Kinetic and Equilibrium Modeling for Cr(III) and Cr(VI) Removal from Aqueous Solutions by Citrus reticulata Waste Biomass

The pulp left after the extraction of juice from Citrus reticulate (kinnow), is a waste material, which was used as a potential sorbent for Cr(III) and Cr(VI) in the present study. The effect of experimental parameters such as pH, biosorbent dosage, biosorbent particle size, initial metal concentrations, temperature, shaking speed and sorption time on the Cr removal is apparent from the obtained results. The Freundlich isotherm and pseudo second order kinetic models fitted well to the data of Cr(III) and Cr(VI) biosorption by Citrus reticulata waste biomass. Effect of several pretreatments such as gases, natural coagulant and many other chemicals on Cr(III) and Cr(VI) sorption capacity of Citrus reticulata waste biomass was first time analyzed in the present study. The metal sorption capacity of Citrus reticulata waste biomass after a specific pretreatment was not only related to the nature of chemical but also strongly dependent on the oxidation state of the metal.     

Removal of Mercury Ions from Mixed Aqueous Metal Solutions by Natural and Modified Zeolitic Minerals

Research works on the removal of mercury from water by zeolitic mineralshow that small quantities of this element are sorbed. In this work the mercury sorption from aqueous solutions in the presence and absence of Cu(II), Ni(II) and Zn(II) onto a Mexican zeolitic mineral unmodified and modified with cysteamine hydrochloride or cystamine dihydrochloride was investigated in acidic pH. The zeolitic minerals were characterized by thermogravimetric analysis, scanning electron microscopy, X-ray diffraction and FTIR. The sorption kinetics behavior and the retention isotherms for mercury were determined in the natural and treated zeolitic mineral samples. It was found that the amounts of sulfur on the modified zeolitic minerals were 0.375 (cysteamine hydrochloride) and 0.475 (cystamine dihydrochloride) mmol g^-1, which were not saturated to their total capacities of adsorption for the maximum concentration used (0.310 mM). Under the experimental conditions, the retention of mercury was the highest for the zeolitic minerals treated with the organic compounds, with adsorption capacities ranging from 0.0107 to 0.0509 mmol Hg g^-1.The retention was not affected by the presence of others heavy metals studied in this work as expected.     

Polydopamine Nanoparticles as a New and Highly Selective Biosorbent for the Removal of Copper (II) Ions from Aqueous Solutions

The adsorption and desorption of copper (II) ions from aqueous solutions were investigated using polydopamine (PD) nanoparticles. The nanoscale PD nanoparticles with mean diameter of 75?nm as adsorbent were synthesized from alkaline solution of dopamine and confirmed using scanning electron microscopy and X-ray diffraction analysis. The effects of pH (2?C6), adsorbent dosage (0.2?C0.8?g?L^?1), temperature (298?C323?K), initial concentration (20?C100?mg?L^?1), foreign ions (Zn²⁺, Ni²⁺, Cd²⁺, Fe²⁺, and Ag⁺), and contact time (0?C360?min) on adsorption of copper ions were investigated through batch experiments. The isotherm adsorption data were well described by the Langmuir isotherm model. The maximum uptake capacity of Cu²⁺ ions onto PD nanoparticles was found to 34.4?mg/g. The kinetic data were fitted well to pseudo-second-order model. Moreover, the thermodynamic parameters of the adsorption (the Gibbs free energy, entropy, and enthalpy) were studied.     

Kinetic, Isotherm and Thermodynamic Analysis on Adsorption of Cr(VI) Ions from Aqueous Solutions by Synthesis and Characterization of Magnetic-Poly(divinylbenzene-vinylimidazole) Microbeads

