Selective Separation of Nickel (II) and Cobalt (II) from Waste Water by Using Continuous Cross-Flow Micellar Enhanced Ultrafiltration with Addition of Chelating Agent

The performance of continuous cross-flow micellar enhanced ultrafiltration (MEUF) is evaluated for the selective separation of nickel (Ni²⁺) and cobalt (Co²⁺) from the aqueous stream using anionic surfactant sodiumdodecyl sulfate (SDS) and the mixture of the anionic and nonionic surfactant (SDS+TritonX-100) with the addition of iminodiacetic acid (IDA) as a chelating agent. Operating parameters like operating time (upto 100 min), cross flow rate (100–175 mL/min.), pH of the feed solution (3-6 Cheryan , M. ( 1998 ) Process Design in Ultrafiltration and Microfiltration Handbook ; Technomic Publishing Co. Inc : USA . Scamehorn , J.F. ; Ellington , R.T. ; Christian , S.D. ; Penny , B.W. ; Dunn , R.O. ; Bhat , S.N. ( 1986 ) Removal of multivalent metal cations from water using micellar-enhanced ultrafiltration . AIChE Symp. Ser. , 82 ( 250 ): 48 – 58 . Baek , K. ; Yang , J.W. ( 2004 ) Cross flow micellar-enhanced ultrafiltration for removal of nitrate and chromate: competitive binding . J. Hazard. Mater. , B108 : 119 – 123 . Yurlova , L. ; Kryvoruchko , A. ; Kornilovich , B. ( 2002 ) Removal of Ni (II) ions from waste- water by micellar-enhanced ultrafiltration . Desal. , 144 : 255 – 260 . ), molar concentration ratio of the chelating agent to metals (C/M ratio, 0.5–2.5), and molar concentration ratio of the surfactant to metals (S/M ratio, 5–9) were studied to investigate the effectiveness of the process on selective separation. For the single surfactant system at all empirically selected parameters, 92% Ni²⁺ in the permeate and 94% Co²⁺ in the retentate was achieved whereas for the mixed surfactant system 93% Ni²⁺ in permeate and 84% Co²⁺ in retentate was achieved. Flux variation for single and mixed surfactant system was studied. Flux observed for the single surfactant system was 36 L/m².h and for the mixed surfactant system was 31.5 L/m².h. Flux measurement also indicates insignificant fouling of the membrane.     

Removal of Lead(II) from Aqueous Solutions using Pre-boiled and Formaldehyde-Treated Onion Skins as a New Adsorbent

The adsorption characteristics of Pb²⁺ on pre-boiled treated onion skins (PTOS) and formaldehyde-treated onion skins (FTOS) were evaluated. The effects of Pb²⁺ initial concentration, agitation rate, solution pH, and temperature on Pb²⁺ adsorption were investigated in batch systems. Pb²⁺ adsorption was found to increase with increase in initial concentration. The point of zero net charge (PZC) was 6.53. The optimum pH for the maximum removal of Pb²⁺ was 6.0. The adsorption equilibrium data was best represented by the Langmuir isotherm model for FTOS and the Freundlich isotherm model for PTOS. The maximum amounts of Pb²⁺ adsorbed (qm), as evaluated by the Langmuir isotherm, was 200 mgg^?1 for FTOS. The efficiencies of PTOS and FTOS for Pb²⁺ removal were 84,8.0% and 93.5% at 0.15 g/200 mL^?1 adsorbent dose, respectively. (C ₀ = 50 mg L^?1). Study concluded that onion skins, a waste material, have good potential as an adsorbent to remove toxic metals like Pb²⁺ from water. Boehm titration analysis was conducted to determine the surface groups. It was found that the adsorption kinetics of Pb²⁺ obeyed pseudo-first-order kinetic model as based on Δq (%) values. FTIR and SEM images before and after adsorption was recorded to explore changes in adsorbent-surface morphology. Activation energy (Ea) was obtained as 25.596 kJ/mol.     

