镉在胡敏酸上的吸附动力学和热力学研究

采用镉离子选择电极研究了镉在胡敏酸上的吸附特征。实验结果表明 ,胡敏酸对镉的等温吸附规律与介质pH有关。当pH为 3 0 0和 3 50时符合Freundlich方程 ,当pH在 4 0 0～ 6 50之间更好地符合Langmuir方程 ;在pH为 3 0 0～ 6 50之间 ,吸附量与pH成显著正相关。温度升高吸附量降低 ,吸附热与反应介质的pH有关 ,pH升高 ,吸附反应放热增加 ;胡敏酸对镉的吸附作用力随介质pH改变发生较大变化 ,当pH为6 50时主要为配位基交换作用。胡敏酸对镉的吸附含有部分不释放氢的静电吸附 ,其吸附反应动力学用Elovich方程拟合效果较好     

白浆土NH_4~+吸附特征的影响因素

为探究白浆土对氮素的吸附规律及其影响因素,有效指导白浆土氮肥的科学施用,本研究采用平衡吸附法,研究了温度、有机质含量、振荡时间和离子强度等因素对白浆土吸附NH4+的影响,结果表明:(1)随初始NH+4浓度(0~1 000 mg/L)的增加,白浆土对其吸附量也增加,当NH+4浓度≥600 mg/L时,吸附渐趋饱和,温度升高(293~313 K)有利于该吸附反应的进行,表观热力学参数(ΔG0、ΔH0、ΔS0)的变化表明,NH+4在白浆土表面的吸附是自发、吸热且混乱度增加的过程。(2)剖面层次所引起的有机质含量递减亦会对白浆土吸附NH+4的数量有所抑制。(3)振荡时间影响白浆土吸附NH+4的动力学过程,该过程可分为起始的快速反应阶段及经过360 min后的慢速反应阶段,所选用的4个动力学方程均能较好拟合这一动态过程。应用过渡态理论所计算的活化热力学参数(ΔG≠0,ΔH≠0,ΔS≠0)表明,NH+4在白浆土上的动力学吸附过程是耗能且体系有序度增高的过程。(4)共存Na+在其不同浓度范围内对白浆土吸附NH+4的影响机制各有不同,当Na+≥0.4 mol/L时,提升其浓度有利于NH+4在白浆土上的吸附。综上所述,在较高土壤养分含量条件下,后移施用氮肥则更有利于其利用率的提升。     

铁、锰、铝氧化物固体吸附剂对胡敏酸和富里酸吸附机理研究

研究了Fe2O3、MnO2或Al2O3固体吸附剂对胡敏酸和富里酸的吸附机制和影响因素。结果表明:相同pH下,Fe2O3、MnO2或Al2O3固体吸附剂对腐殖酸的吸附量随着腐殖酸(胡敏酸HA和富里酸FA)有机碳浓度的增加而增加;不同pH下,对HA的吸附量依照pH3·0>pH5·0>pH7·0的顺序递减。相同pH下,随着HA有机碳浓度的增加,三种固体吸附剂对HA的吸附百分率减小。相同pH下,三种固体吸附剂对FA的吸附百分率呈单峰形,随着酸度的降低,峰位向添加的有机碳低浓度处迁移。吸附量用Langumuir方程拟合能得到极显著相关的方程,在相同pH下,三种固体吸附剂吸附HA的最大吸附量Smax和吸附亲和力常数K小于FA,而标准自由能变ΔGmo却略大于FA;298·2K温度下,三种固体吸附剂吸附胡敏酸和富里酸的ΔGmo<0,表明在等温等压不做非体积功情况下吸附是自发进行的反应。     

