results show that on quartz and phyllosilicate minerals the predominant adsorption reaction is surface complexation, meanwhile both of surface electrostatic attraction and surface complexation are involved on the iron oxide minerals. The reaction constants of surface electrostatic adsorption are usually one to three orders in magnitude, larger than that of surface complexation. The concentration-dependent isotherms can be well fitted by Langmnir equation with the correlation coefficient R〉0.93 for kaolinite and iron oxides. The maximum adsorption is found in the order： hematite 〉 lepidocrocite 〉 goethite 〉 kaolinite 〉 quartz 〉 montmorillonite ≈ illite, which can be interpreted by consideration of both reaction mechanism and surface hydroxyl density. The significant adsorption of PCP onto mineral surfaces suggests that clay and iron oxide minerals will play an important role as HIOCs are adsorbed in laterite or latertoid soil, which is widespread in South China. 相似文献
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Sreejesh Nair Lotfollah Karimzadeh Broder J. Merkel 《Environmental Earth Sciences》2014,71(4):1737-1745
Surface complexation models (SCMs) are widely utilized as a tool to study the mobility of radionuclide to the environment. In this study, two SCMs, electrostatic (ES) and non-electrostatic (NES) models are employed in order to simulate the sorption behavior of U(VI) on quartz in the absence of Mg, Ca, and Sr and ES model in the presence of alkaline earth metals. The surface reaction constants (log K) for ES and NES models were fitted to experimental data by coupling PEST with PHREEQC. The SCM prediction of U(VI) sorption on quartz in the absence of alkaline earth metals is in good agreement with the experimental data in the pH range 6.5–9. The estimated log K values are sensitive to both ES and NES model calculations. In U(VI)-Mg-quartz, U(VI)-Ca-quartz, and U(VI)-Sr-quartz systems, only the ES model shows the general trend of the experimental data. The estimated log K values are sensitive with respect to the surface reactions. Hence, the ES model is more suitable for model calculations of the U(VI)-Mg-quartz, U(VI)-Ca-quartz, and U(VI)-Sr-quartz systems. 相似文献
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Susana Serrano Peggy A. O’Day Maria Teresa García-González 《Geochimica et cosmochimica acta》2009,73(3):543-558
The bioavailability and fate of heavy metals in the environment are often controlled by sorption reactions on the reactive surfaces of soil minerals. We have developed a non-electrostatic equilibrium model (NEM) with both surface complexation and ion exchange reactions to describe the sorption of Pb and Cd in single- and binary-metal systems over a range of pH and metal concentration. Mineralogical and exchange properties of three different acidic soils were used to constrain surface reactions in the model and to estimate surface densities for sorption sites, rather than treating them as adjustable parameters. Soil heterogeneity was modeled with >FeOH and >SOH functional groups, representing Fe- and Al-oxyhydroxide minerals and phyllosilicate clay mineral edge sites, and two ion exchange sites (X− and Y−), representing clay mineral exchange. An optimization process was carried out using the entire experimental sorption data set to determine the binding constants for Pb and Cd surface complexation and ion exchange reactions.Modeling results showed that the adsorption of Pb and Cd was distributed between ion exchange sites at low pH values and specific adsorption sites at higher pH values, mainly associated with >FeOH sites. Modeling results confirmed the greater tendency of Cd to be retained on exchange sites compared to Pb, which had a higher affinity than Cd for specific adsorption on >FeOH sites. Lead retention on >FeOH occurred at lower pH than for Cd, suggesting that Pb sorbs to surface hydroxyl groups at pH values at which Cd interacts only with exchange sites. The results from the binary system (both Pb and Cd present) showed that Cd retained in >FeOH sites decreased significantly in the presence of Pb, while the occupancy of Pb in these sites did not change in the presence of Cd. As a consequence of this competition, Cd was shifted to ion exchange sites, where it competes with Pb and possibly Ca (from the background electrolyte). Sorption on >SOH functional groups increased with increasing pH but was small compared to >FeOH sites, with little difference between single- and binary-metal systems. Model reactions and conditional sorption constants for Pb and Cd sorption were tested on a fourth soil that was not used for model optimization. The same reactions and constants were used successfully without adjustment by estimating surface site concentrations from soil mineralogy. The model formulation developed in this study is applicable to acidic mineral soils with low organic matter content. Extension of the model to soils of different composition may require selection of surface reactions that account for differences in clay and oxide mineral composition and organic matter content. 相似文献
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Surface complexation modeling of Cu(II) adsorption on mixtures of hydrous ferric oxide and kaolinite
Tracy J Lund Carla M Koretsky Christopher J Landry Melinda S Schaller Soumya Das 《Geochemical transactions》2008,9(1):9
Background
The application of surface complexation models (SCMs) to natural sediments and soils is hindered by a lack of consistent models and data for large suites of metals and minerals of interest. Furthermore, the surface complexation approach has mostly been developed and tested for single solid systems. Few studies have extended the SCM approach to systems containing multiple solids. 相似文献17.