The magnetic-poly(divinylbenzene-1-vinylimidazole) [m-poly(DVB-VIM)] microbeads (average diameter 53-212?μm) were synthesized and characterized; their use as adsorbent in removal of Cr(VI) ions from aqueous solutions was investigated. The m-poly(DVB-VIM) microbeads were prepared by copolymerizing of divinylbenzene (DVB) with 1-vinylimidazole (VIM). The m-poly(DVB-VIM) microbeads were characterized by N(2) adsorption/desorption isotherms, ESR, elemental analysis, scanning electron microscope (SEM) and swelling studies. At fixed solid/solution ratio the various factors affecting adsorption of Cr(VI) ions from aqueous solutions such as pH, initial concentration, contact time and temperature were analyzed. Langmuir, Freundlich and Dubinin-Radushkvich isotherms were used as the model adsorption equilibrium data. Langmuir isotherm model was the most adequate. The pseudo-first-order, pseudo-second-order, Ritch-second-order and intraparticle diffusion models were used to describe the adsorption kinetics. The apparent activation energy was found to be 5.024?kJ?mol(-1), which is characteristic of a chemically controlled reaction. The experimental data fitted to pseudo-second-order kinetic. The study of temperature effect was quantified by calculating various thermodynamic parameters such as Gibbs free energy, enthalpy and entropy changes. The thermodynamic parameters obtained indicated the endothermic nature of adsorption of Cr(VI) ions. Morever, after the use in adsorption, the m-poly(DVB-VIM) microbeads with paramagnetic property were separeted via the applied magnetic force. The magnetic beads could be desorbed up to about 97% by treating with 1.0?M NaOH. These features make the m-poly(DVB-VIM) microbeads a potential candidate for support of Cr(VI) ions removal under magnetic field.     

Removal of Cu(II) Ions from Aqueous Solution by Magnetic Chitosan-Tripolyphosphate Modified Silica-Coated Adsorbent: Characterization and Mechanisms

A magnetic chitosan-modified Fe₃O₄@SiO₂ with sodium tripolyphosphate adsorbent (MTPCS) was synthesized by surface modification of Fe₃O₄@SiO₂ with chitosan using sodium tripolyphosphate (STPP) as the cross-linker in buffer solution for the adsorption of Cu(II) ions from aqueous solution. The structure and morphology of this magnetic nanoadsorbent were examined by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), BET surface area measurements, Fourier transform infrared spectrometer (FTIR), and X-ray photoelectron spectroscopy (XPS). The effects of initial pH, adsorbent amount, and initial concentration of heavy metal ions were investigated by batch experiments. Moreover, adsorption isotherms, kinetics, and thermodynamics were studied to understand the mechanism of adsorbing metal ions by synthesized MTPCS. The results revealed that adsorption kinetics was best depicted by the pseudo-second-order rate mode and intraparticle-diffusion models. The adsorption isotherm fitted well to the Langmuir model. Moreover, thermodynamic study verified the adsorption process was endothermic and spontaneous in nature. The maximum adsorption occurred at pH 5 ± 0.1, and the adsorbent could be used as a reusable adsorbent with convenient conditions.     

Adsorptive Removal of Chromium(VI) from Aqueous Solution by an Agricultural Waste-Based Activated Carbon

Activated carbon was prepared from an agricultural waste, coconut coir, and its characteristics were compared with that of a commercial bituminous coal-based activated carbon. The activated carbon possessed higher surface area, micropore area, micropore volume and average pore diameter, and well-developed meso- and micropores. Batch test on adsorption of chromium(VI) by the coconut coir activated carbon showed that the extent of chromium(VI) adsorption was dependent on chromium(VI) concentration, contact time, pH and activated carbon dose. Maximum adsorption occurred at pH 1.0–2.0 and equilibrium adsorption was attained in 2.5 h. Chromium(VI) adsorption followed pseudo second-order kinetics. Equilibrium chromium(VI) adsorption data for the coconut coir activated carbon and the commercial activated carbon were described by the Langmuir and Freundlich isotherm models and indicated higher chromium(VI) adsorption capacity of the coconut coir activated carbon. Chromium(VI) adsorption capacity of the coconut coir activated carbon was compared with that of activated carbon prepared from different waste material and bituminous coal. The coconut coir activated carbon showed high limiting capacity for adsorption of chromium(VI). Coconut coir activated carbon is a suitable substitute for commercial activated carbon in the adsorptive removal of chromium(VI) from water.     