磁性壳聚糖微球吸附苹果汁有机酸的动力学及热力学特性

为充分利用中国丰富的苹果资源,开发多品类的苹果深加工产品,以磁性壳聚糖微球为吸附剂,通过磁分离技术,吸附获得苹果汁中的天然有机酸,并对其吸附过程进行研究。利用Lagergren准一级动力学方程、准二级动力学方程、Elovich方程及内扩散方程对吸附反应动力学过程进行拟合;利用Langmuir等温吸附模型、Freundlich等温吸附模型及Temkin等温吸附模型对吸附等温数据进行拟合,并对其吸附反应热力学特性进行分析。通过比较线性拟合方程的决定系数,发现磁性壳聚糖微球吸附苹果汁中有机酸的动力学过程更加符合Lagergren准二级动力学模型,吸附温度越高,吸附速率常数和初始吸附速率越大,但平衡吸附量越低。等温吸附过程更加符合Langmuir等温吸附模型,表明该吸附过程更趋向于单分子层的化学吸附。298 K时,有机酸的饱和吸附量可达到188.679 2 mg/g,表明磁性壳聚糖微球是苹果汁中有机酸的1种高效吸附剂。热力学参数ΔG°0,ΔH°0,ΔS°0,表明磁性壳聚糖微球对苹果汁有机酸的吸附过程为熵增加的可自发进行的放热过程。动力学及热力学结果为磁性壳聚糖微球吸附苹果汁有机酸的研究提供了理论基础与技术支持。     

镉在针铁矿、针铁矿-腐植酸复合胶体中吸附解吸行为比较研究

采用批平衡试验法,比较研究了重金属镉在针铁矿和针铁矿-腐植酸复合胶体中的吸附热力学和动力学行为。结果表明,在试验浓度范围内,两种吸附剂对Cd2＋的等温吸附特征均可用Langmuir、Freundlich和Linear方程加以描述。其中以Langmuir方程的拟合效果最佳,线性相关系数为：0.991、0.999,由此推导出的最大吸附量分别为41.667和45.455mg·g^-1,表明腐植酸与针铁矿复合胶体较单一针铁矿的吸附力有所提高,且所吸附的镉均难以解吸,平均解吸率分别为5.871%和1.068%。胶体对Cd^2＋的吸附是一个快速反应过程,4h达到吸附平衡。Elovich方程是拟合吸附动力学过程的最优方程（相关系数分别为0.987和0.997）。通过计算镉在针铁矿和针铁矿-腐植酸复合胶体中的吸附自由能变化量（ΔG的绝对值均〈40kJ·mol^-1）,推测镉在两种胶体中的吸附为物理吸附过程,其吸附机理可能有氢键、偶极作用力和范德华力等作用,而不存在化学键合作用。     

磁性壳聚糖微球吸附苹果渣多酚的动力学及热力学分析

为了更好的利用胺基化磁性壳聚糖微球吸附分离苹果渣多酚的工艺,对其反应动力学和热力学进行了研究。主要采用Langmuir准一级动力学模型、Langmuir准二级动力学模型、Elovich方程及内扩散方程对吸附反应动力学过程进行拟合,并利用Langmuir等温吸附模型、Freundlich等温吸附模型及Temkin等温吸附模型对吸附反应热力学特性进行解析。结果表明:吸附动力学过程符合准二级动力学模型的描述,吸附温度越高,吸附速率常数和初始吸附速率越大,且平衡吸附量越高。吸附热力学过程符合Freundlich等温吸附模型,热力学参数ΔG<0,ΔH>0,ΔS>0,表明胺基化磁性壳聚糖微球对苹果渣多酚的吸附过程可以自发进行,并且是伴随着焓变>0的吸热过程。动力学及热力学研究为利用胺基化磁性壳聚糖微球进行苹果渣多酚的提取分离提供了技术依据。     