铁氧化物矿物对苯酚和溶解性有机质表面吸附的初步研究 总被引：2，自引：0，他引：2
文中以铁氧化物矿物对苯酚和溶解性有机质(DOM)的吸附研究为例开展生态矿物学研究。铁氧化物矿物的吸附作用存在多种机制,这些吸附机制发生作用的条件主要取决于溶液化学性质和吸附质的理化性质。批处理实验研究表明,苯酚吸附在酸性微酸性条件下不强,吸附等温线符合Langmuir方程,属于表面分子吸附模型;DOM的吸附强并发生吸附分异,配体交换、憎水键和范氏力等多种模式并存,在酸性中性条件下对DOM在针铁矿上的吸附起着重要贡献。本文实验条件下DOM吸附等温线近于线性,不能采用Langmuir方程拟合,可能原因是DOM浓度较低。矿物表面荷电性对吸附影响显著,例如,当矿物表面净电荷为零(pH=pHpzc)时,矿物表面水化膜减薄甚至消失,苯酚分子、憎水DOM分子或片断都会倾向于在矿物表面上吸附。由于苯酚吸附机制单一,其受到的影响很明显,所以苯酚在pH值7～8范围内出现吸附最大值;由于配体交换作用主要发生在酸性微酸性条件下,所以在本文pH值约7.5的实验条件下,尽管配体交换仍在发生作用,但它不是主要吸附机制,针铁矿对DOM吸附的主要贡献应是憎水键和范氏力作用,此外,DOM吸附等温方程近于线性还可能与此有关。显然,铁矿物表面作用在对有机质含量低而铁矿物含量高的红壤中污染物和DOM的固定与归宿控制中扮演着重要的角色。 相似文献
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Tjisse Hiemstra A.M.D. van Rotterdam Willem H. van Riemsdijk 《Geochimica et cosmochimica acta》2010,74(1):59-8428
Information on the particle size and reactive surface area of natural samples and its interaction with natural organic matter (NOM) is essential for the understanding bioavailability, toxicity, and transport of elements in the natural environment. In part I of this series (Hiemstra et al., 2010), a method is presented that allows the determination of the effective reactive surface area (A, m2/g soil) of the oxide particles of natural samples which uses a native probe ion (phosphate) and a model oxide (goethite) as proxy. In soils, the natural oxide particles are generally embedded in a matrix of natural organic matter (NOM) and this will affect the ion binding properties of the oxide fraction. A remarkably high variation in the natural phosphate loading of the oxide surfaces (Γ, μmol/m2) is observed in our soils and the present paper shows that it is due to surface complexation of NOM, acting as a competitor via site competition and electrostatic interaction. The competitive interaction of NOM can be described with the charge distribution (CD) model by defining a ≡NOM surface species. The interfacial charge distribution of this ≡NOM surface species can be rationalized based on calculations done with an evolved surface complexation model, known as the ligand and charge distribution (LCD) model. An adequate choice is the presence of a charge of −1 v.u. at the 1-plane and −0.5 v.u. at the 2-plane of the electrical double layer used (Extended Stern layer model).The effective interfacial NOM adsorption can be quantified by comparing the experimental phosphate concentration, measured under standardized field conditions (e.g. 0.01 M CaCl2), with a prediction that uses the experimentally derived surface area (A) and the reversibly bound phosphate loading (Γ, μmol/m2) of the sample (part I) as input in the CD model. Ignoring the competitive action of adsorbed NOM leads to a severe under-prediction of the phosphate concentration by a factor ∼10 to 1000. The calculated effective loading of NOM is low at a high phosphate loading (Γ) and vice versa, showing the mutual competition of both constituents. Both constituents in combination usually dominate the surface loading of natural oxide fraction of samples and form the backbone in modeling the fate of other (minor) ions in the natural environment.Empirically, the effective NOM adsorption is found to correlate well to the organic carbon content (OC) of the samples. The effective NOM adsorption can also be linked to DOC. For this, a Non-Ideal Competitive adsorption (NICA) model is used. DOC is found to be a major explaining factor for the interfacial loading of NOM as well as phosphate. The empirical NOM-OC relation or the parameterized NICA model can be used as an alternative for estimating the effective NOM adsorption to be implemented in the CD model for calculation of the surface complexation of field samples. The biogeochemical impact of the NOM-PO4 interaction is discussed. 相似文献
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Adelia J.A. Aquino Daniel Tunega Georg Haberhauer Hans Lischka 《Geochimica et cosmochimica acta》2008,72(15):3587-3602
Density functional theory is used to compute the effect of protonation, deprotonation, and dehydroxylation of different reactive sites of a goethite surface modeled as a cluster containing six iron atoms constructed from a slab model of the (1 1 0) goethite surface. Solvent effects were treated at two different levels: (i) by inclusion of up to six water molecules explicitly into the quantum chemical calculation and (ii) by using additionally a continuum solvation model for the long-range interactions. Systematic studies were made in order to test the limit of the fully hydrated cluster surfaces by a monomolecular water layer. The main finding is that from the three different types of surface hydroxyl groups (hydroxo, μ-hydroxo, and μ3-hydroxo), the hydroxo group is most active for protonation whereas μ- and μ3-hydroxo sites undergo deprotonation more easily. Proton affinity constants (pKa values) were computed from appropriate protonation/deprotonation reactions for all sites investigated and compared to results obtained from the multisite complexation model (MUSIC). The approach used was validated for the consecutive deprotonation reactions of the [Fe(H2O)6]3+ complex in solution and good agreement between calculated and experimental pKa values was found. The computed pKa for all sites of the modeled goethite surface were used in the prediction of the pristine point of zero charge, pHPPZN. The obtained value of 9.1 fits well with published experimental values of 7.0-9.5. 相似文献