恩诺沙星在含水氧化铝和含水氧化铁上的配位吸附及配位增溶效应

采用批平衡试验方法,研究了恩诺沙星(ENR)在含水氧化铝(HAO)和含水氧化铁(HFO)上的吸附行为.结果表明,恩诺沙星在两类不同含水氧化物上的吸附可以用Langmuir等温方程描述,其中,吸附平衡常数K_L (HFO) > K_L (HAO).当溶液中NaCl的浓度在0.01~0.50 mol·L^-1之间时,恩诺沙星的最大吸附量随着溶液离子强度的增大呈下降趋势,但吸附低浓度的恩诺沙星时,离子强度对吸附量的影响不大,表明此时两类含水氧化物对恩诺沙星的吸附均以配位反应为主.实验还发现,在较强的酸性或碱性环境中,恩诺沙星的吸附量都明显减小,配位吸附主要发生在pH为5~8的范围内,配位点主要发生在C-3羧基的位点上,形成ENR∶M (金属离子) =1∶1型的配合物,同时生成的表面配合物促进了恩诺沙星的溶解.     

酸性溶液中铝-氟反应动力学

研究了酸性溶液中铝氟反应的动力学，结果表明，铝氟之间的反应速率随温度和ｐＨ的升高而增加．低ｐＨ下以Ａｌ３＋＋Ｆ－＝ＡｌＦ２＋反应为主，较高ｐＨ下由于ＡｌＯＨ２＋参与反应及ＯＨ－的催化作用，反应速率加快．在铝的浓度比氟过量１０倍的情况下，铝氟之间的反应可以用一级反应动力学方程来拟合，即为假一级反应．当ｐＨ＜３８时，柠檬酸和草酸的存在使反应速度加快，而当ｐＨ＞３８时，有机酸使铝氟反应速度变慢．有机酸在不同的ｐＨ下存在不同的作用机制．     

初始pH值对连续投加铝盐混凝去除小分子有机物的影响机制

以污水厂二级出水中小分子有机物强化混凝去除为目的,提出了连续投加混凝工艺(CDC),并以水杨酸为模型小分子有机物,研究了初始pH值对CDC工艺去除效果的影响以及铝离子与水杨酸的络合特性.结果表明,初始pH值6时CDC工艺的去除率最高,比常规混凝工艺提升了13.8%.但是初始pH值5和7时CDC工艺的提升效果较小.三维荧光结果表明,不同pH值下水杨酸和铝离子的络合特性不同.X射线光电子能谱和电喷雾质谱结果表明,pH值5时CDC工艺前期主要生成1:1络合物Al(OH)(C₇H₄O₃)(H₂O)₂.其络合作用强烈,稳定性较高,难以从水中去除.pH值6时前期主要生成中等聚合铝(如原位Al₁₃),其与水杨酸形成的络合物可以参与到铝离子的生长过程,最终生成表面崎岖形态松散的珊瑚礁状絮体,强化了水杨酸的去除.pH值7时,主要生成不定形氢氧化铝,通过絮体表面吸附小分子有机物.     

Adsorption behavior of condensed phosphate on aluminum hydroxide

Sodium pyrophosphate （pyro-P, Na4P2OT）, sodium tripolyphosphate （tripoly-P, Na3P3O10）, and sodium hexametaphosphate （meta-P, （NaPO3）6） were selected as the model compounds of condensed phosphate to investigate the adsorption behavior of condensed phosphate on aluminum hydroxide. The adsorption was found to be endothermic and divisible into two stages： （1） fast adsorption within 1 h; and （2） slow adsorption between 1 and 24 h. The modified Freundlich model simulated the fast adsorption stage well; the slow adsorption stage was described well by the first-order kinetics. The activation energies of pyro-P, tripoly-P, and meta-P adsorption on aluminum hydroxide were determined to be 20.2, 22.8 and 10.9 kJ/mol P adsorbed, respectively, in the fast adsorption stage and to be 66.3, 53.5 and 72.5 kJ/mol P adsorbed, respectively, in the slow adsorption stage. The adsorption increased the negative charge of the aluminum hydroxide surface. Transmission electron microscopy and energy dispersive X-ray analysis analyses provided evidence that the adsorption was not uniform on the surface and that the small crystals contributed more to the fast adsorption than the normal sites did. The results from X-ray fluorescence spectrometry and X-ray photoelectron spectroscopy tests also revealed the uneven adsorption of condensed phosphate as a function of the penetration depth. More condensed phosphates were adsorbed on the outer surface of aluminum hydroxide than in its inner parts.     

