高放废物深地质处置库蒙脱土对铀酰的吸附阻滞行为:分子模拟研究

核废料处置库在长期运行过程中,地下水渗流会引起膨润土缓冲层水化学环境改变。运用分子动力学模拟方法,揭示含蒙脱土的膨润土缓冲材料对放射性核素铀酰的吸附机理及吸附复合物微观结构。模拟得到的复合物结构展现了铀酰与蒙脱土面的3种主要吸附模式:外球吸附、单键内球吸附、双键内球吸附。定量分析了在复杂水化学环境下3种铀酰种态与蒙脱土表面形成的复合物微观结构组成。通过计算复合物与蒙脱土表面的吸附能,发现高价阳离子和碳酸根离子的存在可以促进铀酰与缓冲材料表面形成稳定吸附。     

聚丙烯酸酯/蒙脱土复合乳液的结构与耐水性能研究

采用胶乳接枝插层法制备了聚丙烯酸酯/蒙脱土纳米复合乳液,利用X-射线衍射(XRD)和透射电镜(TEM)对复合乳液的结构进行了分析,并就蒙脱土添加量对复合体系的表面自由能、吸水率及干燥时间的影响进行了研究。结果表明:蒙脱土在复合乳液中达到了纳米级分散,形成了插层型与剥离型共存的微观结构。蒙脱土用量对胶膜的表面自由能、吸水率和干燥时间都有重要的影响,当蒙脱土用量达到5份时,胶膜的表面自由能和吸水率分别降低11%和67%,但乳液的干燥时间延长。     

基于分子动力学模拟技术的黏土矿物微观行为研究应用

黏土矿物是一类具有层状结构的硅酸盐矿物。土水相互作用对土体许多宏观力学响应、物质运移和传导起重要影响。现有的实验技术和手段即很难在物理上微观探测黏土从绝对干燥至含微量水分子的吸附过程,也很难实现黏土对放射性核素吸附过程的跟踪。使用分子动力学模拟对黏土矿物的水化性质及对放射性污染物吸附性能进行研究。以蛭石、高岭土及蒙脱土三种黏土矿物为研究对象,通过晶层间距、自扩散系数、径向分布函数、吸附复合物结构等模拟测试结果对蛭石的水化性能和黏土对放射性核素的吸附行为阐述。最后,对分子动力学模拟技术在岩土工程的应用发展进行了展望。     

改善聚羧酸超塑化剂与蒙脱土适应性的抗泥剂及其机理研究

采用水泥净浆流动度来评价抗泥剂(JJA-KNJ)对加蒙脱土水泥中聚羧酸超塑化剂(PCE)分散性能的改善效果,并结合有机碳含量(TOC),热重(TG),X射线衍射(XRD),扫描电镜(SEM)分析,研究了JJA-KNJ与蒙脱土之间的作用机理.结果表明:抗泥剂JJA-KNJ可改善PCE对加蒙脱土水泥的初始分散能力,显著改善PCE对加蒙脱土水泥的经时分散能力,提高其保坍性能;当PCE与JJA-KNJ同时存在时,JJA-KNJ能降低蒙脱土对PCE的吸附量,使得蒙脱土表面变得更加光滑,且空隙更小;JJA-KNJ溶于水后,吸附在蒙脱土颗粒的表面上,形成一层有机阳离子聚合物保护膜,阻止PCE的侧链进入蒙脱土的层间;JJA-KNJ在水泥水化的碱性条件下对蒙脱土颗粒具有明显的稳定效果,而且这一效果不会随着时间的延长出现明显衰减.     

离子固化剂改性蒙脱土吸附水特性及持水模型研究

采用不同浓度离子固化剂对天然钙蒙脱土进行改性处理,开展素土与改性土在相对湿度(P/P0)0.01～0.95区间的水汽等温吸—脱附试验,通过持水速率曲线、晶层d001演化曲线及红外光谱特征峰解析蒙脱土吸附水进程中主控因素的演化规律,据此提出水合状态变化的界限相对湿度区间,在此基础上,分别从阳离子水化能和晶层表面水合能角度,建立了离子固化剂改性蒙脱土微观持水方程。试验结果表明:对于钙蒙脱土,在0P/P00.15～0.2,阳离子与水分子结合形成单层"水化壳";在0.15～0.2P/P00.45～0.5,阳离子形成2层"水化壳";当0.45～0.5P/P00.8～0.9,晶层基面进一步吸附水分子形成2层完整水化膜。在极高吸力段(ψ200 MPa),蒙脱土持水能力只受控于层间阳离子水化作用,而在中高吸力段(15 MPaψ200 MPa),晶层基面与水之间的分子作用力是影响蒙脱土表面水合能及持水性状的主要因素。在特定吸力范围内,离子固化剂通过改变相应的物化性质参数(阳离子交换量、比表面积)从而弱化蒙脱土持水能力。基于微观水合机制所构建的持水方程能够很好预测本次试验及文献报道的数据结果,不同吸力段的持水模型可量化表征离子固化剂对蒙脱土吸附水性状的调控机理。     