Layered Double Hydroxides Derived from MIL-88A(Fe) as an Efficient Adsorbent for Enhanced Removal of Lead (II) from Water

The efficient removal of lead (II) from aqueous solution remains a big problem and the development of novel nanomaterials as adsorbents by various technologies to solve this problem is promising. This study contributed a novel nanostructure of MIL-88A-layered double hydroxides (LDHs) as the adsorbent for Pb²⁺, which was synthesized by a two-step solvothermal method with MIL-88A(Fe) as the precursor. The as-prepared material featured a chestnut-like core-shell structure, and exhibited excellent removal performance towards Pb²⁺ from water in comparison to MIL-88A(Fe) and LDHs (directly synthesized). The adsorption of Pb²⁺ by the MIL-88A-LDHs conformed to the pseudo-second-order kinetic model and the Langmuir and Freundlich isotherm models. The maximal adsorption capacity was 526.32, 625.00, and 909.09 mg g⁻¹ at 278, 298, and 318 K, respectively. The thermodynamic parameters suggested that the adsorption was an endothermic, entropy-increasing, and spontaneous reaction. X-ray photoelectron spectroscopy (XPS) analysis indicated that the surface complexation was mostly responsible for Pb²⁺ elimination. The MIL-88A-LDHs can be readily regenerated and showed good cyclic performance towards Pb²⁺. Thus, the as-prepared MIL-88A-LDHs may hold promise for the elimination of aqueous heavy metals.     

Selective Extraction of Precious Metal Ions with Novel Trident Molecules Containing Pyridyl Groups

Trident molecules containing pyridyl groups have been prepared for use as novel extraction reagents to investigate their physicochemical properties for dissolution into the aqueous phase and their ability, together with their corresponding monomeric analogues, to extract precious metal ions. Differences in their behavior were related to the pK _a values of the trident molecules and the position of the nitrogen atom in the pyridyl groups. The trident molecules exhibit the ability to selectively extract silver from mixtures of other precious metals. The extraction mechanism and the coordination site of the silver ion with a 2-pyridyl derivative were determined by slope analysis and peak shift of the ¹H-NMR spectra of the extraction reagent before and after silver loading.     

The photocatalytic reduction of nitrous oxide with propane on lead(II) ion-exchanged ZSM-5 catalysts

UV irradiation of the Pb²⁺/ZSM-5 catalyst prepared by an ion-exchange method in the presence of N₂O leads to the decomposition of N₂O into N₂. This reaction is found to be dramatically enhanced by the addition of propane to produce N₂ and oxygen-containing compounds such as ethanol or acetone. UV light effective for the reaction lies in wavelength regions shorter than 250 nm where the absorption band of the Pb²⁺ ion ([Xe] 4f¹⁴5d¹⁰6s² [Xe] 4f¹⁴5d¹⁰6s¹6p¹) exists, indicating that the excited state of the isolated Pb²⁺ ions plays a significant role in this decomposition of N₂O both in the absence and the presence of propane, and the role of propane is found to be a capture of oxygen atoms formed by the decomposition of N₂O.     

Heavy Metal Complexation of Thiol-Containing Peptides from Soy Glycinin Hydrolysates

Many thiol-containing molecules show heavy metal complexation ability and are used as antidotes. In this study, the potential function associated with thiol-containing peptides (TCPs) from soy protein hydrolysates as natural detoxicants for heavy metals is reported. TCPs enriched by Thiopropyl-Sepharose 6B covalent chromatography had different molecular weight distributions as well as different numbers of proton dissociable groups, depending on the proteases and degree of hydrolysis. The major contribution of sulfhydryl groups was confirmed by the largest pH decrease between 8.0 and 8.5 of the pH titration curves. The complexation of TCPs with heavy metalswas evaluated by stability constants (β_n) of TCP-metal complexes whose stoichiometry was found to be 1:1 (ML) and 1:2 (ML₂). TCPs from degree of hydrolysis of 25% hydrolysates gave high affinities towards Hg²⁺, Cd²⁺, and Pb²⁺ (giving similar or even bigger lgβ values than that of glutathione). A significantly positive correlation was found between the logarithm of stability constants for ML₂ (lgβ₂) and the sulfhydryl group content. Molecular weight distribution of TCPs affected the complexation with Pb²⁺ notably more than Hg²⁺ and Cd²⁺. These results suggest that soy TCPs have the potential to be used in the formulation of functional foods to counteract heavy metal accumulation in humans.     

Selective Transport of Cu2+ Ions through Bulk Liquid Membrane System Mediated by Erythromycin Ethyl Succinate

The carrier mediated transport of Cu²⁺ ions from an aqueous medium has been examined. The ability of Erythromycin Ethyl Succinate (EES) as a carrier to form a complex with Cu²⁺ ions and transport them to the receiving phase is reported. The fundamental parameters influencing the transport of Cu²⁺ ions such as the pH in the source and receiving phases and concentration of the stripping agent in the receiving phase have been optimized and accordingly, the amount of Cu²⁺ transported across the liquid membrane after 5 h was 94.3 ± 1.8% in the presence of L-histidine as a suitable stripping agent. Moreover, the selectivity and efficiency of Cu²⁺ ions transport from aqueous solution over other cations in ternary and quaternary mixtures have been investigated. The results indicate that our fabricated membrane is very sensitive toward Cu⁺² ions in the presence of heavy metal ions.     