天然水体中铝浓度的预测方法探讨

本文概括了天然水体中铝的形态分类和地球化学行为,综述了天然水体中Ａｌ＾３＋和有机铝的浓度的预测方法,提出了由矿物浓度积,无机铝和有机铝经验关系式,有机铝模型辅以配体浓度和热力学常数预测天然水体中各形态铝的浓度的方法。     

富里酸和胡敏酸在蒙脱石上的吸附特性

为进一步揭示有机污染物在黏土矿物上的迁移转化规律,运用1H核磁共振光谱、高效体积排阻色谱、扫描电镜、比表面分析以及傅里叶变换红外光谱等多种分析技术综合分析了富里酸和胡敏酸在蒙脱石上的吸附行为. 结果表明,由于不同官能团与蒙脱石的亲和性不同,富里酸和胡敏酸在吸附过程中均产生组分分级,大分子被优先吸附在蒙脱石表面. 由于疏水性作用,蒙脱石对疏水性更强的胡敏酸的吸附量更大. 蒙脱石吸附富里酸后比表面积和孔容分别下降3.67m2/g和0.005cm3/g,而吸附胡敏酸后则均略微增大,说明具有较大颗粒尺寸的胡敏酸更多地堆积在蒙脱石外表面,而富里酸则更易进入蒙脱石孔隙. 蒙脱石吸附富里酸和胡敏酸后溶液pH分别升高了0.44和0.41,说明发生了配体交换反应. 蒙脱石对富里酸和胡敏酸的吸附量随pH增大和离子强度的降低而减少,表明羟基能够抑制富里酸/胡敏酸负电基团与蒙脱石表面羟基的配体交换反应,而盐离子则能降低蒙脱石和腐殖质间的静电斥力.      

pH和有机酸对氟溶出砖红壤中铝离子的影响

研究砖红壤对F-的吸附反应尤其是随后Al3+的释放过程,有助于增进对土壤酸化过程及其环境影响的理解. 在初步揭示出F-吸附反应以及Al3+释放反应的动力学特征基础上,重点考察了pH和有机酸对上述反应的影响. 结果表明:土壤对F-的吸附反应十分迅速,2 min内吸附量即可达到24 h内总吸附量95%,而土壤中不同含铝矿物的溶解度差异使Al3+的释放过程在前15 min十分迅速,释放量可达24 h内总释放量的80%,随后则逐渐减缓. 降低反应体系pH可促进Al3+释放,但会使F-吸附量减少,这是因为伴随Al3+的释放,部分F-又可以AlF络合物的形态重新进入溶液,尽管在低pH条件下,土壤表面以带正电荷为主而有利于F-吸附. 草酸和抗坏血酸对土壤吸附F-均有抑制作用,但对F-溶出土壤Al3+有促进作用. 此外,草酸对土壤铁氧化物的选择性溶解作用,可使更多F-吸附在土壤铝氧化物位点,并导致Al3+释放量增加.      

水化学条件对海泡石吸附重金属镍(Ni2+)离子的影响及其机制研究

本论文用静态实验法研究了重金属镍(Ni2+)离子在海泡石上的吸附行为和机理,考察了平衡时间、pH值、离子强度、腐殖酸、背景电解质阴、阳离子等水化学条件对吸附作用的影响.结果发现:Ni(Ⅱ)在海泡石上的吸附在很短的时间里就可以达到平衡.Ni(Ⅱ)在海泡石上的吸附受体系pH值和离子强度影响很大,在酸性条件下,主要吸附机理是外层络合和离子交换,而在碱性条件下,主要的吸附机理是内层络合.背景电解质阴、阳离子对Ni(Ⅱ)在海泡石上的吸附有一定的促进或抑制作用.在低pH值下,腐殖酸在海泡石上吸附后形成了新的表面络合物而增强Ni(Ⅱ)的吸附,而在高pH值的条件下,腐殖酸存在于吸附体系时,Ni(Ⅱ)的吸附量明显小于Ni(Ⅱ)/海泡石吸附体系.本为的研究结果为环境中重金属离子和放射性核素的危害评估和有效治理提供了很好的参考.     

