Physicochemical aspects of using natural scavengers in removing methylene blue (basic dye) from solution

Effluent from dyeing and finishing processes is an important source of water pollution. The effectiveness of bentonite, kaolinite and sediment from a local deposit in removing methylene blue as a cationic dye from aqueous solutions has been investigated. The adsorption equilibrium (isotherm) has been determined according to Freundlich and Langmuir equations. The optimum amount is 0.5 g for all adsorbents, and the optimum pH ranges are 2-8 for bentonite and 2-6 for kaolinite and sediment. With respect to kinetic modelling, the adsorption of methylene blue on various adsorbents was fitted to a second-order equation. Also, the thermodynamic parameters were determined. The negative free energy values indicate the feasibility of the process and spontaneous nature of adsorption. The positive ΔH° values indicate the endothermic nature of the process. Thus, Egyptian clay minerals and sediments have a great tendency to remove the dye from solutions.     

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.     

Oxidation of Cr(III) on birnessite surfaces: The effect of goethite and kaolinite

Oxidation of Cr(III) by manganese oxides may pose a potential threat to environments due to the formation of toxic Cr(VI) species. At present, it was still unclear whether the extent of Cr(III) oxidation and fate of Cr(VI) would be changed when manganese oxides co-exist with other minerals, the case commonly occurring in soils. This study investigated the influence of goethite and kaolinite on Cr(III) oxidation by birnessite under acidic pH condition (pH 3.5) and background electrolyte of 0.01 mol/L NaCl. Goethite was found not to affect Cr(III) oxidation, which was interpreted as the result of overwhelming adsorption of cationic Cr(III) onto the negatively-charged birnessite (point of zero charge (PZC) < 3.0) rather than the positively-charged goethite (PZC = 8.8). However, more Cr(VI) would be retained by the surface with the increase in addition of goethite because of its strong ability on adsorption of Cr(VI) at low pH. Moreover, either Cr(III) oxidation or distribution of the generated Cr(VI) between the solid and solution phases was not affected by kaolinite (PZC < 3.0), indicating its low affinity for Cr species. Reactions occurring in the present mixed systems were suggested, which could be partly representative of those in the soils and further indicates that the mobility and risk of Cr(VI) would be decreased if goethite was present.     

Sorption of Pesticides on Kaolinite and Montmorillonite as a Function of Hydrophilicity

Pesticides and other organic species are adsorbed by soil via different mechanisms, with bond strengths that depend on the properties of both the soil and the pesticide. Since the clay fraction in soil is a preferential sorbent for organic matter, reference kaolinite and montmorillonite are useful models for studying the mechanism and the strength of sorption. This paper presents the results of batch experiments to investigate the interactions of kaolinite KGa-1 and montmorillonite SWy-1 with the following pesticides and organic species resulting from the natural degradation of pesticides in the environment: atrazine (1-chloro-3-ethylamino-5-isopropylamino-2,4,6-triazine), simazine (1-chloro-3,5-bisethylamino-2,4,6-triazine), diuron [1,1-dimethyl-3-(3,4-dichlorophenyl)urea], aniline, 4-chlorophenol, 2,4-dichlorophenol, and 2,4,6-trichlorophenol. Each of these chemicals has different hydrophilicity. Systems containing 2.0 g of clay were put in contact with 100.0 mL of solutions of the pesticides at known concentration ranging from 1.0 to 5.0 mg/L, and the amount of solute adsorbed was evaluated through RP-HPLC analysis of the pesticide still present in the aqueous suspension. To test for electrostatic interactions between the clay surface and the pesticides, potentiometric titration was used to determine the permanent surface charge of clays. Experiments were performed at different pH values. The results indicate that, for the chemicals studied, neutral molecules are preferentially retained relative to ionized ones, and that montmorillonite is a more effective sorbent than kaolinite.     

茂名高岭土矿高岭石的矿物学特征及其涂布性能

茂名高岭土矿的高蛉石,有序度高,晶粒细小(<2微米),沿α、b轴横向连结,无书册状、蠕虫状的大集晶,SiO_2/Al_2O_3值接近高岭石的理论值,Fe_2O_3、TiO_2等杂质含量低于0.5％,并可加工分离,为当前有开发前景的优质涂布原料。     

The effect of interaction between Bacillus subtilis DBM and soil minerals on Cu(Ⅱ) and Pb(Ⅱ) adsorption