Suppressing Effect of Na+/Ca2+ Exchanger (NCX) Inhibitors on the Growth of Melanoma Cells

The role of calcium ion (Ca²⁺) signaling in tumorigenicity has received increasing attention in melanoma research. Previous Ca²⁺ signaling studies focused on Ca²⁺ entry routes, but rarely explored the role of Ca²⁺ extrusion. Functioning of the Na⁺/Ca²⁺ exchanger (NCX) on the plasma membrane is the major way of Ca²⁺ extrusion, but very few associations between NCX and melanoma have been reported. Here, we explored whether pharmacological modulation of the NCX could suppress melanoma and promise new therapeutic strategies. Methods included cell viability assay, Ca²⁺ imaging, immunoblotting, and cell death analysis. The NCX inhibitors SN-6 and YM-244769 were used to selectively block reverse operation of the NCX. Bepridil, KB-R7943, and CB-DMB blocked either reverse or forward NCX operation. We found that blocking the reverse NCX with SN-6 or YM-244769 (5–100 μM) did not affect melanoma cells or increase cytosolic Ca²⁺. Bepridil, KB-R7943, and CB-DMB all significantly suppressed melanoma cells with IC₅₀ values of 3–20 μM. Bepridil and KB-R7943 elevated intracellular Ca²⁺ level of melanoma. Bepridil-induced melanoma cell death came from cell cycle arrest and enhanced apoptosis, which were all attenuated by the Ca²⁺ chelator BAPTA-AM. As compared with melanoma, normal melanocytes had lower NCX1 expression and were less sensitive to the cytotoxicity of bepridil. In conclusion, blockade of the forward but not the reverse NCX leads to Ca²⁺-related cell death in melanoma and the NCX is a potential drug target for cancer therapy.     

A Novel Highly Copper(ll)-selective Chelating Ion Exchanger Based on Poly(Glycidyl Methacrylate-coethylene Dimethacrylate) Beads Modified with Aspartic Acid Derivative

Abstract

Anchoring the hydroxyaspartic acid onto poly(glycidyl methacrylate-co-ethylene dimethacrylate) (poly(GMA-co-EDMA)) beads or epoxysuccinic acid onto ammoniummodified poly(GMA-co-EDMA) beads resulted in a novel chelating resin, which contained up to 0.37 mmol of the ligand per gram of resin. Batch extraction experiments showed a very high selectivity for Cu²⁺ over Zn²⁺ and Cd²⁺ ions in buffered solutions under competitive conditions.     

Synthesis,Characterization, and Analytical Applications of a New Composite Cation Exchange Material Acetonitrile Stannic(IV) Selenite: Adsorption Behavior of Toxic Metal Ions in Nonionic Surfactant Medium

A composite cation exchange material acetonitrile stannic(IV) selenite was prepared under different experimental conditions. The ion exchange capacity of the material was improved from 0.75 to 1.83 meq g^?1 in comparison to its inorganic counterpart, stannic selenite. The material was characterized on the basis of X-ray, TGA, FTIR, and SEM studies. Ion-exchange capacity, pH titration, elution behavior, and distribution studies were also carried out to determine the preliminary ion-exchange properties of the material. Furthermore, it was investigated that this ion exchange material has a good reusability after 8 times regeneration. The sorption behavior of metal ions was studied in nonionic surfactants namely triton x-100 and tween. On the basis of distribution coefficient studies, several binary separations of metal ions viz- Pb²⁺-Th⁴⁺, Ni²⁺-Th⁴⁺, Ni²⁺-Zn²⁺, Cu²⁺-Ce⁴⁺, Al³⁺-Bi³⁺, and Al³⁺Zn²⁺ was achieved on the packed column of this ion exchange material. The practical applicability of this cation-exchanger was demonstrated in the separation of Th⁴⁺ from a synthetic mixture of Th⁴⁺, Ca²⁺, Sr²⁺, Ni²⁺, and Mg²⁺ as well as Cu²⁺ and Zn²⁺ from a brass alloy sample. Thus, all the studies suggest that acetonitrile stannic(IV) selenite has excellent potential for the removal of metal ionic pollutant species from aqueous media effectively.     

