Sorption of cadmium(II) and copper(II) by soil humic acids: temperature effects and sorption heterogeneity

Sorption by humic acids is known to modify the bioavailability and toxicity of metals in soils and aquatic systems. The sorption of cadmium(II) and copper(II) to two soil humic acids was measured at pH 6.0 using ion-selective electrode potentiometric titration at different temperatures. Sorption reactions were studied with all components in aqueous solution, or with the humates in suspension. Adsorption reactions were described using a multiple site-binding model, and a model assuming a continuous log-normal distribution of adsorption constants. Adsorption of Cu²⁺ was more favourable than adsorption of Cd²⁺. The log-normal distribution model provided the closest fit to observations and allowed parameterisation of adsorption data using a mean adsorption constant (log K _μ). Sorption of Cd²⁺ to dissolved humic acids increased slightly in extent and sorption affinity with increasing temperature, but the effect was small (log K _μ 2.96–3.15). A slightly greater temperature effect occurred for sorption of Cd²⁺ to solid-phase humic acids (log K _μ 1.30–2.08). Sorption of copper(II) to both aqueous- and colloidal-phase humates showed more pronounced temperature dependence, with extent of sorption, and sorption affinity, increasing with increasing temperature (log K _μ 3.4–4.9 in solution and 1.4–4.5 in suspension). The weaker adsorption of Cd²⁺ than Cu²⁺, and smaller temperature effects for dissolved humates than suspended humates, suggested that the observed temperature effects had a kinetic, rather than thermodynamic, origin. For any metal-to-ligand ratio, free metal ion concentration, and by inference metal bioavailability, decreased with increasing temperature. The consistency of the data with kinetic rather than thermodynamic control of metal bioavailability suggests that equilibrium modelling approaches to estimating bioavailability may be insufficient.     

Adsorptive removal of a synthetic textile dye using cocoa pod husks

The adsorption of a synthetic textile dye (Remazol Brilliant Black Reactive) on cocoa pod husk-based activated carbon was investigated in batch process. The adsorbent prepared was characterized by gas adsorption surface analysis (Brunauer Emmett Teller, BET), scanning electron microscopy, and Fourier transform infrared spectroscopy. The effects of initial dye concentration, contact time, solution temperature, and solution pH were evaluated. Equilibrium data were fitted to Langmuir, Freundlich, Temkin, and Dubinin–Radushkevich isotherm models, the first being the best with maximum monolayer coverage of 111?mg?g^?1. Kinetic data were fitted into pseudo-first-order, pseudo-second-order, intraparticle diffusion, and Elovich models; the pseudo second-order model provided the best correlation. Maximum adsorption was observed at pH 7. Standard free energy, standard enthalpy, and standard entropy were also calculated. The adsorption interaction was found to be endothermic and spontaneous. Both the mean free energy of adsorption and the activation energy show that the mechanism is by physisorption.     

Preparation and characterization of calcium alginate-based composite adsorbents for the removal of Cd,Hg, and Pb ions from aqueous solution

Composite adsorbent materials containing calcium alginate, clinoptilolite, and coal-derived humic acid were prepared. Humic acid (HA), clinoptilolite (CL), alginate (AL), alginate-entrapped humic acid (AL/HA), clinoptilolite (AL/CL), and humic acid/clinoptilolite (AL/HA/CL) samples were characterized. The effectiveness of the samples as adsorbents for the removal of cadmium (Cd), mercury (Hg), and lead (Pb) were studied in a series of batch-adsorption experiments. For the AL, AL/HA, AL/CL, and AL/HA/CL adsorbents, uptake versus time data were evaluated using two kinetic models, a linear and a non-linear pseudo-first-order and a pseudo-second-order model. The data for each metal ion on all adsorbents showed good correspondence with the pseudo-second-order kinetic model. The equilibrium data were fitted to Langmuir, Freundlich, Dubinin–Radushkevich, and Temkin isotherm models. The results show that a non-linear method seems more appropriate for obtaining isotherm parameters. The non-linear Freundlich and Langmuir models for Pb and Hg produced a best fit with high R ² value (0.99). For HA adsorbent, the equilibrium data for Cd removal better fit to the non-linear Dubinin–Radushkevich isotherm.     

Preconcentration of samarium with modified yeast cells for its determination by atomic emission spectroscopy

A chelating-modified biosorbent is produced by coupling of a dye, procion red, to yeast cells. The resulting modified cells have been characterized by Fourier transform infrared, elemental analysis and thermogravimetric analysis and studied for preconcentration and determination of trace Sm(III). The optimum pH value for sorption of the samarium ions is 6.2. The sorption capacity of functionalized modified yeast cells is 7.2 mg g^?1. Recovery was 99% when Sm(III) was eluted with an aqueous solution of 0.1 mol L^?1 ethylenediaminetetraacetic acid. Scatchard analysis suggested that binding sites were homogeneous. The equilibrium data were analyzed using Langmuir, Freundlich, Temkin, and Redlich–Peterson isotherm models, and the respective constants were determined as 1.0 (L mg^?1), 2.9 [(mg g^?1) (L mg^?1)^1/n], 2.4 × 10⁸ (L g^?1), and 30 (dm³ g^?1) at 20 °C. The method was applied for an Sm(III)-containing sample of ceramic industry effluent.     