The effects of interaction between Bacillus subtilis DBM and soil minerals on Cu(Ⅱ)and Pb(Ⅱ)adsorption were investigated.After combination with DBM,the Cu(Ⅱ)and Pb(Ⅱ)adsorption capacities of kaolinite and goethite improved compared with the application of the minerals independently.The modeling results of potentiometric titration data proved that the site concentrations of kaolinite and goethite increased by 80%and 30%,respectively after combination with DBM.However,the involvement of functional groups in the DBM/mineral combinations resulted in lower concentrations of observed sites than the theoretical values and led to the enhancement of desorption rates by NH_4NO_3 and EDTA-Na_2.The DBM-mineral complexes might also help to prevent heavy metals from entering DBM cells to improve the survivability of DBM in heavy metal-contaminated environments.During the combination process,the extracellular proteins of DBM provided more binding sites for the minerals to absorb Cu(Ⅱ)and Pb(Ⅱ).In particular,an especially stable complexation site was formed between goethite and phosphodiester bonds from EPS to enhance the Pb(Ⅱ)adsorption capacity.So,we can conclude that the DBM–mineral complexes could improve the Cu(Ⅱ)and Pb(Ⅱ)adsorption capacities of minerals and protect DBM in heavy metal-contaminated environments.     

活性艳红染料在高岭土上的表面增强拉曼光谱研究

利用化学还原的方法制备银溶胶，通过在吸附了活性艳红的高岭土基体上沉积银，获得了活性艳红在高岭土上的表面增强拉曼光谱，探讨了活性艳红在高岭土上的吸附机理．结果表明，活性艳红和银溶胶均以范德华力和静电引力直接吸附于高岭土上。且银溶胶对活性艳红在高岭土上的拉曼信号有显著的增强效应。     

Physicochemical aspects of using natural scavengers in removing methylene blue (basic dye) from solution

Effluent from dyeing and finishing processes is an important source of water pollution. The effectiveness of bentonite, kaolinite and sediment from a local deposit in removing methylene blue as a cationic dye from aqueous solutions has been investigated. The adsorption equilibrium (isotherm) has been determined according to Freundlich and Langmuir equations. The optimum amount is 0.5 g for all adsorbents, and the optimum pH ranges are 2–8 for bentonite and 2–6 for kaolinite and sediment. With respect to kinetic modelling, the adsorption of methylene blue on various adsorbents was fitted to a second-order equation. Also, the thermodynamic parameters were determined. The negative free energy values indicate the feasibility of the process and spontaneous nature of adsorption. The positive ΔH° values indicate the endothermic nature of the process. Thus, Egyptian clay minerals and sediments have a great tendency to remove the dye from solutions.     

Reduced Adsorption of Ametryn in Clay,Humic Acid,and Soil by Interaction with Ferric Ion Under Fenton Treatment Conditions

Previous work in our laboratory indicated a weak interaction between ferric ion and several triazine/triazinone herbicides during a Fenton treatment process, and the intensity of the interaction was calculated. To further support the existence of this weak interaction, the adsorption of ametryn, a triazine herbicide, was investigated in kaolinite clay, humic acid, and soil under pseudo-Fenton conditions. At a low addition rate of ferric ion, the adsorption of ametryn in clay, humic acid, and soil was enhanced due to the decreased pH resulting from the hydrolysis of ferric ion. But the pH effect was totally neutralized and the adsorption of ametryn was significantly reduced by further addition of ferric ion, demonstrating the existence of the weak interaction between ametryn and ferric acid. Further study showed that the adsorption-reduction effect of ferric ion existed not only with ametryn but also with several other triazine/triazinone herbicides. This weak interaction may accelerate the desorption process during the remediation of triazine/triazinone herbicide-contaminated soil using a Fenton/Fenton-like treatment, but it may also impede the degradation of these herbicides.     

Metal stabilization mechanism of incorporating lead-bearing sludge in kaolinite-based ceramics

The feasibility and mechanism of incorporating simulated lead-laden sludge into low-cost ceramic products was investigated by observing the reaction of lead with two kaolinite-based precursors under sintering conditions. To investigate the phase transformation process of lead, lead oxide (PbO) mixed with a kaolinite or mullite precursor were fired at 500-950 °C for 3 h. Detailed X-ray diffraction analysis of sintered products revealed that both precursors had crystallochemically incorporated lead into the lead feldspar (PbAl₂Si₂O₈) crystalline structure. By mixing lead oxide with kaolinite, lead feldspar begins to crystallize at 700 °C; maximum incorporation of lead into this structure occurred at 950 °C. However, two intermediate phases, Pb₄Al₄Si₃O₁₆ and a polymorph of lead feldspar, were detected at temperatures between 700 and 900 °C. By sintering lead oxide with the mullite precursor, lead feldspar was detected at temperatures above 750 °C, and an intermediate phase of Pb₄Al₄Si₃O₁₆ was observed in the temperature range of 750-900 °C. This study compared the lead leachabilities of PbO and lead feldspar using a prolonged leaching test (at pH 2.9 for 23 d) modified from the toxicity characteristic leaching procedure. The results indicate the superiority of lead feldspar in stabilizing lead and suggest a promising and reliable strategy to stabilize lead in ceramic products.