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.     

Removal of Pb(II) from wastewater using wheat bran

The adsorption of Pb(II) ions from aqueous solutions on wheat bran (WB) has been investigated as a function of initial concentration, adsorbent dose, adsorbent particle size, agitation speed, temperature, contact time and pH of solution. The equilibrium process was described well by the Langmuir isotherm model with maximum sorption capacities of 69.0, 80.7 and 87.0 mgg(-1) of Pb(II) on wheat bran at 20, 40 and 60 degrees C, respectively. Thermodynamic parameters, i.e. DeltaG(0), DeltaH(0) and DeltaS(0) have also been calculated for the system and the sorption process was found to be endothermic. Good correlation coefficients were obtained for the pseudo second-order kinetic model. The metal ion could be stripped by addition of 0.5M HCl, making the adsorbent regeneration and its reutilization possible.     

Batch sorption dynamics and equilibrium for the removal of lead ions from aqueous phase using activated carbon developed from coffee residue activated with zinc chloride

Lignocellulosic materials are good precursors for the production of activated carbon. In this work, coffee residue has been used as raw material in the preparation of powder activated carbon by the method of chemical activation with zinc chloride for the sorption of Pb(II) from dilute aqueous solutions.The influence of impregnation ratio (ZnCl₂/coffee residue) on the physical and chemical properties of the prepared carbons was studied in order to optimize this parameter. The optimum experimental condition for preparing predominantly microporous activated carbons with high pore surface area (890 m²/g) and micropore volume (0.772 cm³/g) is an impregnation ratio of 100%. The developed activated carbon shows substantial capability to sorb lead(II) ions from aqueous solutions and for relative impregnation ratios of 75 and 100%, the maximum uptake is practically the same. Thus, 75% represents the optimal impregnation ratio.Batch experiments were conducted to study the effects of the main parameters such as contact time, initial concentration of Pb(II), solution pH, ionic strength and temperature. The maximum uptake of lead(II) at 25 °C was about 63 mg/g of adsorbent at pH 5.8, initial Pb(II) concentration of 10 mg/L, agitation speed of 200 rpm and ionic strength of 0.005 M. The kinetic data were fitted to the models of pseudo-first order and pseudo-second order, and follow closely the pseudo-second order model. Equilibrium sorption isotherms of Pb(II) were analyzed by the Langmuir, Freundlich and Temkin isotherm models. The Freundlich model gives a better fit than the others.Results from this study suggest that activated carbon produced from coffee residue is an effective adsorbent for the removal of lead from aqueous solutions and that ZnCl₂ is a suitable activating agent for the preparation of high-porosity carbons.     

Efficiency of removal of cadmium from aqueous solutions by plant leaves and the effects of interaction of combinations of leaves on their removal efficiency

Removal of cadmium from aqueous solutions using 20 species of plant leaves and combinations of these leaves have been studied. Several factors affecting the removal efficiency have been studied. The most efficient types of plant leaves for the removal of cadmium are those of styrax, plum, pomegranate and walnut. The interaction effect of the combined leaf samples on the efficiency of removal of cadmium has been found to be additive in combinations involving styrax plant leaves but seems to be antagonistic in all other combinations. The optimum experimental conditions for removal of cadmium have been found to be at pH 4.1, using high concentrations of naturally dried plant leaves, using ground leaves and to remove cadmium from agitated aqueous solutions. The percentage of metal removed at an initial cadmium concentration of 10mg/l by the most efficient types of leaves have been found to be 85% for styrax leaves, 85% for plum leaves, 80% for pomegranate leaves, 78% for walnut leaves and 77% for meddler leaves. The presence of foreign ions or complexing agents has been found to reduce the efficiency of removal of cadmium by plant leaves. About 80-85% of the cadmium in charged plant leaves has been released under the influence of changing the pH of the solution, addition of competing ions and the addition of EDTA. The results of removal of cadmium by plant leaves have been found to follow the Freundlich adsorption isotherm, first-order reaction with respect to cadmium and to have intra-pore diffusion as the rate-limiting step.     