Utilisation of Rubber Wood Shavings for the Removal of Cu(II) and Ni(II) from Aqueous Solution

The potential of heat and chemically treated rubber wood shavings (RWS) to remove Cu(II) and Ni(II) was evaluated at bench-scale by varying parameters such as initial Cu(II) and Ni(II) concentrations, contact time and adsorbent dosage. Maximum Cu(II) and Ni(II) uptake was achieved using NaOH-treated RWS after 5 h of contact time, pH 5.0 (Cu), 5.5 (Ni) and 6.0 (mixed-metal solution), initial Cu(II) and Ni(II) of 100 mg L^?1 and RWS dosage of 0.3% (w/v). Point of zero charge (pH_PZC) value of 4.35 suggests the appropriateness of pH range used. Higher Cu(II) and Ni(II) adsorption following NaOH treatment was due to smaller average pore diameter (34.63 Å), higher mesopore content and higher surface negativity charge. EDAX analysis confirmed the presence of Cu and Ni on the surface of the RWS. The importance of carboxyl and hydroxyl functional groups during Cu(II) and Ni(II) removal is supported by the FTIR analysis and good correlation (R ² of 0.96–0.99) with the pseudo-second-order adsorption kinetic model. The results indicate the potential of using RWS as an alternative adsorbent to remove Cu(II) and Ni(II) from industrial wastewaters.     

Use of Gisenyi Volcanic Rock for Adsorptive Removal of Cd(II), Cu(II), Pb(II), and Zn(II) from Wastewater

Volcanic rock is a potential adsorbent for metallic ions from wastewater. This study determined the capacity of Gisenyi volcanic rock found in Northern Rwanda to adsorb Cd, Cu, Pb and Zn using laboratory scale batch experiments under a variety of experimental conditions (initial metal concentration varied from 1 to 50 mg/L, adsorbent dosage 4 g/L, solid/liquid ratio of 1:250, contact time 120 h, particle size 250–900 μm). The adsorbent had a surface area of 3 m²/g. The adsorption process was optimal at near-neutral pH 6. The maximal adsorption capacity was 6.23, 10.87, 9.52 and 4.46 mg/g for Cd, Cu, Pb and Zn, respectively. The adsorption process proceeded via a fast initial metal uptake during the first 6 h, followed by slow uptake and equilibrium after 24 h. Data fitted well the pseudo second-order kinetic model. Equilibrium experiments showed that the adsorbent has a high affinity for Cu and Pb followed by Cd and Zn. Furthermore, the rock is a stable sorbent that can be reused in multiple sorption–desorption–regeneration cycles. Therefore, the Gisenyi volcanic rock was found to be a promising adsorbent for heavy metal removal from industrial wastewater contaminated with heavy metals.     

Sawdust: Cost Effective Scavenger for the Removal of Chromium(III) Ions from Aqueous Solutions

Cr(III) ions sorption onto sawdust of spruce (Picea smithiana) has been studied thoroughly using radiotracer technique. Maximum sorption (94%) of Cr(III) ions (8.98×10^?5 M) onto sorbent surface is achieved from deionized water in 20 min agitation time using 200 mg of sawdust. The sorption data followed the Freundlich, Dubinin-Radushkevich (D-R) and Langmuir isotherms. Freundlich constants l/n = 0.86 ± 0.07 and C _e = 85.0 ± 25.8 mmole g^?1 have been estimated. Sorption capacity, X _m = 0.82± 0.3 mmole g^?1, β = ?0.00356± 0.00017 kJ² mole^?2 and energy, E = 11.9± 0.3 kJ mole^?1 have been evaluated using D-R isotherm. The Langmuir constants Q = 5.8± 0.2 μmole g^?1 and b = (7.4± 0.5)×10⁴ dm³ mole^?1 have been calculated. The variation of sorption with temperature yields thermodynamic parameters Δ H = ?11.6± 0.3 kJ mole^?1, Δ S = ?16.2± 0.9 J mole^?1 K^?1 and Δ G = ?6.8± 0.3 kJ mole^?1 at 298 K. The negative value of enthalpy and free energy reflect the exothermic and spontaneous nature of sorption respectively. Among the anions studied oxalate, citrate, carbonate and borate have reduced the sorption. The cations Y(III), Ce(II) and Ca(II) suppressed sorption. The sawdust column can be used to separate Cr(III) ion from Cs(I), I(I),Tc (VII) and Se (IV).     

