Kinetic and isotherm error optimization studies for adsorption of atrazine and imidacloprid on bark of Eucalyptus tereticornis L.

The aim of this study was to establish the bark of Eucalyptus tereticornis L. (EB) as a low cost bio-adsorbent for the removal of imidacloprid and atrazine from aqueous medium. The pseudo-first-order (PFO), pseudo-second-order (PSO), Elovich and intra-particle diffusion (IPD) models were used to describe the kinetic data and rate constants were evaluated. Adsorption data was analysed using ten 2-, 3- and 4-parameter models viz. Freundlich, Jovanovic, Langmuir, Temkin, Koble–Corrigan, Redlich–Peterson, Sips, Toth, Radke–Prausnitz, and Fritz-Schluender isotherms. Six error functions were used to compute the best fit single component isotherm parameters by nonlinear regression analysis. The results showed that the sorption of atrazine was better explained by PSO model, whereas the sorption of imidacloprid followed the PFO kinetic model. Isotherm model optimization analysis suggested that the Freundlich along with Koble–Corrigan, Toth and Fritz-Schluender were the best models to predict atrazine and imidacloprid adsorption onto EB. Error analysis suggested that minimization of chi-square (χ²) error function provided the best determination of optimum parameter sets for all the isotherms.     

Kinetics and isotherm modeling of azoxystrobin and imidacloprid retention in biomixtures

The paper reports the kinetics and adsorption isotherm modeling for imidacloprid (IMIDA) and azoxystrobin (AZOXY) in rice straw (RS)/corn cob (CC) and peat (P)/compost (C) based biomixtures. The pseudo-first-order (PFO), pseudo-second-order (PSO), Elovich and intraparticle diffusion models were used to describe the kinetics. The adsorption data were subjected to the Langmuir and the Freundlich isotherms. Results (r²_Adj values) suggested that the modified Elovich model was the best suited to explain the kinetics of IMIDA sorption while different models explained AZOXY sorption kinetics in different biomixtures (PFO in RS?+?C and RS?+?P; PSO in CC?+?P and Elovich in CC?+?C). Biomixtures varied in their capacity to adsorb both pesticides and the adsorption coefficient (K_d) values were 116.8–369.24 (AZOXY) and 24.2–293.4 (IMIDA). The Freundlich isotherm better explained the sorption of both pesticides. Comparison analysis of linear and nonlinear method for estimating the Freundlich adsorption constants was made. In general, r²_Adj values were higher for the nonlinear fit (AZOXY?=?0.938–0.982; IMIDA?=?0.91–0.970) than the linear fit (AZOXY?=?0.886–0.993; IMIDA?=?0.870–0.974) suggesting that the nonlinear Freundlich equation better explained the sorption. The rice straw-based biomixtures performed better in adsorbing both the pesticides and can be used in bio-purification systems.     

Application of zeolite-activated carbon macrocomposite for the adsorption of Acid Orange 7: isotherm, kinetic and thermodynamic studies

In this study, the adsorption behavior of azo dye Acid Orange 7 (AO7) from aqueous solution onto macrocomposite (MC) was investigated under various experimental conditions. The adsorbent, MC, which consists of a mixture of zeolite and activated carbon, was found to be effective in removing AO7. The MC were characterized by scanning electron microscopy (SEM), energy dispersive X-ray, point of zero charge, and Brunauer–Emmett–Teller surface area analysis. A series of experiments were performed via batch adsorption technique to examine the effect of the process variables, namely, contact time, initial dye concentration, and solution pH. The dye equilibrium adsorption was investigated, and the equilibrium data were fitted to Langmuir, Freundlich, and Tempkin isotherm models. The Langmuir isotherm model fits the equilibrium data better than the Freundlich isotherm model. For the kinetic study, pseudo-first-order, pseudo-second-order, and intraparticle diffusion model were used to fit the experimental data. The adsorption kinetic was found to be well described by the pseudo-second-order model. Thermodynamic analysis indicated that the adsorption process is a spontaneous and endothermic process. The SEM, Fourier transform infrared spectroscopy, ultraviolet–visible spectral and high performance liquid chromatography analysis were carried out before and after the adsorption process. For the phytotoxicity test, treated AO7 was found to be less toxic. Thus, the study indicated that MC has good potential use as an adsorbent for the removal of azo dye from aqueous solution.     

