Extended geometric method: a simple approach to derive adsorption rate constants of Langmuir-Freundlich kinetics

A new and simple equation has been presented here for calculation of adsorption and desorption rate constants of Langmuir-Freundlich kinetic equation. The derivation of new equation is on the basis of extension and correction to the geometric method which has been presented by Kuan et al. [Kuan, W.-H., Lo, S.-L., Chang, C.M., Wang, M.K., 2000. A geometric approach to determine adsorption and desorption kinetic constants. Chemosphere 41, 1741-1747] for the kinetics of adsorption/desorption in aqueous solutions. The correction is to consider that the concentration of solute is not constant and changes as adsorption proceeds. The extension is that we applied Langmuir-Freundlich kinetic model instead of Langmuir kinetic model to consider the heterogeneity and therefore it is more applicable to the real systems. For solving Langmuir-Freundlich kinetic model, some geometric methods and also Taylor expansion were used and finally a simple and novel equation was derived (Eq. (20)) for calculation of adsorption rate constant. This new method was named "extended geometric method". The input data of the obtained equation can be simply derived from initial data of adsorption kinetics. Finally the adsorption of methyl orange onto granular activated carbon was carried out at dynamic and equilibrium conditions and the capabilities of extended geometric method were examined by the experimental data.     

Immobilization of Pb(II), Cd(II) and Ni(II) ions on kaolinite and montmorillonite surfaces from aqueous medium

The present study investigates the immobilization of Pb(II), Cd(II) and Ni(II) on clays (kaolinite and montmorillonite) in aqueous medium through the process of adsorption under a set of variables (concentration of metal ion, amount of clay, pH, time and temperature of interaction). Increasing pH favours the removal of metal ions till they are precipitated as the insoluble hydroxides. The uptake is rapid with maximum adsorption being observed within 180 min for Pb(II) and Ni(II) and 240 min for Cd(II). A number of available models like the Lagergren pseudo first-order kinetics, second-order kinetics, Elovich equation, liquid film diffusion and intra-particle diffusion are utilized to evaluate the kinetics and the mechanism of the immobilization interactions. Two isotherm equations due to Langmuir and Freundlich showed good fits with the experimental data. Kaolinite and montmorillonite have considerable Langmuir monolayer capacity with respect to Pb(II), Cd(II) and Ni(II), the values being in the range of 6.8-11.5mg/g (kaolinite) and 21.1-31.1mg/g (montmorillonite). The Freundlich adsorption capacity follows a similar order. The thermodynamics of the immobilization process indicates the same to be exothermic with Pb(II) and Ni(II), but endothermic with Cd(II). The interactions with Pb(II) and Ni(II) are accompanied by decrease in entropy and Gibbs energy while the endothermic immobilization of Cd(II) is supported by an increase in entropy and an appreciable decrease in Gibbs energy. The results have established good potentiality for kaolinite and montmorillonite to remove heavy metals like Pb(II), Cd(II) and Ni(II) from aqueous medium through adsorption-mediated immobilization.     

Attenuation of divalent toxic metal ions using natural sericitic pyrophyllite

The present study investigated the effectiveness of an inexpensive and ecofriendly alumino silicate clay mineral, sericitic pyrophyllite, as an adsorbent for the possible application in the removal of some divalent toxic metal cations such as Pb(2+), Cu(2+)and Zn(2+) from aqueous systems. Batch scale equilibrium adsorption studies were carried out for a wide range of initial concentration from 24.1 to 2410mumolL(-1) for lead, 78.65 to 7865mumolL(-1) for copper and 76.45 to 7645mumolL(-1) for zinc solutions. The removal of Pb(2+) was almost complete at low concentration (maximum lead removal capacity, LRC, 32mg of lead/g of pyrophyllite) with 10gL(-1) of adsorbent in a 30min equilibration time. The effects of temperature on adsorption of heavy metal ions were studied. The applicability of the Langmuir, Freundlich and Dubinin-Radushkevich adsorption models in each case of lead, copper and zinc adsorption was examined separately at different temperatures. The adsorption process was found to be endothermic and the Freundlich adsorption model was found to represent the data at different temperatures more suitably.     

Adsorption of basic dye from aqueous solution onto fly ash

The fly ash treated by H₂SO₄ was used as a low-cost adsorbent for the removal of a typical dye, methylene blue, from aqueous solution. An increase in the specific surface area and dye-adsorption capacity was observed after the acid treatment. The adsorption isotherm and kinetics of the treated fly ash were studied. The experimental results were fitted using Langmuir and Freundlich isotherms. It shows that the Freundlich isotherm is better in describing the adsorption process. Two kinetic models, pseudo-first order and pseudo-second order, were employed to analyze the kinetic data. It was found that the pseudo-second-order model is the better choice to describe the adsorption behavior. The thermodynamic study reveals that the enthalpy (ΔH⁰) value is positive (5.63 kJ/mol), suggesting an endothermic nature of the adsorption.     