天然土壤对BDE-47的吸附特征

研究了BDE-47在3种不同有机质含量的天然土壤上的吸附行为,包括吸附过程动力学和热力学等温线。结果表明,双室一级动力学模式较单室一级动力学模式更适于描述BDE-47在天然土壤上的吸附过程动力学特征,尤其是在吸附初始阶段（0-49h）。快吸附在自吸附初始到表观吸附平衡的整体吸附过程中占据优势地位,而慢吸附的贡献率则逐渐增加并在97h后达到相对稳定。快吸附达到其吸附容量的时间远快于慢吸附。在吸附开始阶段的3~5h,BDE-47吸附总量的增加主要决定于快吸附,但在后续的吸附阶段,慢吸附的影响逐渐成为主导。因BDE-47水相溶解度很低,在较窄的平衡浓度范围内,线性分配模式和非线性Freundlich模式对BDE-47的吸附等温线都能提供很好的拟合结果。在Freundlich模型结果中,具有较低（0.72%）和较高（7.90%）TOC分数的土样的非线性指数n都明显低于1.0（分别为0.75±0.03和0.74±0.02）,表明2种土样在相应的BDE-47平衡浓度范围内表现出一定的非线性吸附特征;而另一TOC分数居中（2.86%）的土样则表现出显著的线性行为,其非线性指数n明显接近1.0（1.03±0.03）。     

不同来源天然有机质对菲与诺氟沙星光降解的影响研究

为了探究天然有机质结构对有机污染物光降解的影响,选取7种天然有机质,在以氙灯为光源模拟太阳光条件下,研究这7种天然有机质对菲、诺氟沙星光解的影响。菲、诺氟沙星在纯水中光化学降解反应均符合准一级动力学。加入胡敏酸组分的溶液中菲、诺氟沙星降解速度普遍大于加入富里酸组分的溶液中菲、诺氟沙星的降解速度。黑土富里酸、胡敏酸之间结构差异较大,有机肥富里酸、胡敏酸之间结构差异较小。将天然有机质结构特征与菲、诺氟沙星降解系数进行相关性分析得出,胡敏酸类有机质比富里酸类有机质腐殖化程度更高,吸光能力更强,更容易吸收光子跃迁到激发三重态,将能量传递给基态污染物,促进菲、诺氟沙星更快地降解。     

蒙脱石对不同施肥处理土壤胡敏酸及其级分的吸附特征Ⅰ.蒙脱石对胡敏酸的

以１７年不同施肥处理土壤胡敏酸为材料,研究不同性质胡敏酸与钙饱和蒙脱石的吸附特征。结果表明,钙饱和蒙脱石对娄土不同施肥处理胡敏酸的吸附曲线可用单表面Ｌａｎｇｍｕｉｒ方程、双表面Ｌａｎｇｍｕｉｒ方程以及Ｆｒｅｕｎｄｉｃｈ方程来描述。由单表面Ｌａｎｇｍｕｉｒ方程计算的有机肥处理（厩肥、秸秆）胡敏酸的吸附量和吸附强度大于无肥、化肥处理。温度升高各处理胡敏酸吸附量增加,但吸附强度下降。双表面Ｌａｎｇｍｕｉｒ揭示,蒙脱石对胡敏酸的吸附呈现高低两种能位的吸附。高能点位的吸附以化学吸附为主,是吸热反应,低能点位的吸附以物理吸附为主,是放热反应。有机肥处理和无肥、化肥处理相比,高能点位吸附相对减弱,低能点位吸附相对增强。     

几种有机物对紫色土镉的溶出效应与吸附-解吸行为影响的研究

研究了天然有机物胡敏酸和富里酸 ,螯合剂EDTA和DTPA和四种简单有机酸对紫色土镉的溶出效应和吸附解吸行为的影响。结果表明 ,供试八种有机物均能显著促进镉从紫色土中的溶出。作用大小顺序为 :EDTA≥DTPA >柠檬酸 >胡敏酸 >草酸 >富里酸 >酒石酸≥水杨酸。有机物对土壤镉溶出和迁移的影响是其对土壤镉吸附和解吸综合作用的结果。有机物显著降低了紫色土对镉的吸附 ,其作用大小顺序与其对镉的溶出能力的相对大小顺序一致 ,同时也改变了吸附镉的解吸特性。有机物影响下 ,紫色土镉的吸附动力学模型以双常数方程拟合最佳。而吸附等温曲线以Freundlich方程拟合最好 ,吸附常数n与有机物对土壤镉的溶出率之间存在良好的相关性。     