氨基酸改性耐泥聚羧酸减水剂的制备及其作用机理

将苯丙氨酸接枝到马来酸酐聚乙二醇酯末端,合成了氨基酸改性不饱和酸酯,并将其引入到聚羧酸减水剂(PCE)中,制备了耐泥PCE;研究了氨基酸改性不饱和酸酯、引发剂和链转移剂用量对水泥-蒙脱土净浆耐泥性能的影响,并结合蒙脱土吸附量、层间距和孔结构的变化,对耐泥PCE的作用机理进行了研究.结果表明:与普通PCE相比,采用耐泥PCE制备的水泥-蒙脱土净浆初始流动度增大18.6％,经时损失率从39.5％降低至13.7％;氨基酸改性不饱和酸酯有效降低了蒙脱土对PCE的吸附量,抑制了蒙脱土的插层吸附和表面吸附.     

蒙脱土对聚羧酸超塑化剂的吸附行为

测定了蒙脱土对聚羧酸超塑化剂(PCE)分散性能的影响,研究了蒸馏水和水泥滤液中蒙脱土对PCE的静态吸附和动态吸附行为,拟合了吸附过程的动力学模型.结果表明:水泥中掺入蒙脱土会导致PCE对水泥分散能力的显著降低;蒙脱土对PCE的吸附量与PCE质量浓度近似成正比关系;水泥滤液中,PCE在蒙脱土上的平衡吸附量要远高于蒸馏水中的平衡吸附量;PCE在蒙脱土上的吸附过程均符合准二级反应动力学模型.     

高吸力段黏土水合机制及微观持水模型研究

采用水汽吸附法测定3种蒙脱土在高吸力段的持水特征曲线,基于X射线衍射及BET吸附理论架构,提出了两类水合概化模型并建立了阳离子交换量、比表面积等参数的计算方法。基于极低相对湿度范围段(RH0.15)持水能力只受控于层间阳离子水合的机理认识,通过阳离子与水分子相互作用能量方程,推导了极高吸力下(ψ250 MPa)持水曲线微观参数模型。研究表明:层间阳离子水合能力的差异会导致蒙脱土吸附起始阶段呈现不同趋势,对于低水合能阳离子交换土,水分子首先吸附于黏土颗粒外表面,之后随相对湿度增加逐渐进入层间吸附,反之,则直接进入层间离子水合阶段;基于BET曲线计算的阳离子交换量、比表面积值与实测值之间吻合较好,构建的持水模型能够对文献报道数据进行有效预测,该模型可量化表征阳离子交换量、化合价、离子半价等微观参数对吸力势的影响程度。     

含AMPS组元的聚羧酸减水剂对黏土敏感性的研究

在传统丙烯酸-异戊烯基聚氧乙烯醚(AA-TPEG)聚羧酸减水剂(PCE)基础上引入2-丙烯酰胺-2-甲基丙烯磺酸(AMPS)单体,合成了AA-TPEG-AMPS聚羧酸减水剂(ATS),研究了其在水泥-蒙脱土浆体系统中的分散性.结果表明:ATS减水剂在蒙脱土上的吸附行为与PCE无明显差别,但在水泥颗粒上的吸附量较小,吸附层厚度较大,能显著降低水泥颗粒表面的Zeta电位,对水泥-蒙脱土浆体系统仍具有较好的分散性及分散保持性,降低了聚羧酸减水剂对蒙脱土的敏感性.     

膨润土表面分维的试验确定

压实膨润土因其膨胀特性被用作高放射性核废料深地质处置工程的缓冲材料,膨润土的膨胀特性与其表面特性有关。对原始膨润土粉末以及被不同浓度的NaCl溶液浸泡过的膨润土进行N₂分子吸附实验,测得N₂吸附等温线,对吸附等温线采用Frenkel-Halsey-Hill(FHH)方程和Neimark热力学方法计算表面分维,计算结果表明,采用两种方法计算的表面分维基本相同。膨润土的表面性质受NaCl溶液浓度的影响较大,表面分维随NaCl浓度的增加呈现出先增大后减小的趋势,这是由于浓度不同膨润土表面吸附的Na⁺量不同所引起的。     

Reactions between bacterial exopolymers and goethite: A combined macroscopic and spectroscopic investigation