Adsorption studies of hazardous malachite green onto treated ginger waste

Adsorption of malachite green (MG) from aqueous solution onto treated ginger waste (TGW) was investigated by batch and column methods. The effect of various factors such as initial dye concentration, contact time, pH and temperature were studied. The maximum adsorption of MG was observed at pH 9. Langmuir and Freundlich isotherms were employed to describe the MG adsorption equilibrium. The monolayer adsorption capacities were found to be 84.03, 163.9 and 188.6 mg/g at 30, 40 and 50 °C, respectively. The values of thermodynamic parameters like ΔG°, ΔH° and ΔS° indicated that adsorption was spontaneous and endothermic in nature. The pseudo second order kinetic model fitted well in correlation to the experimental results. Rechienberg's equation was employed to determine the mechanism of adsorption. The results indicated that film diffusion was a major mode of adsorption. The breakthrough capacities were also investigated.     

Release dynamic process identification for a cement based material in various leaching conditions. Part II. Modelling the release dynamics for different leaching conditions

This paper deals with process identification and model development for the case of a porous reference material leaching under certain hydrodynamic conditions. Four different dynamic leaching tests have been applied in order to take into account different types of solid/liquid contact conditions corresponding to various real leaching scenarios: monolithic and granular material with sequential eluate renewal, and granular material and continuously renewed eluate with different hydrodynamic conditions (dispersion, residence time). A coupled chemical-mass transfer model has been developed to describe the leaching behaviour under all experimental conditions. Diffusion has been considered as the mass transport mechanism inside the saturated porous material and dispersive convection as that in the leachate. Two specific phenomena have been identified and considered in the model: (i) the early surface dissolution of the material which results in high Ca concentration and (ii) the late weak dissolution of Na and K giving rise to a long-term residual release. The intrinsic material parameters such as the initial concentrations in the pore water and solid phases were determined by applying equilibrium leaching tests and geochemical modelling. Diffusion coefficients for different elements and the late solubility of alkalines have been found to reach the same values in the four tests. The estimated values of the surface dissolution kinetic constant have shown a dependence on leachate hydrodynamics when the thickness of the degraded layer is nearly the same in the four tests (intrinsic parameter of the material). The competition between the four main dynamic processes, i.e. diffusion, convection, late dissolution, and surface dissolution, has been emphasized and compared in the four leaching tests: the hydrodynamic dispersion and the residence time had no effect on the leaching behaviour of alkalines, which is controlled by diffusion, whereas the behaviour of calcium (a major element of the material) was strongly influenced. This has significant effects on eluate pH values and on the concentration of Pb (the monitored pollutant). The model was then applied to simulate a landfill scenario in the case of a stabilized/solidified incinerator residue containing heavy metals and chloride. A high rain infiltration level and the use of small blocs are favourable conditions for enhanced pollutant release.     

Application of cupuassu shell as biosorbent for the removal of textile dyes from aqueous solution

The cupuassu shell (Theobroma grandiflorum) which is a food residue was used in its natural form as biosorbent for the removal of C.I. Reactive Red 194 and C.I. Direct Blue 53 dyes from aqueous solutions. This biosorbent was characterized by infrared spectroscopy, scanning electron microscopy, and nitrogen adsorption/desorption curves. The effects of pH, biosorbent dosage and shaking time on biosorption capacities were studied. In acidic pH region (pH 2.0) the biosorption of the dyes were favorable. The contact time required to obtain the equilibrium was 8 and 18 h at 298 K, for Reactive Red 194 and Direct Blue 53, respectively. The Avrami fractionary-order kinetic model provided the best fit to experimental data compared with pseudo-first-order, pseudo-second-order and chemisorption kinetic adsorption models. The equilibrium data were fitted to Langmuir, Freundlich, Sips and Radke-Prausnitz isotherm models. For both dyes the equilibrium data were best fitted to the Sips isotherm model.     