菲和Cu^2＋在黑垆土上的吸附及其交互影响

采用批平衡法,研究了菲和Cu2＋在黑垆土上的吸附及其交互影响。结果表明,菲和Cu2＋在黑垆土上的吸附动力学曲线较好符合一级动力学方程,菲在黑垆土上的吸附主要通过分配作用,其吸附等温曲线符合线性Henry方程,Cu2＋的存在抑制菲在黑垆土上的吸附;而Cu2＋在黑垆土上的吸附主要通过表面吸附和专性吸附作用,其吸附等温曲线符合Freundlich方程,菲的存在促进了Cu2＋的吸附;对菲和Cu2＋来说,pH均是影响黑垆土吸附的主要因素,黑垆土对Cu2＋的吸附量随着土壤溶液pH值的增加而增加,而对菲的吸附量随着pH增加而降低。     

Fluoride Removal from Aqueous Solutions by Boehmite

Boehmite was used for the removal of fluoride ions from aqueous solutions in a batch system. The pH, contact time, and fluoride concentration in the removal of fluoride ions by boehmite were evaluated. The removal of fluoride ions by boehmite was the highest between the pH values of 4.5 and 7.5. The kinetic fluoride sorption from aqueous solutions by boehmite was best described by the pseudo-second-order model, and equilibrium was reached in about 24 h. The Freundlich model described the isotherm sorption process; the results indicate that the sorption mechanism is chemisorption on a heterogeneous material.     

毒死蜱有毒代谢物3,5,6-TCP在土壤中的吸附-解吸研究

应用OECD106批平衡方法,研究了毒死蜱的有毒代谢物3,5,6-TCP在6种典型土壤中的吸附-解吸行为。结果表明：Elovich方程、双常数方程和抛物线扩散方程能较好地拟合3,5,6-TCP在第四纪红土、黑土、黄壤和褐土中的吸附动力学过程,而对紫色土和潮沙土的拟合度较低（拟合相关系数小于0.85）;应用Freundlich方程和线性方程拟合第四纪红土、黑土、黄壤和褐土的经验常数nfads均小于1（非线性吸附）,而紫色土和潮沙土的nfads值则接近于1（线性吸附）;3,5,6-TCP在6种土壤中解吸的滞后系数H值均大于1,即解吸速率大于吸附速率。6种土壤对3,5,6-TCP的吸附常数Kfads从1.37-6.74μg1-n·fmLn·fg^-1,吸附系数Kd值从0.50-1.30mL·g^-1,其中第四纪红土和黑土对其吸持力较强（Kd〉1）,因而更应注意环境安全;其他4种土壤的Kd值则均小于1,淋溶风险较大。     

活性污泥胞外聚合物（EPS）对Pb~（2＋）吸附性能的研究

以活性污泥中提取的胞外聚合物（EPS）作为吸附剂,考察了pH、EPS投加量及温度对Pb2＋吸附效果的影响,通过响应面法对其吸附条件进行优化,并对其热力学吸附特征和吸附动力学进行了探讨。研究结果表明,EPS对Pb2＋的最佳吸附条件组合为：温度35℃,pH4.2,m（EPS）：m（Pb2＋）=2.5：1,在此条件下Pb2＋实际去除率达到89.16%。EPS对Pb2＋的吸附等温线能较好地用Langmuir方程和Freundlich方程来描述,但更适合用Langmuir方程拟合,3种不同温度下（20、30、40℃）最大单分子层吸附量分别为0.9229、1.0129、1.1191mg·mg-1。EPS对Pb2＋的吸附过程可以用准二级动力学方程描述,并在240min达到吸附平衡,平衡时理论最大吸附量为0.45mg·mg-1。     