The adsorption to goethite of extracellular polymeric substances (EPS) isolated from Pseudomonas putida was investigated using batch adsorption experiments, electrophoretic mobility (EM) measurements, Fourier transform infrared (FTIR) spectroscopy, isothermal titration calorimetry (ITC) and X-ray absorption fine structure (XAFS) spectroscopy. The adsorption of EPS decreased the point of zero charge of goethite from 7.6 to 3.2, suggesting the formation of negatively charged inner-sphere surface complexes. The adsorption isotherms of EPS on goethite conformed to the Langmuir equation. The adsorption energy constant (K) of EPS on goethite was in the sequence of EPS phosphate-containing moieties > nitrogen-containing moieties > carbon-containing moieties, indicating those containing phosphate were the most strongly adsorbed. FTIR showed ligand exchange of phosphate groups of EPS with surface hydroxyls on goethite. Extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge structure (XANES) spectroscopy results further demonstrated phosphate groups of EPS can form monodentate inner-sphere complexes at lower pH 3.0, while form bidentate inner-sphere complexes at higher pH 9.0. The oxidation state of iron in goethite was not changed after the reaction with EPS at different pH values. The information obtained in this study is of fundamental significance for the understanding of the interaction mechanisms between bacteria and minerals in soil and aquatic environments.     

膨润土在高碱环境中的反应变化特征

膨润土具有高膨胀性、低渗透性以及优良的核素吸附能力,被选为高放废物处置库的缓冲回填材料。然而,作为处置库主要建造材料的混凝土会随着时间衰退分解产生高碱性溶解物,与地下水形成高碱性孔隙水,膨润土会与之反应,使得孔隙结构和性能发生较大的变化而影响处置库的封闭性。本文分析了膨润土和高碱性孔隙水的反应过程以及两者之间反应的主要影响因素,总结出高碱性环境中膨润土的反应变化特征。     

Poorly humified peat as an adsorbent for metals in wastewater

Metal adsorption and surface charge determinations were performed previously on well-characterised Sphagnum and Carex peat samples. The aim of this investigation was to determine metal adsorption from complex wastewaters onto these peat samples and compare it to the adsorption onto peat granules, clinoptilolite, glauconite and a flue dust from steel production. A sulphide mine leachate, a landfill leachate and a laundry wastewater were chosen, giving a variation in pH, ionic strength, total organic carbon and concentrations of metals. Metal adsorption was determined in batch and column experiments. The wastewater composition was of great importance for metal removal efficiency, mainly due to the difference in dominating metal species. In the sulphide mine leachate, containing free metal ions, a high metal adsorption was observed onto both peat and inorganic adsorbents. In the landfill leachate the metals formed carbonate and organic complexes and a low metal removal was achieved. Contrary to the leachates, the laundry wastewater contained suspended particles. The high amount of metals removed, 80% of the Cu and 30-60% of the Zn concentration, was probably withdrawn bound to the particle fraction. The highest removal of metal ions was obtained in the sulphide mine leachate with Carex peat, removing 97-99% of the Zn and 85-100% of the Cu content. The Sphagnum peat sample removed 37-77% of the Zn and 80-100% of the Cu content. The differences found between Sphagnum and Carex peat were attributed to the original chemistry of the plant material and the habitat conditions at the time of peat formation. Generally, the combination of glauconite or clinoptilolite with the peat samples in column experiments gave a minor improvement in metal removal.     

The nature of activated sludge flocs

Previous work has suggested that the settling properties of sludge depend on the chemical and physical nature of the floc surface and that in at least one case the sludge volume index was directly related to the surface charge carried by the sludge particles. This relationship has now been confirmed for sludges from three other works. These sludges all had surface “slime-layers” which contained a polysaccharide composed of neutral sugars and glucuronic acid. In addition to this however, a lysozyme sensitive material was found which also contributed to the overall charge on the particles. This latter material was thought to originate from dead bacteria. Polyvalent cations were also found to be involved in the floc structure and also had an influence on the surface charge. The adsorption of cations by bacteria and biopolymers showed that there were two different types of adsorption behaviour for the activated sludge surface polymer depending on whether it was in the solid state or in solution. It was therefore suggested that different adsorption sites were available to the cations, carboxyl groups being proposed for soluble polymers and hydroxyl groups for the solid. The significance of this adsorption data to the removal of heavy metal ions by the activated sludge process is also discussed.     

重金属Pb(II)在膨润土上去除特性研究

深入研究成本低廉的膨润土对水溶液中Pb(II)的吸附特性,采用Batch试验方法,分析了土水比、pH、离子强度、反应时间、温度及Pb(II)的初始浓度对Pb(II)在膨润土上吸附性能的影响,并对吸附动力学和吸附平衡试验进行了探讨。Pb(II)在膨润土上去除率与pH、离子强度有很强的依赖性。当pH<7时,膨润土对Pb(II)的吸附主要是离子交换,而当7相似文献   