Sorption of Copper(II) from Aqueous Solution by Peat

The use of peat for removal of copper(II) from aqueous solution has been investigated at various initial copper ion concentrations and masses of peat. The equilibrium sorption study can be described by the Langmuir equation and defined in terms of the operating lines for each batch contacting system. The mechanisms of the rate of sorption of copper(II) were analysed using the Elovich equation and a pseudo-second-order model. Both rate mechanisms provided a very high degree of correlation of the experimental sorption rate data suggesting either model could be used in design applications.     

Kinetic,Equilibrium, and Thermodynamic Analyses of Ni(II) Biosorption from Aqueous Solution by Acorn Shell of <Emphasis Type="Italic">Quercus crassipes</Emphasis>

Exposure to divalent nickel [Ni(II)] poses a significant risk to human health. The present study was conducted to evaluate the biosorption capacity of acorn shell of Quercus crassipes Humb. & Bonpl. (QCS) for removal of Ni(II) ions from aqueous solutions in terms of kinetics, equilibrium, and thermodynamics. Batch biosorption studies showed that the Ni(II) biosorption behavior of QCS is strongly dependent on solution pH, shaking contact time, initial Ni(II) concentration, and temperature. Specifically, Ni(II) biosorption was found to increase with increasing solution pH, contact time, initial Ni(II) concentration, and temperature. Modeling of the Ni(II) biosorption kinetic and equilibrium data showed that the best agreement of experimental data was achieved with the pseudo-second-order kinetics model and the Freundlich isotherm model, respectively. The calculated thermodynamic parameters indicated that the Ni(II) biosorption process was endothermic, non-spontaneous, and chemical in nature. Fourier-transform infrared (FTIR) spectroscopy analysis showed that acidic functional groups, namely hydroxyl, carbonyl, and carboxyl functional groups, present on the QCS surface are likely to be involved in the biosorption of Ni(II) ions. The performance of QCS was compared with those of other reported biosorbents in terms of the efficiency of Ni(II) removal from aqueous solutions, revealing that QCS is highly effective in terms of its biosorption capacity. These findings indicate that QCS can be used as a low-cost, highly effective, and environmentally friendly alternative biosorbent for the detoxification of Ni(II)-contaminated water and wastewater.     

Batch Chromium(VI), Cadmium(II) and Lead(II) Removal from Aqueous Solutions by Horticultural Peat

The selectivity and uptake capacity of horticultural peat available in Romania was evaluated with respect to the removal of Cd(II), Cr(VI) and Pb(II) ions from aqueous solution. The kinetics, sorption capacities, selectivity and pH dependence of sorption were determined. The influence of metal concentration in solution is discussed in the terms of Langmuir and Freundlich isotherm and constants. Sorption capacities increased with increasing metal concentration in solution. For solutions containing 300 mg/l of metal, the observed uptake capacities were 20 mg Cd(II)/g peat, 15 mg Cr(VI)/g peat and 30 mg Pb(II)/g peat. The study proved that horticultural peat is a suitable material for the removal of the studied heavy metal ions from aqueous solutions, achieving removal efficiencies higher than 90%, and could be considered as a potential material for treating effluent polluted with Cd(II), Cr(VI) and Pb(II) ions.     

Combined Removal of Zinc (II) and Cadmium (II) from Aqueous Solutions by Adsorption onto High-Calcium Turkish Fly Ash

The aim of this work is the investigation of possible use of flyash in the removal of zinc (Zn²⁺) and cadmium (Cd²⁺) contained in aqueous solutions. Batch adsorption experiments wereperformed in order to evaluate the removal efficiency oflignite-based fly ash. The parameters studied include contact time, pH,temperature, initial concentration of the adsorbate and fly ashdosage. The contact time necessary to attain equilibrium was found to be two hours. Maximum adsorption occurred in the pH range of 7.0 to 7.5. The percent adsorption of Zn²⁺ and Cd²⁺ increased with an increase in concentration of Zn²⁺ and Cd²⁺, dosage of fly ash and temperature. Theapplicability of Langmuir isotherm suggests the formation ofmonolayer coverage Zn²⁺ and Cd²⁺ ions at the outer surface of the adsorbent. Thermodynamic parameters suggested the endothermic nature of the adsorption process. The fly ashwas found to be an metal adsorbent as effective as activated carbon.     