Equilibrium and Kinetic Characteristic of Adsorption of Cu2+, Pb2+ on a Novel Anionic Starch Microspheres

Neutral starch microspheres (NSMs) were synthesized with epichlorohydrin as the cross-linking agent from soluble starch by inverse microemulsion method. Anionic starch microspheres (ASMs) were prepared from NSMs by the secondary polymerization with chloroacetic acid as the anionic etherifying agent. Scanning electron microscopy (SEM) revealed that microspheres had good sphericity and fine dispersibility, and the average particle size was about 75 ??m. The adsorption procedure of Cu²⁺, Pb²⁺ on ASMs was carried out by batch experiments, Langmuir and Freundlich adsorption models were applied to describe the experimental isotherms, the adsorption equilibrium data were found to fit the Langmuir and Freundlich isotherm model, the Freundlich isotherm was more adequate than the Langmuir isotherm in simulating the adsorption isotherm of Cu²⁺,the adsorption of Cu²⁺, Pb²⁺ on ASMs was a spontaneous, the isosteric heat of adsorption at different adsorption levels was always negative and indicative of an exothermic process. The pseudo first- and second-order kinetic models were used to describe the kinetic data, and the rate constants were evaluated. The experimental data fitted well to the second-order kinetic model, which indicated that the chemical sorption was the rate-limiting step, instead of mass transfer.     

Adsorption Kinetics and Capacity of Fatty Acid-Modified Banana Trunk Fibers for Oil in Water

Oil spill leaves detrimental effects to environment, living organisms, and economy. As such, it is of considerable interest to find an effective, simple, and inexpensive method to treat this calamity. This work reports the use of banana trunk fibers (BTF) modified with oleic acid, stearic acid, castor oil, and palm oil for oil spill recovery. The maximum sorption capacity, effect of oil to water ratio, effect of light oil fractions, and effect of dissolved organic compounds in weathered oil-contaminated seawater were studied. It is found that BTF treated with oleic acid exhibited the best sorption capacity for engine oil, dissolved organic compounds in weathered oil, and light oil fractions. The equilibrium process was described well by the Freundlich isotherm model, and the kinetic studies show good correlation coefficients for a pseudo-second-order kinetic model.     

Sorption of polycyclic aromatic hydrocarbons to mineral surfaces

Minerals contribute crucially to the retention of polycyclic aromatic hydrocarbons (PAHs) in subsurface environments. To investigate the sorption behaviour to mineral surfaces batch sorption experiments were conducted using three PAHs (phenanthrene, pyrene, benzo(a)pyrene) and three mineral sorbents that were representative of subsurface materials (quartz, goethite‐coated quartz, quartz‐montmorillonite mixture). Sorption kinetics showed an instantaneous, considerable PAH sorption to all minerals, except for phenanthrene sorption to quartz at small aqueous‐phase concentrations. Apparent sorption equilibrium was achieved after 4 hours of contact time. The sorption characteristics were fitted to six isotherm models by applying Monte Carlo simulation and nonlinear regression. Best‐fit models were obtained by a model discrimination approach. Phenanthrene and pyrene sorption were best described by the Freundlich isotherm model, with the exception of phenanthrene sorption to quartz (linear isotherm). Good fit results for quartz were also obtained for the combined linear‐Freundlich isotherm. Benzo(a)pyrene sorption to all minerals followed linear high‐affinity isotherms. In the case of phenanthrene and pyrene, the Monte Carlo simulations resulted in mean values with small standard deviations for the isotherm parameters, indicating a negligible influence of the experimental uncertainties on the accuracy of the fitted parameters. For phenanthrene, (i) linear isotherms to quartz and goethite‐coated quartz and (ii) a nonlinear concave‐shaped isotherm to quartz–montmorillonite, assuming a pore‐filling process to micropores formed by clay aggregates, were confirmed. For pyrene, nonlinear convex‐shaped isotherms to the mineral surfaces were assessed. A specific sorption affinity of pyrene to the goethite surface indicated a non‐covalent cation‐π interaction. Small sorption affinities to quartz–montmorillonite support an unfavourable partitioning into the adjacent water.     