Adsorption of Cu(II) ions from aqueous solutions on biochars prepared from agricultural by-products

In this study, the adsorption of Cu(II) from aqueous solutions by agricultural by-products, such as rice husks, olive pomace and orange waste, as well as compost, was evaluated. The aim was to obtain sorbent materials (biochars) through hydrothermal treatment (300?°C) and pyrolysis (300?°C and 600?°C). The effect of adsorbent dose, pH, contact time and initial Cu(II) concentration in batch-mode experiments was investigated. The optimum Cu(II) adsorption conditions was found to occur at 5-12?g/L adsorbent dose, initial pH 5-6, and reaction time 2-4?h. Furthermore, the adsorption kinetics were best described by the pseudo-second order model for all the tested materials, while the adsorption equilibrium best fitted by the linear and Freundlich isotherms. Comparing rice husks and olive pomace, the higher adsorption capacity resulted after pyrolysis at 300?°C. With respect to the orange waste and compost, the highest adsorption capacity was observed using biochars obtained after hydrothermal treatment and pyrolysis at 300?°C.     

Experimental investigation of adsorption capacity of anthill in the removal of heavy metals from aqueous solution

In the present work, the adsorption capacity of anthill was investigated as a low‐cost adsorbent to remove the heavy metal ions, lead (II) ion (Pb²⁺), and zinc (II) ion (Zn²⁺) from an aqueous solution. The equilibrium adsorption isotherms of the heavy metal ions were investigated under batch process. For the study we examined the effect of the solution's pH and the initial cations concentrations on the adsorption process under a fixed contact time and temperature. The anthill sample was characterized using a scanning electron microscope (SEM), X‐ray fluorescence (XRF), and Fourier transform infrared (FTIR) techniques. From the SEM analysis, structural change in the adsorbent was a result of heavy metals adsorption. Based on the XRF analysis, the main composition of the anthill sample was silica (SiO₂), alumina (Al₂O₃), and zirconia (ZrO₂). The change in the peaks of the spectra before and after adsorption indicated that there was active participation of surface functional groups during the adsorption process. The experimental data obtained were analyzed using 2‐ and 3‐parameter isotherm models. The isotherm data fitted very well to the 3‐parameter Radke–Prausnitz model. It was noted that Pb²⁺ and Zn²⁺ can be effectively removed from aqueous solution using anthill as an adsorbent.     

Adsorptive removal of Cd(II) and Pb(II) ions from aqueous solutions by using Turkish illitic clay

The ability of Turkish illitic clay (TIC) in removal of Cd(II) and Pb(II) ions from aqueous solutions has been examined in a batch adsorption process with respect to several experimental conditions including initial solution pH, contact time, initial metal ions concentration, temperature, ionic strength, and TIC concentration, etc. The characterization of TIC was performed by using FTIR, XRD and XRF techniques. The maximum uptake of Cd(II) (11.25 mg g⁻¹) and Pb(II) (238.98 mg g⁻¹) was observed when used 1.0 g L⁻¹ of TIC suspension, 50 mg L⁻¹ of initial Cd(II) and 250 mg L⁻¹ of initial Pb(II) concentration at initial pH 4.0 and contact time of 240 min at room temperature. The experimental data were analyzed by the Langmuir, Freundlich, Temkin and Dubinin Radushkevich (D-R) isotherm models. The monolayer adsorption capacity of TIC was found to be 13.09 mg g⁻¹ and 53.76 mg g⁻¹ for Cd(II) and Pb(II) ions, respectively. The kinetics of the adsorption was tested using pseudo-first-order, pseudo-second-order, Elovich and intraparticle diffusion models. The results showed that the adsorption of Cd(II) and Pb(II) ions onto TIC proceeds according to the pseudo-second-order model. Thermodynamic parameters including the Gibbs free energy (ΔG), enthalpy (ΔH), and entropy (ΔS) changes indicated that the present adsorption process was feasible, spontaneous and endothermic in the temperature range of 5–40 °C.     