Adsorption of glyphosate on resin supported by hydrated iron oxide: equilibrium and kinetic studies

Hydrated iron oxide supported on resin (D301) was prepared as a new sorbent for the removal of glyphosate from wastewater. Batch adsorption studies were performed on glyphosate aqueous solutions with different initial glyphosate concentrations and temperatures. Experimental data were analyzed using the Langmuir and Freundlich isotherms, and the adsorption data were best fit to the Langmuir isotherm model. The thermodynamic parameters AG, AH, and AS also were calculated for the adsorption processes. Adsorption rate constants were determined using the pseudo-first-order and pseudo-second-order rate equations and Kannan-Sundaram intraparticle diffusion models. Adsorption of glyphosate clearly followed the pseudo-second-order model and was controlled by both film diffusion and intraparticle diffusion.     

粉煤灰砖块对磷酸盐的吸附特性

以建筑废料粉煤灰砖块为吸附剂材料,通过静态吸附实验研究其对磷酸盐的吸附特征,以及磷酸盐初始浓度、吸附剂投加量、pH等因素对吸附反应的影响。Langmuir、Freundlich和Temkin等温模型的分析发现,Langmuir等温式方程最适合描述吸附过程,对磷酸盐的理论饱和吸附容量为44.62 mg/g。利用伪一级动力学模型、伪二级动力学模型和颗粒内扩散模型考察了吸附过程特征,其中伪二级动力学模型为最适于描述粉煤灰砖块对磷酸盐的吸附过程的动力学模型。通过颗粒内扩散模型、Bangham方程及Boyd模型对吸附动力学机理进行的探讨表明,颗粒内扩散速率不是粉煤灰砖块吸附磷酸盐反应的惟一速率控制步,膜扩散速率和颗粒内扩散速率共同影响着吸附反应速率。磷酸盐浓度较低时主要是膜扩散限制吸附反应速率,而磷酸盐浓度较高时则颗粒内扩散成为速率控制步。研究证明,粉煤灰砖块粉末作为湿地基质具有对磷酸盐很强的吸附能力,在减少了固体废弃物的数量的同时又可以实现水污染控制的目的。     

铁基膨润土对水中磷酸根的吸附热力学及动力学研究

采用铁盐改性制得铁基膨润土,研究了其对水中磷酸根的吸附性能及影响因素,结果表明,通过对膨润土的改性提高了磷的去除率,含磷废水初始pH值的大小对磷的去除率影响不大,初始浓度越低越有利于磷的去除。磷的去除率随改性膨润土的投加量增大而提高,随温度升高而增大。进一步研究表明,改性膨润土对磷的吸附是吸热反应,其吸附等温线可采用Langmuir等温吸附方程拟合;改性膨润土对磷的吸附是快速吸附,在20 min内,磷去除率达70%以上,符合准二级吸附动力学模型。     

Adsorption characteristics of 2,4-dichlorophenoxyacetic acid (2,4-D) from aqueous solution on powdered activated carbon

The removal of 2,4-dichlorophenoxyacetic acid (2,4-D), one of the most commonly used phenoxy acid herbicides, from aqueous solution was studied by using acid-washed powdered activated carbon (PAC) as an adsorbent in a batch system. Adsorption equilibrium, kinetics, and thermodynamics were investigated as a function of initial pH, temperature, and initial 2,4-D concentration. Powdered activated carbon exhibited the highest 2,4-D uptake capacity of 333.3 mg g(-1) at 25 degrees C and an initial pH value of 2.0. Freundlich, Langmuir, and Redlich-Peterson isotherm models were used to express the equilibrium data of 2,4-D depending on temperature. Equilibrium data fitted very well to the Freundlich equilibrium model in the studied concentration range of 2,4-D at all the temperatures studied. Three simplified models including pseudo-first-order, pseudo-second-order, and saturation-type kinetic models were used to test the adsorption kinetics. It was shown that the adsorption of 2,4-D on PAC at 25, 35, and 45 degrees C could be best fitted by the saturation-type kinetic model with film and intraparticle diffusions being the essential rate-controlling steps. The activation energy of adsorption (EA) was determined as--1.69 kJ mole(-1). Using the thermodynamic equilibrium coefficients obtained at different temperatures, the thermodynamic constants of adsorption (deltaG degrees, deltaH degrees, and deltaS degrees) were also evaluated.     