有机物对重金属在粘土中吸附行为的影响

实验选用填埋场垃圾降解过程中“产酸阶段”和“产甲烷阶段”产生的己酸和腐殖酸及重金属 Cd、Pb、Ni、Zn和 Mn为研究对象 ,研究有机物存在对粘土吸附重金属的影响 .结果表明 :粘土对纯重金属的吸附随着溶液 p H值升高而增强 ;对己酸的吸附随着溶液 p H值升高而增强 ,对腐殖酸的吸附随着溶液 p H值升高而减弱 .当溶液中己酸和重金属共存时 ,由于竞争吸附使得粘土对重金属的吸附能力普遍有较小幅度的下降 ;当溶液中存在腐殖酸和重金属共存时 ,粘土对重金属的吸附能力增强 ,主要是由于酸性条件下富里酸发生解离后与重金属络合 ,其络合物与粘土颗粒有一定的结合能力 ,增强了粘土对重金属的吸附能力 .     

低分子量有机酸影响可变电荷土壤吸附铜的机制

采用平衡实验法研究了水杨酸和邻苯二甲酸对砖红壤吸附铜的影响,并通过吸附铜的解吸实验探讨了有机酸对铜吸附的影响机制.结果表明,有机酸可以增加土壤对铜的吸附量,与对照相比,有机酸体系中吸附的铜的解吸量高.有机酸对铜吸附的影响随体系pH值的增加而增大,约在pH4.3(水杨酸体系)或pH4.5(邻苯二甲酸体系)达最大,然后逐渐减小.土壤对有机酸的吸附量越高,有机酸对铜吸附的影响程度越大.有机酸可以通过形成表面三元络合物和改变土壤的表面电荷2种机制影响土壤对铜的吸附.水杨酸体系中铜的解吸增量与吸附增量的百分比在76%～89%之间,说明水杨酸主要是通过增加土壤表面的净负电荷量来增加铜的静电吸附量.     

乐安江沉积物对重金属的吸附模式研究──表面络合模式在天然沉积物研究中的应用

应用表面络合理论及其研究方法对乐安江沉积物的表面特征及对重金属的吸附特性进行了研究．进行了乐安江沉积物样品的表面电位滴定实验及样品对重金属Ｃｕ、Ｃｄ的吸附实验．应用图解法及ＦＩＴＥＱＬ优化程序确定了表面络合模式中的相应参数，并对模式的预测能力进行了检验．研究了３种表面络合模式即恒定容量模式，扩散层模式和三层模式的拟合应用情况．结果表明，３种表面络合模式均能较好地描述天然沉积物的吸附过程，但哪种模式从化学原理上看更正确尚不能证明．从模式计算的难易程度分析，扩散层模式有一定优势．模式应用中应特别强调的是模式参数间的相关性和一致性．     

Heavy metal adsorption on the Le An River sediment —The adsorption model

In this study,the surface properties and adsorption properties of the Le An River sediment were modelled via surface complexation approach.The model parameters were determined based on the data of our potentiometric titration experiments and the metal adsorption experiments with the Le An River sediment samples.Consequently,the surface complexation models for the natural sediment,in our case the Le An River sediments,which can interpret the experimental data very well were successfully established.Three typical surface complexation models that is the constant capacitance model,the diffuse layer model and the triple layer model,were considered in this research.This work indicated that the consistency and the interdependency among model parameters together with the selection of the surface adsorbed species should be emphasized.     