Adsorption mechanism of selenate and selenite on the binary oxide systems

Removal of selenium oxyanions by the binary oxide systems, Al- or Fe-oxides mixed with X-ray noncrystalline SiO₂, was previously not well understood. This study evaluates the adsorption capacity and kinetics of selenium oxyanions by different metal hydroxides onto SiO₂, and uses X-ray absorption spectroscopy (XAS) to assess the interaction between selenium oxyanions and the sorbents at pH 5.0. The binary oxide systems of Al(III)- or Fe(III)-oxides mixed with SiO₂ were prepared, and were characterized for their surface area, point of zero charge (PZC), pH envelopes, X-ray diffraction analysis (XRD), and then macro-scale adsorption isotherm and kinetics of selenite and selenate, micro-scale adsorption XAS. The adsorption capacity of selenite and selenate on Al(III)/SiO₂ is greater than on Fe(III)/SiO₂. Adsorption isothermal and kinetic data of selenium can be well fitted to the Langmuir isotherm and pseudo-second-order kinetic models. Based on simple geometrical constraints, selenite on both the binary oxide systems forms bidentate inner-sphere surface complexes, and selenate on Fe(III)/SiO₂ forms stronger complexes than on Al(III)/SiO₂.     

Adsorption characteristics of some Cu(II) complexes on aluminosilicates

The adsorption of Cu(II) by aluminosilicates with varying Si/Al ratios was investigated. The presence of complex-forming organic ligands [nitrilotriacetate (NTA) and glycine (Gly)] alters metal electrovalency and, in so doing, modifies Cu(II) adsorption characteristics which can influence its fate, biological activity and transport in aquatic systems. Electrostatic attraction by a positively-charged aluminosilicate surface is an important mechanism whereby anion CuNTA⁻ complexes were adsorbed. Two distinct mechanisms are involved in the adsorption of cationic complexes: (1) an exchange reaction at permanent structural sites and (2) interfacial accumulation in response to the pH-dependent surface charge. The contribution of each mechanism to the total amount of CuGly⁺ adsorbed is related to the Si/A1 ratio. At the critical Si/A1 ratio (Si/A1_iso), the aluminosilicates have zero net pH-dependent surface charge. In the absence of specific adsorption, aluminosilicates for which Si/A1 ≥ Si/A1_iso can only function as cation exchangers. For Si/A1 < Si/A1_iso simultaneous adsorption of anions and cations is possible.     

盐渍土环境中输电线路基础外防护技术对比试验研究

分析对比了密封型和渗透型两种表面防护材料在不同环境中的性能,通过吸水率、结晶膨胀性能、抗碳化性能、氯离子电迁移系数、氯离子自然扩散性能和抗冻性能等指标进行评价。结果表明:吸附重腐蚀区宜选用密封型防护材料,对介质传输与化学腐蚀有良好阻隔作用,但不宜使用在冻融循环部分,该部分可以使用渗透结晶型防护材料;吸附普通腐蚀区宜选用硅烷类憎水密封型防护材料,对介质传输与化学腐蚀具有一定阻隔作用,控制每平方米涂覆量保障防护效果;无水位变化的区域宜选用渗透型无机表层强化材料,在较低成本下实现掺合料混凝土碳化的防护和养护的保障。     

pH-dependent effect of zinc on arsenic adsorption to magnetite nanoparticles

The effect of Zn²⁺ on both the kinetic and equilibrium aspects of arsenic adsorption to magnetite nanoparticles was investigated at pH 4.5-8.0. At pH 8.0, adsorption of both arsenate and arsenite to magnetite nanoparticles was significantly enhanced by the presence of small amount of Zn²⁺ in the solution. With less than 3 mg/L of Zn²⁺ added to the arsenic solution prior to the addition of magnetite nanoparticles, the percentage of arsenic removal by magnetite nanoparticles increased from 66% to over 99% for arsenate, and from 80% to 95% for arsenite from an initial concentration of ∼100 μg/L As at pH 8.0. Adsorption rate also increased significantly in the presence of Zn²⁺. The adsorption-enhancement effect of Zn²⁺ was not observed at pH 4.5-6.0, nor with ZnO nanoparticles, nor with surface-coated Zn-magnetite nanoparticles. The enhanced arsenic adsorption in the presence of Zn²⁺ cannot be due to reduced negative charge of the magnetite nanoparticles surface by zinc adsorption. Other cations, such as Ca²⁺ and Ag⁺, failed to enhance arsenic adsorption. Several potential mechanisms that could have caused the enhanced adsorption of arsenic have been tested and ruled out. Formation of a ternary surface complex by zinc, arsenic and magnetite nanoparticles is a possible mechanism controlling the observed zinc effect. Zinc-facilitated adsorption provides further advantage for magnetite nanoparticle-enhanced arsenic removal over conventional treatment approaches.

Synopsis

Arsenic adsorption to magnetite nanoparticles at neutral or slightly basic pH can be significantly enhanced with trace amount of Zn²⁺ due to the formation of a ternary complex.