Loofa egyptiaca as a novel adsorbent for removal of direct blue dye from aqueous solution

In this paper, Loofa egyptiaca (LE), an agricultural plant cultivated in Egypt, was used to prepare low-cost activated carbon (LE_C1 and LE_C2) adsorbents. The adsorbents (LE, LE_C1 and LE_C2) were evaluated for their ability to remove direct blue 106 dye from aqueous solutions. Batch mode experiments were conducted using various parameters such as pH, contact time, dye concentration and adsorbent concentration. The surface chemistry of LE, LE_C1 and LE_C2 was analyzed by scanning electron microscopy (SEM). The experimental data were examined using Langmuir, Freundlich, Temkin and Harkins–Jura isotherms. The results showed that the adsorption of direct blue 106 was maximal at the lowest value of pH (pH = 2). Removal efficiency was increased with an increase in dye concentration and a decrease in amount of adsorbent. Maximum adsorption capacity was found to be 57.14, 63.3 and 73.53 mg/g for LE, LE_C1 and LE_C2 respectively. Kinetics were also investigated using pseudo-first-order, pseudo-second-order and intra-particle diffusion models. The experimental data fitted very well with the pseudo-first-order and pseudo-second-order kinetic models. The results indicate that LE, LE_C1 and LE_C2 could be employed as adsorbents for the removal of direct blue dye from aqueous solutions.     

Adsorption of methylene blue from aqueous solution by jackfruit (Artocarpus heteropyllus) leaf powder: A fixed-bed column study

Continuous fixed-bed studies were undertaken to evaluate the efficiency of jackfruit leaf powder (JLP) as an adsorbent for the removal of methylene blue (MB) from aqueous solution under the effect of various process parameters like bed depth (5–10 cm), flow rate (30–50 mL/min) and initial MB concentrations (100–300 mg/L). The pH at point of zero charge (pH_PZC) of the adsorbent was determined by the titration method and a value of 3.9 was obtained. A FTIR of the adsorbent was done before and after the adsorption to find the potential adsorption sites for interaction with methylene blue molecules. The results showed that the total adsorbed quantities and equilibrium uptake decreased with increasing flow rate and increased with increasing initial MB concentration. The longest breakthrough time and maximum MB adsorption were obtained at pH 10. The results showed that the column performed well at low flow rate. Also, breakthrough time and exhaustion time increased with increasing bed depth. The bed-depth service time (BDST) model and the Thomas model were applied to the adsorption of MB at different bed depths, flow rates, influent concentrations and pH to predict the breakthrough curves and to determine the characteristic parameters of the column that are useful for process design. The two model predictions were in very good agreement with the experimental results at all the process parameters studied indicating that they were very suitable for JLP column design.     

Removal of Fe(II) from the wastewater of a galvanized pipe manufacturing industry by adsorption onto bentonite clay

Bentonite clay has been used for the adsorption of Fe(II) from aqueous solutions over a concentration range of 80-200 mg/l, shaking time of 1-60 min, adsorbent dosage from 0.02 to 2 g and pH of 3. The process of uptake follows both the Langmuir and Freundlich isotherm models and also the first-order kinetics. The maximum removal (>98%) was observed at pH of 3 with initial concentration of 100 mg/l and 0.5 g of bentonite. The efficiency of Fe(II) removal was also tested using wastewater from a galvanized pipe manufacturing industry. More than 90% of Fe(II) can be effectively removed from the wastewater by using 2.0 g of the bentonite. The effect of cations (i.e. zinc, manganese, lead, cadmium, nickel, cobalt, chromium and copper) on the removal of Fe(II) was studied in the concentration range of 10-500 mg/l. All the added cations reduced the adsorption of Fe(II) at high concentrations except Zn. Column studies have also been carried out using a certain concentration of wastewater. More than 99% recovery has been achieved by using 5 g of the bentonite with 3M nitric acid solution.     