纳米有机膨润土对苯酚的吸附性能研究

通过对天然膨润土改性,制备纳米有机膨润土并用于吸附苯酚,探讨了吸附时间、溶液pH、纳米有机膨润土投加量等因素对苯酚吸附的影响。结果表明,吸附在5 min内快速达到平衡,溶液pH可以影响苯酚在溶液中的状态,是影响苯酚吸附性能的重要因素。纳米有机膨润土吸附苯酚的过程可用伪二级反应动力学方程来描述,伪二级吸附速率常数为1.3 g/(mg.min)。吸附等温线符合Langmuir等温方程,在25℃时,Langmuir理论最大吸附容量可达到536.32 mg/g,吸附热力学参数表明吸附过程是自发的、放热的物理吸附过程。     

Preparation and characterization of surfactant-modified hydroxyapatite/zeolite composite and its adsorption behavior toward humic acid and copper(II)

A novel composite material, i.e., surfactant-modified hydroxyapatite/zeolite composite, was used as an adsorbent to remove humic acid (HA) and copper(II) from aqueous solution. Hydroxyapatite/zeolite composite (HZC) and surfactant-modified HZC (SMHZC) were prepared and characterized by X-ray diffraction, Fourier transform infrared spectroscopy, and field emission scanning electron microscope. The adsorption of HA and copper(II) on SMHZC was investigated. For comparison purposes, HA adsorption onto HZC was also investigated. SMHZC exhibited much higher HA adsorption capacity than HZC. The HA adsorption capacity for SMHZC decreased slightly with increasing pH from 3 to 8 but decreased significantly with increasing pH from 8 to 12. The copper(II) adsorption capacity for SMHZC increased with increasing pH from 3 to 6.5. The adsorption kinetic data of HA and copper(II) on SMHZC obeyed a pseudo-second-order kinetic model. The adsorption of HA and copper(II) on SMHZC took place in three different stages: fast external surface adsorption, gradual adsorption controlled by both film and intra-particle diffusions, and final equilibrium stage. The equilibrium adsorption data of HA on SMHZC better fitted to the Langmuir isotherm model than the Freundlich isotherm model. The equilibrium adsorption data of copper(II) on SMHZC could be described by the Langmuir, Freundlich, and Dubinin–Radushkevich isotherm models. The presence of copper(II) in solution enhanced HA adsorption onto SMHZC. The presence of HA in solution enhanced copper(II) adsorption onto SMHZC. The mechanisms for the adsorption of HA on SMHZC at pH 7 may include electrostatic attraction, organic partitioning, hydrogen bonding, and Lewis acid–base interaction. The mechanisms for the adsorption of copper(II) on SMHZC at pH 6 may include surface complexation, ion exchange, and dissolution–precipitation. The obtained results indicate that SMHZC can be used as an effective adsorbent to simultaneously remove HA and copper(II) from water.     

Adsorption properties of kaolinite-based nanocomposites for Fe and Mn pollutants from aqueous solutions and raw ground water: kinetics and equilibrium studies