Evaluating Binary Sorption of Phenol/Aniline fromAqueous Solutions onto Granular Activated Carbon and Hypercrosslinked Polymeric Resin (MN200)

Sorption equilibrium of phenol and aniline onto the granular activated carbon and hyperreticulated un-functionalized polymeric resin (MN200) was investigated in single and binary component aqueous systems. Higher loading was obtained for aniline than phenol onto both sorbents, which is probably due to hydrophobic difference between both solutes and the greater electronic density of the aromatic ring of the aniline. Granular activated carbon reported larger uptake than resin MN200 for both solutes, which may be attributed to the better physical properties of the granular activated carbon, for instance, larger surface area. The experimental sorption could be properly described by the Langmuir and Freundlich isotherms. Five models for predicting the binary equilibrium sorption isotherm were compared in order to determine the best fit model to correlate binary experimental data: the extended Langmuir isotherm with and without a constant interaction factor, a simplified model based on the single equilibrium factors, the empirical extended Freundlich isotherm and the modified extended Langmuir equation, which considers the synergistic interactions between sorbate–sorbate and not only the competition between them defined by the extended Langmuir model. The modified extended Langmuir model provides the best agreement between predicted and experimental data indicating that the synergistic interactions between solutes play an important role in the binary phenol/aniline sorption system.     

Effects of drinking water treatment residuals on nickel retention in soils: a macroscopic and thermodynamic study

Purpose

Recent research has focused on using water treatment residuals (WTRs) as cost-effective materials to remove potential environmental contaminants. To better understand and predict how WTRs affect the mobility and retention of nickel (Ni) in soils with time, it is crucial that the kinetics and thermodynamics of these reactions be understood. Such information is lacking in the literature and would aid in evaluating the suitability of WTR as a soil amendment for adsorbing Ni contaminant. Accordingly, we focused on investigating the retention of Ni in differing soils and the subsequent influence of WTR application on Ni retention.

Materials and methods

To examine the effects of WTR application on the characteristics of Ni retention, equilibrium, and kinetics, sorption batch experiments were performed on three soils having different properties. The sorption data were applied to the first-order kinetic model, and the Arrhenius equation was used to determine the thermodynamic parameters.

Results and discussion

The quantity of Ni sorbed by the soils followed the trend Typic Torrifluvent > Typic Calciorthids > Typic Torripsamment. Soil sorption isotherms shift toward a higher sorption of Ni indicating addition of more sorption sites as a result of WTRs’ application. Data generated at different temperatures for soils and WTR-amended soils fitted well to Freundlich isotherm and first-order kinetic models. The energy of activation (E _a) and enthalpy (ΔH ^#), entropy (ΔS ^#), and free energy of activation (ΔG ^#) related to Ni sorption were calculated using the Arrhenius equation. The activation energy (E _a) values (51.65–130.0 kJ mol^?1) and the positive ΔH ^# values characterize Ni sorption process onto the sorbents studied as chemisorption with an endothermic nature. The large negative ΔS ^# values (?262 to ?290 J?mol^?1) and the large positive ΔG ^# values (88.11–89.14 kJ mol^?1) indicate the involvement of an associative mechanism in the Ni sorption process.

Conclusions

WTR addition has led to an overall increase in Ni sorption by the amended soils. Such increase in Ni sorption provides evidence that WTR has the potential for land application as a Ni sorbent in soil remediation techniques. The sorption capacity of the soils and WTR-amended soils enhanced with an increase in temperature. Therefore, to truly understand the potential fate and mobility of Ni in the natural environment, temperature, in particular, should be considered.