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.     

Immobilization of Calcined Layered Double Hydroxide into Alginate Hydrogel Beads for PNP and PAP Removal: Kinetics,Isotherms, Thermodynamics,and Mechanism

The calcined layered double hydroxide (CLDH)-alginate hydrogel beads were synthesized by embedding CLDH into alginate hydrogel beads. The beads were used to remove p-nitrophenol (PNP) and p-aminophenol (PAP) from aqueous solution. The structure and composition of CLDH-alginate hydrogel beads were characterized by scanning electron microscopy (SEM) with energy dispersive spectroscopy (EDS), elemental mapping, transmission electron microscope (TEM), X-ray powder diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, BET, and X-ray photoelectron spectroscopy (XPS). The adsorption kinetic, isothermal, thermodynamic properties and adsorption mechanism of PNP and PAP on CLDH-alginate hydrogel beads were studied. The results demonstrated that the adsorption kinetic data fitted the pseudo-second-order model well with the correlation coefficients (R²) of 0.9975 and 0.9995 for PNP and PAP, respectively. The isothermal data followed the Freundlich equation, and the values of R² for PNP and PAP were 0.9728 and 0.9946, respectively. The adsorption processes were feasible, spontaneous, and endothermic. The adsorption mechanism was predominated by anionic exchange and hydrogen bonding for PNP and hydrogen bonding for PAP, which was evidenced by the results of adsorption experiments, characterization of FTIR and XPS, and theoretical calculation. Furthermore, the CLDH-alginate hydrogel beads can be separated easily due to their larger particle size. This will provide convenience in practice application.     

Preparation, Characterization, and Adsorption Behavior of Cu(II) Ions onto Alkali-Treated Weed (Imperata cylindrica) Leaf Powder

The adsorption of Cu(II) ions by sodium-hydroxide-treated Imperata cylindrica (SoHIC) leaf powder was investigated under batch mode. The influence of solution pH, adsorbent dosage, shaking rate, copper concentration, contact time, and temperature was studied. Copper adsorption was considered fast as the time to reach equilibrium was 40–90 min. Several kinetic models were applied and it was found that pseudo-second-order fitted well the adsorption data. In order to understand the mechanism of adsorption, spectroscopic analyses involving scanning electron microscope (SEM) coupled with energy-dispersive spectroscopy (EDS) and Fourier transform infrared (FTIR) spectrophotometer were carried out. Ion exchange was proven the main mechanism involved as indicated by EDS spectra and as there was a release of light metal ions (K⁺, Na⁺, Mg²⁺, and Ca²⁺) during copper adsorption. Complexation also occurred as demonstrated by FTIR spectra involving hydroxyl, carboxylate, phosphate, ether, and amino functional groups. The equilibrium data were correlated with Langmuir, Freundlich, and Dubinin–Radushkevich isotherm models. Based on Langmuir model, the maximum adsorption capacity was recorded at the highest temperature of 310 K, which was 11.64 mg g^?1.     

Study of Ni(II), Cu(II), Pb(II), and Zn(II) Removal Using Sludge and Minerals Followed by MF/UF

This work examined the removal of heavy metals in a system consisting of ultrafiltration (UF) or microfiltration (MF) membranes combined with sludge and minerals. The metals under examination were Ni(II), Cu(II), Pb(II), and Zn(II), while the system performance was investigated with respect to several operating parameters. Metal removal was achieved through various processes including chemical precipitation, biosorption, adsorption, ion exchange, and finally retention of the metals by the membranes. The pH had a profound effect on metal removal, as the alkaline environment favored the metal removal process. The use of sludge resulted in increased levels of metal uptake which was further enhanced with the addition of minerals. The metal removal mechanisms depended on the pH, the metal, and mineral type. The combined sludge?Cmineral?CUF system could effectively remove metal ions at an alkaline environment (pH?=?8), meeting the US EPA recommended long-term reuse limits of lead and copper and the short-term reuse limits of nickel and zinc for irrigation purposes, provided that specific mineral dosages were added.     

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.     

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 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.     

Surfactant-Enhanced Removal of Cu (II) and Zn (II) from a Contaminated Sandy Soil

Batch tests were conducted to know the effectiveness of using surfactants only and surfactants with a complexing agent to remove Cu (II) and Zn (II) from an artificially contaminated sandy soil. SDS (sodium dodecyl sulfate), AOT (alpha-olefin sulfonate) and Tx-100 (Triton X-100) were the surfactants selected as the washing liquids. Complexing agent EDTA (ethylenediaminetetraacetic acid) was also selected for washing the soil. To avoid external factors from interfering with the cleaning process, artificial soil formed by a mixture of clean sand and bentonite was used to form contaminated soil samples. The amount of organic matter present was insignificant. Compared to extraction by distilled water, tests indicated that a six-fold increase in copper extraction occurred due to the presence of surfactants and/or the complexing agent EDTA. Compared to extraction by distilled water, zinc extraction by surfactants and or the complexing agent EDTA was nearly 1.2 to 1.3 times more. Effects of competition as well as interference associated with the adsorption and desorption of these metals are also very briefly reported.     