The use of ion exchange membranes for isotope analyses on soil water sulfate: laboratory experiments

To investigate the potential use of anion exchange membranes (plant root simulator [PRS] probes) for isotope investigations of the soil sulfur cycle, laboratory experiments were performed to examine the sulfate exchange characteristics and to determine the extent of sulfur and oxygen isotope fractionation during sulfate sorption and desorption on the probes in aqueous solutions and simulated soil solutions. The sulfate-exchange tests in aqueous solutions under varying experimental conditions indicated that the amount of sulfate exchanged onto PRS probes increased with increasing reaction time, initial sulfate concentration, and the number of probes used (= surface area), whereas the percentage of removal of available sulfate was constant irrespective of the initial sulfate concentration. The competition of nitrate and chloride in the solution lowered the amount of exchanged sulfate. The exchange experiments in a simulated soil under water-saturated and water-unsaturated conditions showed that a considerable proportion of the soil sulfate was exchanged by the PRS probes after about 10 d. There was no evidence for significant sulfur and oxygen isotope fractionation between soil sulfate and sulfate recovered from the PRS probes. Therefore, we recommend the use of PRS probes as an efficient and easy way to collect soil water sulfate for determination of its isotope composition.     

纳米零价铁去除磷酸盐机理研究

纳米零价铁(nanoscale zero-valent iron,nZVI)颗粒具有独特核-壳结构,使其具有较强氧化还原特性,比表面积大和表面活性高等特点,因此被广泛用于不同环境介质中多种污染物的去除修复。本研究采用传统的液相化学还原法合成nZVI颗粒并用于去除水溶液中的磷酸盐。通过扫描电子显微镜(SEM)、透射电子显微镜(TEM)和X射线衍射仪(XRD)表征nZVI颗粒的性质。实验研究了nZVI投加量、PO3-4初始浓度、溶液初始pH值对nZVI去除PO3-4效率的影响及微米零价铁(micro-ZVI)和nZVI去除PO3-4的对比。实验结果表明,当PO3-4初始浓度为20mg/L时,随着nZVI投加量从200mg/L增加到1000mg/L,PO3-4去除效率从32.94%上升到90.17%;当nZVI投加量为600mg/L时,随着PO3-4初始浓度从10mg/L增加到100mg/L,PO3-4去除效率从87.33%下降到45.77%;当nZVI投加量为600mg/L且PO3-4初始浓度为20mg/L,溶液pH分别为3和4时,PO3-4去除效率分别为83.63%和92.36%;nZVI和mZVI投加量均为600mg/L且PO3-4初始浓度为10mg/L,nZVI的PO3-4去除率(87.33%)是mZVI(8.86%)的9.86倍。研究结果表明,nZVI能够高效去除水体中的磷酸盐,主要去除机理是吸附和化学沉淀的双重作用。     

Removal of phenol from aqueous solution by adsorption onto OTMAC-modified attapulgite

The potential of octodecyl trimethyl ammonium chloride (OTMAC)-modified attapulgite (AT) for phenol adsorption from aqueous solutions was studied. The comparison of natural AT and modified AT showed that it is possible to utilize the sonication-modified OTMAC-AT in the treatment of phenol-contaminated wastewaters. Batch sorption studies were carried out to evaluate the effect of contact time, shaking frequency, temperature and the amount of AT. The results showed that in a lab-scale reactor, at room temperature, with an amount of the modified AT added (2.5 g), and a shaking frequency of 140 rev/min, the adsorption rate of phenol could be 60.4% for a duration of 60 min. The sorption kinetics were described by a pseudo-second-order model, and the values of k and q(e) were 1.367 mg/ig min and 0.7901 ig/mg, respectively. The analysis of equilibrium data showed that the Freundlich isotherms were found to be applicable for the adsorption equilibrium data. K and 1/n were estimated to be 14.53 and 0.8438, respectively.     

Effects of impurities on the removal of heavy metals by natural limestones in aqueous systems