无机纳米材料吸附分离放射性核素的研究进展

介绍了无机纳米材料特殊的理化性质,综述了纳米氧化物、纳米含氧酸盐和碳纳米管等无机纳米材料在放射性核素吸附分离中的研究进展。提出应对纳米材料进行负载、修饰或功能化研究,制备高性能的复合纳米材料,提高其稳定性和选择性;寻求更经济可行的制备方法,降低纳米材料的生产成本,逐步实现产业化;深入研究纳米材料对放射性核素的吸附机理;在辐射效应对纳米吸附剂的结构稳定性影响方面开展研究,并与现有方法作比较,评价其应用的有效性和可靠性。     

Performance of a small-scale solar-powered adsorption cooling system

In this study, an experimental investigation on the performance of a small-scale residential-size solar-driven adsorption (silica gel-water) cooling system that was constructed at Assiut University campus, Egypt is carried out. As Assiut area is considered as hot, arid climate, field tests for performance assessment of the system operation during the summer season are performed under different environmental operating conditions. The system consists of an evacuated tube with a reflective concentration parabolic surface solar-collector field with a total area of 36 m², a silica gel-water adsorption chiller of 8 kW nominal cooling capacity, and hot and cold water thermal storage tanks of 1.8 and 1.2 m³ in volume, respectively. The results of summer season field test show that under daily solar insolation varying from 21 to 27 MJ/m², the solar collectors employed in the system had high and almost constant thermal efficiency. The daily solar-collector efficiency during the period of system operation ranged from about 50% to 78%. The adsorption chiller performance shows that the chiller average daily coefficient of performance (COP) was 0.41 with the average cooling capacity of 4.4 kW when the cooling-water and chilled-water temperatures were about 31°C and 19°C, respectively. As the chiller cooling water is cooled by the cooling tower in the hot arid area, the cooling water is at a higher temperature than the design point of the chiller. Therefore, an experiment was carried out using the city water for cooling. The results show that an enhancement in the chiller COP by 40% and the chilling power by 17% has been achieved when the city water was 27.7°C.     

New methodological improvements in the Microtox® solid phase assay

The classic Microtox® solid phase assay (MSPA) based on the inhibition of light production of the marine bacteria recently renamed Aliivibrio fischeri suffers from various bias and interferences, mainly due to physico-chemical characteristics of the tested solid phase. To precisely assess ecotoxicity of sediments, we have developed an alternative method, named Microtox® leachate phase assay (MLPA), in order to measure the action of dissolved pollutants in the aqueous phase. Two hypotheses were formulated to explain the observed difference between MSPA and MLPA results: a real ecotoxicity of the solid phase or the fixation of bacteria to fine particles and/or organic matter. To estimate the latter, flow cytometry analyses were performed with two fluorochromes (known for their ability to stain bacterial DNA), allowing correction of MSPA measurements and generation of new (corrected) IC50. Comparison of results of MLPA with the new IC50 MSPA allows differentiating real ecotoxic and fixation effect in classic MSPA especially for samples with high amount of fines and/or organic matter.     

Adsorption of Pb(II) on variable charge soils amended with rice-straw derived biochar

Two Ultisols and one Oxisol from tropical regions of southern China were incubated with rice straw biochar to investigate the effect of biochar on their surface charge and Pb(II) adsorption using batch methods. The incorporation of biochar induced a remarkable increase in soil cation exchange capacity after 30 d of incubation. The incorporation of biochar significantly increased the adsorption of Pb(II) by these variable charge soils; the enhancement of adsorption of Pb(II) by these soils increased with the addition level of biochar. Adsorption of Pb(II) involved both electrostatic and non-electrostatic mechanisms; however, biochar mainly increased Pb(II) adsorption through the non-electrostatic mechanism via the formation of surface complexes between Pb²⁺ and functional groups on biochar. There was greater enhancement of biochar on the non-electrostatic adsorption of Pb(II) by the variable charge soils at relatively low pH. Therefore, the incorporation of biochar decreased the activity and availability of Pb(II) to plants through increased non-electrostatic adsorption of Pb(II) by acidic variable charge soils.     

Immobilization of non-point phosphorus using stabilized magnetite nanoparticles with enhanced transportability and reactivity in soils

Laboratory batch and column experiments were conducted to investigate the immobilization of phosphorus (P) in soils using synthetic magnetite nanoparticles stabilized with sodium carboxymethyl cellulose (CMC-NP). Although CMC-stabilized magnetite particles were at the nanoscale, phosphorus removal by the nanoparticles was less than that of microparticles (MP) without the stabilizer due to the reduced P reactivity caused by the coating. The P reactivity of CMC-NP was effectively recovered when cellulase was added to degrade the coating. For subsurface non-point P pollution control for a water pond, it is possible to inject CMC-NP to form an enclosed protection wall in the surrounding soils. Non-stabilized “nanomagnetite” could not pass through the soil column under gravity because it quickly agglomerated into microparticles. The immobilized P was 30% in the control soil column, 33% when treated by non-stabilized MP, 45% when treated by CMC-NP, and 73% when treated by both CMC-NP and cellulase.     

Deposition of aerially sprayed mexacarbate on balsam fir canopy and the forest floor: Relevance to ULV applications

Abstract

Spray deposit patterns were measured on aluminum coils and live balsam fir needles at different canopy heights, following aerial application of mexacarbate (4‐dimethylamino‐3,5‐xylyl N‐methylcarbamate) over a conifer forest in New Brunswick. Droplet size spectra of the spray cloud were determined on cylindrical Kromekote® cards placed at the corresponding crown heights. Ground deposits were collected on cylindrical Kromekote cards, aluminum coils and natural balsam fir foliage placed In forest clearings and under different types of vegetation.

Canopy deposits decreased progressively from the top to the bottom level of the tree crown. This trend was observed on aluminum coils, live fir foliage, and Kromekote cards. Droplet size spectra were similar at all sampling heights of the tree crown, and were comparable to those obtained on the ground cards placed in the forest clearings. Deposits of mexacarbate obtained on ground samplers on the open forest floor were markedly lower than those found at the top canopy but were similar to those at the mid or bottom canopy level. Droplet size spectra and mexacarbate deposits obtained on samplers placed under different types of forest vegetation indicated a selective filtration of the large droplets present in the spray cloud by plant canopies.