A Comparative Study of Batch and Continuous Bulk Liquid Membranes in the Removal and Recovery of Cu(II) Ions from Wastewater

The aim of this work was to compare the performance between a batch bulk liquid membrane (BBLM) and a continuous bulk liquid membrane (CBLM) in the removal and recovery of Cu(II) ions from wastewater. Effects of operating parameters affecting the resistance of Cu(II) ion transfer such as stirring speeds of phases in BBLM, flow rates of phases through CBLM and operating temperature of both BBLM and CBLM on the removal and recovery of Cu(II) ions from aqueous solutions were explored. The variations in Reynolds number and thickness of boundary layer of all phases with stirring speed in BBLM and with flow rate in CBLM, as well as changes in the viscosity of membrane phase with temperature in both BBLM and CBLM were also investigated. A comparison of performance between BBLM and CBLM in the treatment of real industrial wastewater was also conducted and evaluated. It was found that BBLM achieved higher extraction (removal) and stripping (recovery) of Cu(II) ions of up to 16% than CBLM over the range of experimental conditions studied. Both BBLM and CBLM were found to remove and recover Cu(II) ions effectively from real industrial wastewater.     

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.     

Cu(Ⅱ)、Pb(Ⅱ)和Cd(Ⅱ)在红壤胶体和非胶体颗粒上吸附的比较

研究了湖南长沙和海南昆仑的2种红壤胶体和非胶体的矿物组成、阳离子交换量(CEC)及Cu(Ⅱ)、Pb(Ⅱ)和Cd(Ⅱ)在土壤胶体和非胶体颗粒表面的吸附行为,以明确红壤胶体对土壤表面化学性质的贡献。X射线衍射分析结果表明,两种红壤胶体的矿物组成均以次生矿物为主,次生矿物又以1∶1型高岭石所占比例最高。土壤非胶体颗粒中石英等原生矿物含量较高。土壤铁铝氧化物主要富集在土壤胶体部分,土壤胶体颗粒中游离氧化铁和游离氧化铝含量明显高于非胶体颗粒,如湖南长沙红壤胶体颗粒游离氧化铁的含量为78.03 g kg~(-1),而非胶体颗粒中仅为9.93 g kg~(-1)。土壤胶体颗粒的CEC显著高于非胶体颗粒部分,2种红壤胶体的CEC约为非胶体的12倍。等温吸附实验结果表明,土壤胶体颗粒对Cu(Ⅱ)、Pb(Ⅱ)与Cd(Ⅱ)的最大吸附量和吸附亲和力均显著大于非胶体颗粒,湖南红壤胶体对3种重金属的吸附量大于海南红壤胶体,与土壤胶体的矿物组成和CEC大小一致。Cd(Ⅱ)在红壤胶体和非胶体颗粒表面主要发生静电吸附,而静电吸附和非静电吸附两种机制均对Cu(Ⅱ)和Pb(Ⅱ)的吸附有重要贡献。     

A Study of Diffusive Gradients in Thin Films for the Chemical Speciation of Zn(II), Cd(II), Pb(II), and Cu(II): The Role of Kinetics

The lability and mobility of Zn(II)–, Cd(II)–, Pb(II)–, and Cu(II)–humic acid complexes were studied using diffusive gradients in thin films (DGT). A unique feature of this research was (1) the use of DGTs with diffusive layer thicknesses ranging from 0.4 to 2.0 mm to study lability and mobility of Zn(II)–, Cd(II)–, Pb(II)–, and Cu(II)–humic acid complexes, combined with (2) the application of a competing ligand exchange (CLE) method using Chelex 100, the same chelating resin that is used in DGT, to study the kinetic speciation. The CLE experiments were run immediately after the completion of the DGT experiments, thereby allowing effects of the competing ligand to be separated from the effects introduced by the use of the polyacrylamide gel that is used in DGT. The results indicate that Zn(II) and Cd(II) tend to form more labile and more mobile complexes with humic acid than Pb(II) or Cu(II). The dissociation rate constants of Zn(II), Cd(II), and Pb(II) were found to increase with the ionic potential of the metal, suggesting that the binding between some trace metals and humic acid has a significant covalent component. Furthermore, the results suggest that the Eigen mechanism may not be strictly obeyed for metals such as Cu(II) which have high rate constants of water exchange, k _w. Consequently, the markedly slow kinetics of Cu(II)-HA species suggests that the usual equilibrium assumption may not be valid in freshwaters.     

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.     