Raw kaolinite was used in the synthesis of metakaolinite/carbon nanotubes (K/CNTs) and kaolinite/starch (K/starch) nanocomposites. Raw kaolinite and the synthetic composites were characterized using XRD, SEM, and TEM techniques. The synthetic composites were used as adsorbents for Fe and Mn ions from aqueous solutions and natural underground water. The adsorption by the both composites is highly pH dependent and achieves high efficiency within the neutral pH range. The experimental adsorption data for the uptake of Fe and Mn ions by K/CNTs were found to be well represented by the pseudo-second-order kinetic model rather than the intra-particle diffusion model or Elovich model. For the adsorption using K/starch, the uptake results of Fe ions was well fitted by the second-order model, whereas the uptake of Mn ions fitted well to the Elovich model rather than pseudo-second-order and intra-particle diffusion models The equilibrium studies revealed the excellent fitting of the removal of Fe and Mn ions by K/CNTs and Fe using K/starch with the Langmuir isotherm model rather than with Freundlich and Temkin models. But the adsorption of Mn ions by K/starch is well fitted with Freundlich rather than Temkin and Langmuir isotherm models. The thermodynamic studies reflected the endothermic nature and the exothermic nature for the adsorption by K/CNTs and K/starch nanocomposites, respectively. Natural ground water contaminated by 0.4 mg/L Fe and 0.5 mg/L Mn was treated at the optimum conditions of pH 6 and 120 min contact time. Under these conditions, 92.5 and 72.5% Fe removal efficiencies were achieved using 20 mg of K/CNTs and K/starch nanocomposites, respectively. Also, K/CNTs nanocomposite shows higher efficiency in the removal of Mn ions as compared to K/starch nanocomposite.     

Utilization of Arachis hypogaea hull,an agricultural waste for the production of activated carbons to remove phenol from aqueous solutions

Arachis hypogaea hulls, an agricultural waste, were used to prepare activated carbon by chemical activation with zinc chloride under four different activation atmospheres. The most important parameter in chemical activation was found to be the chemical ratio (activating agent/precursor). Carbonization temperature and time are the other two important variables, which had significant effect on the pore structure of carbon. The maximum Brunquer-Emmett-Teller (BET) surface area and micropore volume of the activated carbon was found to be 418 m²/g and 0.28 cm³/g, respectively. The activated carbon developed shows substantial capability to adsorb phenol from aqueous solutions. The kinetic data were fitted to the models of intraparticle diffusion, pseudo-second-order, and Lagergren, and followed more closely the pseudo-second-order chemisorption model. The isotherm equilibrium data were well fitted by the Langmuir and Freundlich models. Solution pH has significant effect on adsorption and the maximum uptake of phenol was reported at pH 3.5.     

In vitro study of oxytetracycline adsorption on activated charcoal

Abstract

In vitro adsorption experiments simulating pH in gastric environment and using Langmuir isotherm, showed that 408 mg of oxytetracycline was adsorbed per gram of activated charcoal. Langmuir isotherm fitted adsorption data better than a Freundlich isotherm. Freundlich isotherm showed a specific adsorption capacity of 518 mg/g for activated charcoal. Both isotherm parameters indicated a strong oxytetracycline adsorption on activated charcoal in terms of quantity and binding strength. The results demonstrate that the concomitant use of oxytetracyline and activated charcoal should be avoided.     

Adsorption of Cu2+ and methyl orange from aqueous solutions by activated carbons of corncob-derived char wastes

Corncob-derived char wastes (CCW) obtained from biomass conversion to syngas production through corncob steam gasification, which were often discarded, were utilized for preparation of activated carbon by calcination, and KOH and HNO₃ activation treatments, on the view of environment protection and waste recycling. Their adsorption performance in the removal of heavy metal ions and dye molecules from wastewater was evaluated by using Cu²⁺ and methyl orange (MO) as the model pollutant. The surface and structure characteristics of the CCW-based activated carbons (CACs) were investigated by N₂ adsorption, CO₂ adsorption, FT-IR, and He-TPD. The adsorption capacity varied with the activation methods of CACs and different initial solution concentrations, indicating that the adsorption behavior was influenced by not only the surface area and porosity but also the oxygen functional groups on the surface of the CACs. The equilibrium adsorption data were analyzed with the Langmuir, Freundlich, and Temkin isotherm models, and the adsorption kinetics was evaluated by the pseudo-first-order and pseudo-second-order models.     