Adsorption of methylene blue onto activated carbon derived from periwinkle shells: kinetics and equilibrium studies

Periwinkle shell, an abundant and inexpensive natural resource, was used to prepare activated carbon by physicochemical activation with potassium hydroxide (KOH) and carbon dioxide (CO₂) as the activating agents at 850 °C for 2 h. The adsorption equilibrium and kinetics of methylene blue dye on such carbon were then examined at 25 °C. Adsorption isotherm of the methylene blue (MB) on the activated carbon was determined and correlated with common isotherm equations. The equilibrium data for methylene blue adsorption well fitted to the Langmuir equation, with maximum monolayer adsorption capacity of 500.00 mg/g. Two simplified kinetic models including pseudo-first-order and pseudo-second-order equation were selected to follow the adsorption processes. The adsorption of methylene blue on activated carbon derived from periwinkle shell could best be described by the pseudo-second-order equation. The kinetic parameters of this best-fit model were calculated and discussed.     

Sorption,cellular distribution,and cytotoxicity of imidazolium ionic liquids in mammalian cells – influence of lipophilicity

In order to assist an integrated development of ionic liquids (ILs), a study on the sorption, distribution, and cytotoxicity of a series of 1-alkyl-3-methyl imidazolium tetrafluoroborates with C6 rat glioma cells has been performed. Cellular sorption and distribution among three cellular fractions (cytosol, nuclei, and membranes) were analysed by reversed-phase HPLC (RP-HPLC). Compounds with longer 1-alkyl substituents were sorbed with higher enrichment factors and sorption coefficients per protein than those with shorter 1-alkyl chains. The 1-octyl-3-methyl imidazolium cation (C₈MIM) was enriched 17-folds whereas C₆MIM and C₄MIM were enriched by factors of 3.5 and 2.3, respectively. After fractionation of cells by centrifugation, about 8% of C₈MIM was found in the nuclear fractions. The cytotoxicity as estimated by the tetrazolium reductase assay was increasing with the lengths of the 1-alkyl chains from C₄MIM to C₁₀MIM. Consistently, cell proliferation rates were decreasing with increasing lengths of the 1-alkyl chains. The results reveal the correlations between lipophilicity, cellular sorption, and cytotoxicity.     

废啤酒酵母去除水中重金属镉的作用机理

利用废啤酒酵母为生物吸附材料处理水溶液中的Cd2+.为了考察废啤酒酵母表面官能团在生物吸附过程中的作用,分别对废啤酒酵母进行甲醇、甲醛化学修饰,使其表面的羧基发生酯化反应、胺基发生甲基化反应.同时对反应前后溶液pH值的变化进行了监测.结果表明,酯化反应后,废啤酒酵母吸附Cd2+的能力降低,证实羧基在Cd2+吸附中起到了重要作用;甲基化反应后,废啤酒酵母吸附Cd2+的能力升高,是因为反应后pH值变化使Cd2+发生无机微沉淀作用而去除.表面官能团以及pH升高引起的沉淀对镉去除起重要作用.     

菲和萘在黄土上的吸附等温线和吸附热力学

研究了菲和萘在黄土上的吸附行为,比较分析了Linear方程、Freundlich方程和Langmuir方程描述吸附等温线的准确性.结果表明,菲和萘在黄土上的吸附等温线呈非线性,Freundlich方程最符合其吸附行为.菲和萘在天然黄土上的吸附量随温度升高而降低.其吸附是一个放热过程,吸附热分别为0.017 74 kJ·mol-1和-0.061 25 kJ·mol-1; 吸附的标准自由能改变量分别为-9.939 kJ·mol-1和-7.333 kJ·mol-1.标准自由能的变小是菲和萘在黄土上吸附的推动力.经过阳离子表面活性剂改性后的黄土对菲和萘的吸附能力,随加入的表面活性剂占原土阳离子交换容量(CEC)的百分数增大明显增强,能更加有效地去除水环境中的多环芳烃类污染物.     

不同粒径沉积物对1,2,4,5-四氯苯的吸附/解吸特性

采用静态吸附实验,研究不同粒径沉积物的基本性质及其对1,2,4,5-四氯苯吸附/解吸性能的影响.结果表明,不同粒径沉积物所含天然有机质(NOM)质和量的不同,导致其对1,2,4,5-四氯苯吸附性能的不同.颗粒最细的沉积物因其主要结合聚合度较低的无定型腐殖物质,导致1,2,4,5-四氯苯吸附等温线的非线性程度最低,在沉积物上的吸附亲和力和吸附.解吸滞后现象也最弱.而颗粒最粗的沉积物因为含有一些煤炭和木炭等高比表面积的碳黑类物质,NOM聚合度较高,导致1,2,4,5-四氯苯吸附等温线的非线性程度最高,在沉积物上的吸附亲和力和吸附-解吸滞后现象也最强.而粒径中等的沉积物本身的性质和吸附性能介于颗粒最粗和最细的两种组分之间.     

阳离子型可逆表面活性剂在膨润土上的吸附行为

研究可逆表面活性剂十一烷基二茂铁三甲基溴化铵(FTMA)在膨润土上的吸附机理,并与CTAB进行对比;同时考察土壤关键因子对FTMA吸附的影响.结果表明,FTMA与CTAB在膨润土上的吸附变化规律一致,饱和吸附量为66cmol/kg,约为膨润土1倍CEC,吸附机制主要为阳离子交换作用.不同温度下FTMA吸附等温线均可用Langmuir模型描述,吸附量随温度升高(298→318K),由280.6mg/g增大至350.8mg/g.吸附在8h达到平衡,吸附速率较CTAB慢,并符合准二级动力学方程,化学吸附是主要控制速率步骤.热力学参数计算得出,该吸附是自发吸热过程.随体系离子强度的增大,吸附量下降;共存阳离子对吸附有抑制作用,且影响程度大小为: Ca2+>K+>Na+; pH值对吸附影响较小;腐植酸(HA)的加入促进了FTMA的吸附.