Cu(II) Biosorption and Competitive Studies in Multi-ions Aqueous Systems by Arthrobacter sp. Sphe3 and Bacillus sphaericus Cells: Equillibrium and Thermodynamic Studies

Arthrobacter sp. Sphe3 and Bacillus sphaericus cells were used for Cu(II) biosorption. The effect of contact time, biosorbent dose, equilibrium pH, temperature and the presence of other ions on the efficiency of the process were extensively studied. Optimum pH value and biomass concentration were determined at 5.0 and 1.0?g/l, whereas contact time was found to be 5 and 10?min for Arthrobacter sp. Sphe3 and Bacillus sphaericus biomass, respectively. Equilibrium data fitted very well to Freundlich model (R ²?=?0.996, n?=?2.325, K _f?=?8.141) using Arthrobacter sp. Sphe3. In the case of B. sphaericus, a Langmuir adsorption model [R ²?=?0.996, Q _max?=?51.54?mg-Cu(II)/g] showed to better describe the results. Potentiometric titration and Fourier transform infrared (FTIR) spectroscopy showed that amine, carboxyl and phosphate groups participate in Cu(II)-binding. The calculated thermodynamic parameters indicated the spontaneous and feasible nature of Cu(II) biosorption on both biosorbents. Selectivity of Cu(II) biosorption was examined in binary and multi-ions systems with various anions and cations which are commonly found in municipal and industrial wastewater. A specificity towards Cu(II) was observed in binary mixtures with Cl^-, CO ₃ ^-2 , NO ₃ ^- , SO ₄ ^-2 , PO ₄ ^-3 , Mg⁺² and Ca⁺², and As(V) with the maximum uptake capacity remaining constant even at high competitive ion??s concentrations of 200?mg/l. Desorption studies showed that Cu(II) could be completely desorbed from Cu(II)-loaded Arthrobacter strain Sphe3 and B. sphaericus biomass using 1.0 and 0.8?M HCl, respectively, and both bacterial species could be effectively reused up to five cycles, making their application in wastewater detoxification more attractive.     

Simultaneous determination of Cd(II), Cu(II), Pb(II), and Zn(II) in citrus essential oils by derivative potentiometric stripping analysis

Citrus essential oils are widely used in the food, cosmetics, and pharmaceutical industries, so the determination of heavy metals content is of great importance to guarantee their quality. The present work deals with the quantification of Cd(II), Cu(II), Pb(II), and Zn(II) in different varieties of citrus essential oils, using derivative potentiometric stripping analysis. Two different metals extraction procedures, involving concentrated hydrochloric acid treatment and acid-alcoholic dissolution, are tested on lemon, mandarin, sweet orange, and bergamot essential oils, and they give very similar results. Cd(II), Cu(II), Pb(II), and Zn(II) recovery tests spanned from 95 to 100.50%, providing evidence that metals quantification remained unaffected by the cleanup steps of the two procedures. The repeatability of the hydrochloric acid extraction method, applied on different varieties of essential oils, is >95.00% for Cd(II), Cu(II), Pb(II), and Zn(II), whereas the repeatability of the acid-alcoholic dissolution method is >93.00% for Cu and Cd only in lemon oil. Detection limits obtained for the four analytes, using both procedures, ranged from 0.10 to 0.98 ng g(-)(1) in lemon, mandarin, sweet orange, and bergamot essential oils.     

Removal of Remazol Brilliant Blue Dye from Dye-Contaminated Water by Adsorption Using Red Mud: Equilibrium, Kinetic, and Thermodynamic Studies

Utilization of industrial solid wastes for the treatment of wastewater from another industry could help environmental pollution abatement, in solving both solid waste disposal as well as liquid waste problems. Red mud (RM) is a waste product in the production of alumina and it poses serious pollution hazard. The present paper focuses on the possibility of utilization of RM as an adsorbent for removal of Remazol Brilliant Blue dye (RBB), a reactive dye from dye-contaminated water. Adsorption of RBB, from dye-contaminated water was studied by adsorption on powdered sulfuric acid-treated RM. The effect of initial dye concentration, contact time, initial pH, and adsorbent dosage were studied. Langmuir isotherm model has been found to represent the equilibrium data for RBB?CRM adsorption system better than Freundlich model. The adsorption capacity of RM was found to be 27.8?mg dye/g of adsorbent at 40?°C. Thermodynamic analysis showed that adsorption of RBB on acid-treated RM is an endothermic reaction with ?H ⁰ of 28.38?kJ/mol. The adsorption kinetics is represented by second-order kinetic model and the kinetic constant was estimated to be 0.0105?±?0.005?g/mg?min. Validity of intra-particle diffusion kinetic model suggested that among the mass transfer processes during the dye adsorption process, pore diffusion is the controlling step and not the film diffusion. The process can serve dual purposes of utilization of an industrial solid waste and the treatment of liquid waste.     

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.