Preparation of Titanate Whiskers Starting from Metatitanic Acid and Their Adsorption Performances for Cu(II), Pb(II), and Cr(III) Ions

The accumulation of metals and nutrients in biosolid-amended soils and the risk of their excess uptake by plants is a topic of great concern. This study examines the elemental uptake and accumulation in five vegetable plants grown on biosolid-applied soils and the use of spectral reflectance to monitor the resulting plant stress. Soil, shoot, root, and fruit samples were collected and analyzed for several elemental concentrations. The chemical concentrations in soils and all the plant parts increased with increase in applied biosolid concentrations. The Cu and Zn concentrations in the plant shoots increased in the order of collard?<?radish?<?lettuce?<?tomato?<?pepper. The Cu and Zn concentrations accumulated significantly in the fruits of the tomato plants compared to other plants. Among all the plants, the shoot concentration factor (SCF) of Zn was significantly higher for pepper plants, indicating increase in uptake of Zn. The shoot relative uptake index (SRUI) of Cu and Zn increased in the order of collard?<?radish?<?lettuce?<?tomato?<?pepper. The shoot dry weight and spectral reflectance of the radish plants in the near-infrared (NIR) region (800–1,300 nm) decreased significantly with increase in biosolid concentration compared to other plants. Increase in plant stress with increase in biosolid dose was evident in radish plants through significant reduction in Normalized Difference Vegetative Index (NDVI). This study indicates the potential use of spectral reflectance as a tool for the screening and monitoring of stress-sensitive plant species and their physiology and as a result, indirectly assesses the chemical concentrations in soils and plants.     

Chemically Modified Silica Gel with N-(2-aminoethyl)-Salicylaldimine for Simultaneous Solid Phase Extraction and Preconcentration of Cu(II), Ni(II), Cd(II) and Zn(II) in waters

In this study, N-(2-aminoethyl)salicylaldimine bonded silica gel was synthesized and characterized using Fourier transform infrared and C, H, N elemental analysis. The analytical conditions such as the pH and volume of the solution, flow rates of the sample solution and the type of eluent to achieve the simultaneous preconcentration of Cu(II), Ni(II), Cd(II) and Zn(II) were optimised using the modified silica gel loaded column using a solid phase extraction technique. Samples (50?C500?ml) containing metal ions at optimal pH of 8 were passed through the column filled with the modified silica gel at 7?ml min^?1 and then elution was achieved using 5?ml of 0.25?M HCl. The concentrations of metal ions in the eluates were determined using flame atomic absorption spectrometry (FAAS). The effects of matrix ions were also studied and none of the major ions interfered to the proposed method. The accuracy of the developed method was validated using a certified reference water sample (Ontario Lake water, NWTMDA-54.4). The method was successfully applied to the analysis of various natural water samples. The adsorption capacities of the modified silica gel for Cu(II), Ni(II), Cd(II) and Zn(II) ions were determined and found to be 0.332, 0.261, 0.130 and 0.375?mmol g^?1, respectively.     