砂岩储层中有机酸对主要矿物的溶蚀作用及机理研究综述

砂岩储层中有机酸对矿物的溶解和沉淀在很大程度上影响着次生孔隙的发育。研究发现,有机酸之所以能提高石英的溶蚀速率和长石的溶解度,主要是由于在矿物的表面及溶液中形成络合物,有效地降低了矿物表面反应的活化能及溶液中硅、铝离子浓度的结果。有机酸与粘土矿物的吸附或催化反应可抑制长石等其他矿物的溶解。有机酸与CO2一起共同控制着体系中碳酸盐的溶解或沉淀。     

氧化剂与新型絮凝剂协同去除酸性大红的研究

选取浓度为25mg/L的酸性大红-GR溶液为模拟染料废水,采用氧化-絮凝耦合工艺,探索了氧化剂种类、絮凝剂种类、废水pH值、氧化剂和絮凝剂投加量对氧化-絮凝耦合处理酸性大红染料的影响,确定最佳处理条件为:酸性大红溶液初始pH值不变,高锰酸钾和PTSS的投加量分别为为20mg/L和10mg/L(以钛离子计),脱色率和COD去除率均最大,分别为96.3%、56.5%。通过FTIR光谱扫描、絮体的显微形貌观察、酸性大红和新型絮凝剂聚硅硫酸钛(PTSS)的表面电动电位随pH值的变化的测定,分析了氧化-絮凝耦合法的反应历程:高锰酸钾破坏酸性大红的发色基团后,自身被还原成新生态二氧化锰胶体;二氧化锰胶体吸附酸性大红及其氧化产物,并被无机高分子絮凝剂PTSS通过电中和及架桥网捕等作用卷裹成絮体。     

土壤与酸性含氟溶液相互作用特征及机理研究

通过反复多次提取实验方法模拟了酸性含氟溶液与红壤和赤红壤相互作用过程。结果表明：在相互作用过程中，土壤中氟含量不同对土壤溶液pH有明显不同的影响。当氟含量较低时氟离子对土壤溶液pH的影响不明显；当浓度较高时则可大大提高土壤溶液的pH，缓冲土壤酸化。在第一次提取中因氟的大量吸附可减少溶液中铝的浓度，且氟含量越高铝浓度越少量越大。随提取次数增加土壤溶液中铝、氟浓度同时增加，且氟含量越高铝浓度越大，其中氟以AI－F络合物为主。     

Two-dimensional correlation spectroscopic analysis on the interaction between humic acids and aluminum coagulant

In this study, two-dimensional correlation spectroscopy integrated with synchronous fluorescence and infrared absorption spectroscopy was employed to investigate the interaction between humic acids and aluminum coagulant at slightly acidic and neutral p H. Higher fluorescence quenching was produced for fulvic-like and humic-like fractions at p H 5. At p H 5, the humic-like fractions originating from the carboxylic acid, carboxyl and polysaccharide compounds were bound to aluminum first, followed by the fulvic-like fractions originating from the carboxyl and polysaccharide compounds. This finding also demonstrated that the activated functional groups of HA were involved in forming the Al-HA complex, which was accompanied by the removal of other groups by co-precipitation.Meanwhile, at p H 7, almost no fluorescence quenching occurred, and surface complexation was observed to occur, in which the activated functional groups were absorbed on the amorphous Al(OH)3. Two-dimensional FT-IR correlation spectroscopy indicated the sequence of HA structural change during coagulation with aluminum, with IR bands affected in the order of COOH COO-NH deformation of amide Ⅱ aliphatic hydroxyl C\OH at p H 5, and COO-aliphatic hydroxyl C\OH at p H 7. This study provides a promising pathway for analysis and insight into the priority of functional groups in the interaction between organic matters and metal coagulants.     

沉积物中氧化物结合态镉对芦苇的生物有效性研究：氧化物种类、结合形式、老化的影响

沉积物中重金属的生物有效性在很大程度上取决于其赋存形态.选用沉积物中2种典型氢氧化物矿物:氢氧化铁和氢氧化铝,以水培法和矿物结合态Cd为培养介质,以芦苇为受试植物,研究环境中吸附和共沉淀态Cd生物有效性差别,并探究老化过程对生物有效性的影响.经过13 d的培养,发现2种结合形式的Cd均可被芦苇富集,不同处理体系中富集强度不同,根中富集量为9.1~37.8 mg.kg-1;地上部分富集量为0~10.0 mg.kg-1.其中,结合在Fe0.5Al0.5(OH)3矿物上的Cd的生物有效性最大,其次是Fe(OH)3和老化的Fe0.5Al0.5(OH)3,富集量最少的是老化的Fe(OH)3的处理.采用2种低分子量有机酸对Cd进行解吸实验,Cd的解吸规律与芦苇对Cd的富集规律一致.因此,共沉淀处理降低了Cd的富集,矿物的理化性质决定了含铝矿物对Cd的结合较差,老化作用抑制了吸附态Cd的富集,有机酸解吸实验也验证了不同形态Cd生物有效性的差异.     