Effects of impurities on the removal of heavy metals by natural limestones in aqueous solutions were studied by evaluating various factors including limestone concentration, pH, contact time and temperature. Solutions of Pb(II), Cd(II), Cu(II) and Zn(II), prepared from chloride reagents at a concentration of 10 mg/L, were studied in a batch method. Four natural limestone samples, collected from the Campanian-Maastrichtian limestone beds in Tunisia, were used as adsorbents. Sorption experiments indicated that high removal efficiencies could be achieved. Limestone samples containing impurities, such as silica, iron/aluminum oxides and different kinds of clay minerals, demonstrated enhanced sorption capacity, nearing 100% removal in some cases. Kinetic experiments showed that the sorption of metal ions occurred rapidly at a low coverage stage, and that solutions were nearly at equilibrium after 60 min. Data trends generally fit pseudo-second order kinetic, and intra-particle diffusion, models. The following conditions were found to promote optimum, or near-optimum, sorption of heavy metals: 1) contact time of more than 60 min, 2) pH = 5, 3) >3 g/L limestone concentration and 4) T = 35 °C. The results of this study suggest that the limestones from northern Tunisia, that contain higher amounts of silica and iron/aluminum oxides, are promising adsorbents for the effective removal of toxic heavy metals from wastewaters.     

EFFECTS OF SUSPENDED SOLIDS ON THE ACUTE TOXICITY OF ZINC TO DAPHNIA MAGNA AND PIMEPHALES PROMELAS1

ABSTRACT: Current procedures for setting site-specific water quality criteria consider abiotic and biotic factors. Suspended solids were shown to be important in reducing zinc toxicity to water column organisms. At zinc concentrations of ～ 1 mg/L in solutions with < 100 mg/L of all suspended solids tested, zinc toxicity to D. magna was reduced. Sorption of zinc to suspended solids and/or changes in water chemistry due to the addition of suspended solids appear to have been the factors causing reductions in zinc toxicity to D. magna. Only suspended solids levels of 483–734 mg/L of a type that increased total alkalinity, total hardness, and total dissolved carbon clearly reduced the toxicity of ～ 20 mg/L zinc to P. promelas. The toxic form of zinc to these organisms appears to reside in the aqueous phase. Characteristics of suspended solids did not influence the partition coefficient of zinc in sorption experiments of 96 h. The slopes of dose-response curves proved to be useful for assessing the potential of an organism to respond to changes in aqueous phase zinc concentrations, and may be a useful biological parameter when considering site-specific water quality criteria for chemicals.     

Sorption of cadmium and zinc from aqueous solutions by zeolite 4A, zeolite 13X and bentonite

The sorption and desorption of cadmium and zinc on zeolite 4A, zeolite 13X and bentonite has been studied using batch sorption studies. Parameters such as equilibrium time, effect of pH and sorbent dose were studied. The sorbents exhibited good sorption potential for cadmium and zinc with a peak value at pH 6.0 and 6.5, respectively. The sorption followed the Freundlich sorption model. More than 70% sorption occurred within 20 min and equilibrium was attained at around 90 min for the three sorbents. The metals sorption by zeolite 4A was higher than that by zeolite 13X and bentonite. The desorption studies were carried out using NaCl solution and the effect of NaCl concentration on desorption was also studied. Maximum desorption of 76% for cadmium and 80% for zinc occurred with 10% NaCl.     

Development of activated carbon from Nerium oleander flower and their rapid adsorption of direct and reactive dyes

The present study investigates the thermally activated carbon derived from Nerium oleander flower which was used an adsorbent. Physicochemical properties of Nerium oleander flower carbon (NOFC) were characterized by scanning electron microscopy, X-ray diffraction, and Fourier transform infrared for the removal of DTB (Direct Turquoise Blue) and RR-HE7B (Reactive red–HE7B) dyes from aqueous solution. Adsorption studies were carried out with different pH, adsorbent dose, contact time, and initial concentration dye solution. Optimum conditions for maximum removal of DTB and RR-HE7B was achieved to be pH 2 for both dyes, adsorbent dose of 100 mg and equilibrium time of 35 and 60 min, respectively, for NOFC. The maximum adsorption capacity of NOFC was found to be 33.33 and 19.60 mg g^?1, respectively, for the removal of dye solution. The mechanism of adsorption was studied by using different kinetic models and isotherms. The results clearly showed that the NOFC adsorption was fitted to pseudo–first-order for DTB and pseudo–second-order for RR-HE7B. Equilibrium data were well fitted with both isotherm models. According to the results, NOFC can effectively remove DTB and RR-HE7B from aqueous solutions.