Highly Efficient Removal of Cu(II) from Aqueous Solution by Using Graphene Oxide

Chemical reagents used by the textile industry are very diverse in their composition, ranging from inorganic compounds to polymeric compounds. Strong color is the most notable characteristic of textile effluents, and a large number of processes have been employed for color removal. In recent years, attention has been directed toward various natural solid materials that are able to remove pollutants from contaminated water at low cost, such as sugarcane bagasse. Cell immobilization has emerged as an alternative that offers many advantages in the biodegradation process, including the reuse of immobilized cells and high mechanical strength, which enables metabolic processes to occur under adverse conditions of pH, sterility, and agitation. Support treatment also increases the number of charges on the surface, thereby facilitating cell immobilization processes through adsorption and ionic bonds. Polyethyleneimine (PEI) is a polycationic compound known to have a positive effect on enzyme activity and stability. The aim of the present study was to investigate a low-cost alternative for the biodegradation and bioremediation of textile dyes, analyzing Saccharomyces cerevisiae immobilization in activated bagasse for the promotion of Acid Black 48 dye biodegradation in an aqueous solution. A 1 % concentration of a S. cerevisiae suspension was evaluated to determine cell immobilization rates. Once immobilization was established, biodegradation assays with free and immobilized yeast in PEI-treated sugarcane bagasse were evaluated for 240 h using UV–vis spectrophotometry. The analysis revealed significant relative absorbance values, indicating the occurrence of biodegradation in both treatments. Therefore, S. cerevisiae immobilized in sugarcane bagasse is very attractive for use in biodegradation processes for the treatment of textile effluents.     

Removal of Ammonia from Aqueous Solutions,Ground Water,and Wastewater Using Mechanically Activated Clinoptilolite and Synthetic Zeolite-A: Kinetic and Equilibrium Studies

Natural zeolite clinoptilolite and synthetic zeolite Na-A were characterized using XRD and SEM to be used as adsorbents for ammonia from aqueous solutions, ground water, and sewage water. Clinoptilolite was mechanically activated for 2, 4, 6, and 8 h to study the effect of activation in enhancing the adsorption capacity. The adsorption by activated natural zeolite and synthetic zeolite is high pH dependent and achieve the best values at pH?=?7. The adsorption capacity of activated natural zeolite increases with increasing the activation from 2 to 8 h achieving removal percentage close to that obtained using synthetic zeolite. The equilibrium was obtained after 60 min for synthetic zeolite and all the activated natural zeolite (except 2-h-activated product, the equilibrium was achieved after 30 min). The kinetic studies reflected the high fitness of the adsorption results of activated natural zeolite products and synthetic zeolite with pseudo-second-order model rather than the other kinetic models. The obtained isotherms reflected the formation of S-type isotherm curve for the adsorption using mechanically activated clinoptilolite and L-type curve for the uptake using synthetic zeolite. The results represented well with Langmuir model followed by Temkin and Freundlich model for adsorption using synthetic zeolite. The uptake using mechanically activated clinoptilolite can be represented by Temkin model rather than both Langmuir and Freundlich models. Thermodynamic parameters indicate spontaneous endothermic adsorption of ammonia using all the zeolitic products under investigation. Finally, the mechanically activated natural zeolite and synthetic zeolite exhibit high efficiency in the removal of ammonia and other water pollutants from ground water and sewage water.     

Removal of Pb(II), Cr(III) and Cr(VI) from Aqueous Solutions Using Alum-Derived Water Treatment Sludge

The sorption of Pb(II), Cr(III) and Cr(VI) from aqueous solution using alum-derived water treatment sludge was investigated using the batch adsorption technique. Samples of sludge from two separate water treatment plants were used (one where alum was used alone and one where it was used in combination with activated C). The sorption characteristics of the two samples were generally very similar. Sorption isotherm data for all three ions fitted equally well to both Freundlich and Langmuir equations. Maximum sorption capacity and indices of sorption intensity both followed the order: Cr(III)?>?Pb(II)?>?Cr(VI). Kinetic data correlated well with a pseudo-second-order kinetic model suggesting the process involved was chemisorption. Sorption was pH-dependant with percentage sorption of Cr(III) and Pb(II) increasing from <30% to 100% between pH?3 and 6 whilst that of Cr(VI) declined greatly between pH?5 and 8. HNO₃ at a concentration of 0.1?M was effective at removing sorbed Cr(III) and Pb(II) from the sludge surfaces and regeneration was successful for eight sorption/removal cycles. It was concluded that water treatment sludge is a suitable material from which to develop a low-cost adsorbent for removal of Cr and Pb from wastewater streams.