The role of organic and inorganic substituents of roxarsone determines its binding behavior and mechanisms onto nano-ferrihydrite colloidal particles

The retention and fate of Roxarsone (ROX) onto typical reactive soil minerals were crucial for evaluating its potential environmental risk. However, the behavior and molecular-level reaction mechanism of ROX and its substituents with iron (hydr)oxides remains unclear. Herein, the binding behavior of ROX on ferrihydrite (Fh) was investigated through batch experiments and in-situ ATR-FTIR techniques. Our results demonstrated that Fh is an effective geo-sorbent for the retention of ROX. The pseudo-second-order kinetic and the Langmuir model successfully described the sorption process. The driving force for the binding of ROX on Fh was ascribed to the chemical adsorption, and the rate-limiting step is simultaneously dominated by intraparticle and film diffusion. Isotherms results revealed that the sorption of ROX onto Fh appeared in uniformly distributed monolayer adsorption sites. The two-dimensional correlation spectroscopy and XPS results implied that the nitro, hydroxyl, and arsenate moiety of ROX molecules have participated in binding ROX onto Fh, signifying that the predominated mechanisms were attributed to the hydrogen bonding and surface complexation. Our results can help to better understand the ROX-mineral interactions at the molecular level and lay the foundation for exploring the degradation, transformation, and remediation technologies of ROX and structural analog pollutants in the environment.     

Preparation and characterization of organic polymer modified composite polyaluminum chloride

Compared with traditional aluminum salts, polyaluminum chloride （PACI） has better coagulation-flocculation performance in turbidity removal. However, it is still inferior to organic polymers in terms of bridging function. In order to improve the aggregating property of PACl, different composite PACl flocculants were prepared with various organic polymers. The effect of organic polymer on the distribution or Al（Ⅲ） species in composite flocculants was studied using ^27TAl NMR and Al-ferron complexation methods. The charge neutralization and surface adsorption characteristics of composite flocculants were also investigated. Jar tests were conducted to evaluate the turbidity removal efficacy of organic polymer modified composite flocculants. The study shows that cationic polymer and anionic polymer have significant influences on the coagulation-flocculation behaviors of PACl. Both cationic and anionic polymers can improve the turbidity removal performancc of PACl but the mechanisms arc much different： cationic organic polymer mainly increases the charge neutralization ability, but anionic polymer mainly enhances the bridging function.     

Removal of arsenate with hydrous ferric oxide coprecipitation：Effect of humic acid

Insights from the adverse effect of humic acid(HA) on arsenate removal with hydrous ferric oxide(HFO) coprecipitation can further our understanding of the fate of As(V) in water treatment process. The motivation of our study is to explore the competitive adsorption mechanisms of humic acid and As(V) on HFO on the molecular scale. Multiple complementary techniques were used including macroscopic adsorption experiments, surface enhanced Raman scattering(SERS), extended X-ray absorption fine structure(EXAFS) spectroscopy, flow-cell attenuated total reflectance Fourier transform infrared(ATR-FTIR) measurement, and charge distribution multisite complexation(CDMUSIC) modeling. The As(V) removal efficiency was reduced from over 95% to about 10% with the increasing HA concentration to 25 times of As(V) mass concentration. The SERS analysis excluded the HA-As(V) complex formation. The EXAFS results indicate that As(V) formed bidentate binuclear surface complexes in the presence of HA as evidenced by an As-Fe distance of 3.26–3.31 ?. The in situ ATR-FTIR measurements show that As(V) replaces surface hydroxyl groups and forms innersphere complex. High concentrations of HA may physically block the surface sites and inhibit the As(V) access. The adsorption of As(V) and HA decreased the point of zero charge of HFO from 7.8 to 5.8 and 6.3, respectively. The CD-MUSIC model described the zeta potential curves and adsorption edges of As(V) and HA reasonably well.