Kinetic, equilibrium isotherm and thermodynamic studies of Cr(VI) adsorption onto low-cost adsorbent developed from peanut shell activated with phosphoric acid

A particular agricultural waste, peanut shell, has been used as precursor for activated carbon production by chemical activation with H₃PO₄. Unoxidized activated carbon was prepared in nitrogen atmosphere which was then heated in air at a desired temperature to get oxidized activated carbon. The prepared carbons were characterized for surface area, surface morphology, and pore volume and utilized for the removal of Cr(VI) from aqueous solution. Batch mode experiments were conducted to study the effects of pH, contact time, particle size, adsorbent dose, initial concentration of adsorbate, and temperature on the adsorption of Cr(VI). Cr(VI) adsorption was significantly dependent on solution pH, and the optimum adsorption was observed at pH 2. Pseudo-first-order, pseudo-second-order, and intraparticle diffusion models were used to analyze the kinetic data obtained at different initial Cr(VI) concentrations. The adsorption kinetic data were described very well by the pseudo-second-order model. Equilibrium isotherm data were analyzed by the Langmuir, Freundlich, and Temkin models. The results showed that the Langmuir adsorption isotherm model fitted the data better in the temperature range studied. The adsorption capacity which was found to increase with temperature showed the endothermic nature of Cr(VI) adsorption. The thermodynamic parameters, such as Gibb’s Free energy change (ΔG°), standard enthalpy change (ΔH°), and standard entropy change (ΔS°) were evaluated.     

Sorption of pentachlorophenol on peat-bentonite mixtures.

Batch kinetic and isotherm studies were carried out to determine the adsorptive characteristics of peat and bentonite mixtures for pentachlorophenol, and to examine the hydraulic conductivity of peat-bentonite mixtures to determine if they are applicable for use as cutoff barriers. Batch kinetic studies showed that over 90% of PCP was removed from water spiked with approximately 1 mg/l of PCP using a peat-bentonite (5%) mixture. The equilibrium time was 8 hours. The optimum pH range for adsorption of PCP by the peat-bentonite mixture was found to be 3-3.5. Batch isotherm studies showed that the adsorption of PCP by the peat-bentonite mixture from aqueous solution was best described by the Freundlich isotherm equation. Batch adsorption studies using various ratios of bentonite in the mixture showed that the adsorption of PCP decreased linearly with increased amount of bentonite in the mixture, indicating that adsorption of PCP by the peat moss portion of the mixture was the dominant process. The inverse of the hydraulic conductivity was found to increase exponentially with an increase in the bentonite content of the mixture over the range studied. The minimum hydraulic conductivity observed was 3.3 x 10(-7) cm/s for a 50% peat-50% bentonite mixture. Peat-bentonite mixtures can be used to successfully remove PCP from aqueous media and can be used effectively as a barrier to attenuate the migration of PCP through soil and groundwater systems.     

Utilization of nSiO2, fly ash, and nSiO2/fly ash composite for the remediation of triphenyltin (TPT) from contaminated seawater

The removal of triphenyltin chloride from contaminated simulated seawater with adsorption method was discussed. The adsorbents used are fly ash, nSiO₂, and nSiO₂/fly ash composite. The results showed that the adsorption of the adsorbents increases with increase in the adsorbent dose, contact time, pH, stirring speed, initial TPT concentration, and decreased with increase in temperature. The adsorption fitted well with the Freundlich isotherm, showing that the adsorbent and TPT combined with function groups and the adsorption kinetics followed the pseudo-second-order kinetic model. The thermodynamic parameters were also evaluated. Optimal conditions for the adsorption of TPT from simulated seawater were applied to TPT removal from natural seawater. A higher removal efficiency of TPT (>99 %) was obtained for the nSiO₂/fly ash composite but not for fly ash and nSiO₂.     

Utilization of Arachis hypogaea hull, an agricultural waste for the production of activated carbons to remove phenol from aqueous solutions

Arachis hypogaea hulls, an agricultural waste, were used to prepare activated carbon by chemical activation with zinc chloride under four different activation atmospheres. The most important parameter in chemical activation was found to be the chemical ratio (activating agent/precursor). Carbonization temperature and time are the other two important variables, which had significant effect on the pore structure of carbon. The maximum Brunquer-Emmett-Teller (BET) surface area and micropore volume of the activated carbon was found to be 418 m(2)/g and 0.28 cm(3)/g, respectively. The activated carbon developed shows substantial capability to adsorb phenol from aqueous solutions. The kinetic data were fitted to the models of intraparticle diffusion, pseudo-second-order, and Lagergren, and followed more closely the pseudo-second-order chemisorption model. The isotherm equilibrium data were well fitted by the Langmuir and Freundlich models. Solution pH has significant effect on adsorption and the maximum uptake of phenol was reported at pH 3.5.     

3种人工湿地基质对磷的吸附特性

选用页岩、陶粒和砾石3种基质进行等温吸附和吸附动力学试验,研究其对磷的吸附特性。结果表明,Freun-dlich和Langmuir方程均能较好地拟合各基质对磷的吸附特征,并且用Freundlich方程的拟合效果要好于Langmuir方程;基质对磷的理论饱和吸附量大小依次为页岩(527.992 mg/kg)>陶粒(328.165 mg/kg)>砾石(129.729 mg/kg);页岩最大磷吸附量随粒径增加而减小;各基质对磷的吸附过程分为快、中、慢3个阶段,3种基质对磷的吸附速率依次为页岩>陶粒>砾石;准二级动力学方程、双常数方程和Elovich方程均能较好地描述人工湿地基质对磷的吸附动力学特征,但从相关系数来看,准二级动力学方程的描述更为准确。     

Mechanisms of chromium and arsenite adsorption by amino-functionalized SBA-15

The adsorption of Cr(VI) and As(III) by amino-functionalized SBA-15 (NH₂-SBA-15) from single and binary systems were investigated in this work. The effects of pH and temperature on the adsorption of NH₂-SBA-15 were studied. Adsorption kinetics, isotherm model, and thermodynamics were studied to analyze the experimental data. pH 2 was the optimum condition for the adsorption of Cr(VI) and pH 4 for As(III) adsorption. Increasing temperature had a positive effect on the removal of both Cr(VI) and As(III). The Freundlich isotherm model can depict the adsorption process best. The pseudo-second-order kinetic model fitted well with the kinetic data of Cr(VI) and As(III) in the single-component system. In the binary system, the adsorption of As(III) by NH₂-SBA-15 was slightly enhanced with the presence of Cr(VI); however, As(III) had no obvious effect on the removal of Cr(VI). Regeneration experiments indicated that 0.1 mol/L NaHCO₃ was an efficient desorbent for the recovery of Cr(VI) and As(III) from NH₂-SBA-15; the desorption rates for Cr(VI) and As(III) were 91.6 and 33.59 %, respectively. After five recycling cycles, the removal rates were 88 and 7 % for Cr(VI) and As(III) adsorption by NH₂-SBA-15, respectively.     

Esterification of sugarcane bagasse by citric acid for Pb2+ adsorption: effect of different chemical pretreatment methods

In this study, different pretreatment strategies of sugarcane bagasse prior to citric acid modification were investigated in terms of Pb²⁺ adsorption capacity. Pretreatment strategies included the use of NaOH, HCl, and C₂H₅OH in various concentrations. In order to fundamentally understand how these pretreatment methods affect the modification of sugarcane bagasse by citric acid as well as the Pb²⁺ adsorption capacity of sugarcane bagasse, three main components of sugarcane bagasse namely cellulose, hemicellulose, and lignin were isolated and esterified by citric acid under the same conditions. ATR-FTIR, XPS, SEM, and an analysis of the number of carboxylic acid groups were used to investigate the physicochemical and chemical properties of the materials. These three components were proved to participate in adsorption and induce the esterification with citric acid. Hence, pretreatment with ethanol and 0.01 M NaOH which could retain cellulose, hemicellulose, and lignin in sugarcane bagasse achieved a high Pb²⁺ adsorption capacity, i.e., 122.4 and 97 mg/g after the esterification with citric acid. In contrast, pretreatment with 0.5 M NaOH and 0.1 M HCl removed lignin and hemicellulose, leading to the lowest value of approximately 45 mg/g for citric acid esterified-pretreated sugarcane bagasse. XPS analysis and number of carboxylic group measurement confirmed the esterification between bagasse and citric acid. To understand the adsorption mechanism of adsorbent, two kinetic models including pseudo-first-order model and pseudo-second-order model were applied. The experimental data were well described by the pseudo-second-order model. The adsorption isotherm data were fitted Langmuir and Freundlich.