Sorption Properties of Ni2+ Loaded Iron Hydroxide Toward Phosphate and Cd2+ Ions

Abstract

Ni²⁺ ion loaded iron hydroxide was used for sorption of both Phosphate and Cd²⁺ ions from aqueous solution at 303 K and pH range 3–7 in 0.1 M KNO₃ as a background electrolyte. The surface charge density of the loaded surface was computed from potentiometric titrations both in the presence of 0.1 M KNO₃ and 0.01 M Phosphate. It was noted that the presence of phosphate alters the surface and decreases the point of zero charge toward lower pH. The sorption of phosphate was observed to increase with concentration and decrease with increase in pH of the system. However, the sorption of Cd²⁺ was observed to increase both with increase in concentration and pH of the system. The Freundlich equation was successfully applied to the sorption data which gives a straight line with the R² (regression coefficient) values in between 0.94 to 0.99.     

Preparation of Heterogeneous Vanadium (VO2+) Catalyst for Selective Hydroxylation of Cyclohexane by Molecular Oxygen

A vanadium(II) Schiff base ligand, [1,4-bis (salicylidene amino)-phenylene] vanadium oxo complex bonded on carbamate-modified silica gel, has been synthesized. The liquid-phase oxidation reaction of cyclohexane with this catalyst was found to give cyclohexanol at moderate condition (reaction temperature 200 °C, pressure 23.8 atm, catalyst concentration 1.0% and 16 h of reaction time) with considerably higher specificity (18:1 ratio with cyclohexanone and negligible acid formation). The catalyst has been tested for 200 h of reaction and the leaching of the metal occurs negligibly.     

Photoanodic response of iron oxide electrode in aqueous solution and its application to Pb removal under visible light irradiation

The iron oxide electrode was prepared from thermal oxidation of iron at 600 °C for 3 h in air atmosphere. This electrode with the structure of Fe₃O₄ and α-Fe₂O₃ showed the response of photoanodic current to the light with wavelength shorter than 600 nm. The band gap energy of this electrode was 1.99 eV. The onset potential of distinct steady photocurrent and also the flatband potential were 0.80 and 0.09 V vs. Ag/AgCl, respectively, in 0.1 M HNO₃ aqueous solution. The cell consisting of the iron oxide photoanode in HNO₃-Pb(NO₃)₂ and the graphite cathode in H₂SO₄-Ce(SO₄)₂ caused the PbO₂ deposit on the surface of the former electrode due to visible light irradiation without application of voltage. By holding the potential of this electrode at more positive value than 0.90 V, the photoanodic removal rate of Pb²⁺ in HNO₃-Pb(NO₃)₂ solution was higher than that observed when Ce⁴⁺ was used as electron acceptor.     

Determination of neodymium(III) ions in soil and sediment samples by a novel neodymium(III) sensor based on benzyl bisthiosemicarbazone

The PVC membrane, containing benzyl bisthiosemicarbazone (BTC) as a suitable ionophore, exhibited a Nernstian response for the Nd³⁺ ions over a wide concentration range between 1.0 × 10⁻² and 1 × 10⁻⁶ M, with a detection limit of 6.2 × 10⁻⁷ M in the pH range of 3.7-8.3. It demonstrated a fast response time (<10 s) and it could be used for at least 7 weeks without any major potential deviation. Furthermore, the electrode revealed high selectivity with respect to all the common alkali, alkaline earth, transition and heavy metal ions, including the members of the lanthanide family other than Nd³⁺. Concerning its applications, it was effectively employed for the determination of neodymium ions in soil and sediment samples and its validation with CRM.     

A new rhodamine-based single molecule multianalyte (Cu, Hg) sensor and its application in the biological system

A new single molecule multianalyte sensor, vanillic aldehyde rhodamine 6G hydrazone has been designed for the selective detection of Cu²⁺ and Hg²⁺ ions. UV/Vis spectroscopy indicates that the sensor is a good chromogenic chemosensor for Cu²⁺ in 1:99 (v/v) ethanol-water media. Whereas, other ions, such as Li⁺, Na⁺, Mg²⁺, K⁺, Ca²⁺, Cr³⁺, Mn²⁺, Fe³⁺, Co²⁺, Ni²⁺, Zn²⁺, Ag⁺, Cd²⁺, Ba²⁺, Hg²⁺ and Pb²⁺ failed to generate a distinct response. Fluorescence spectral data reveals that the sensor is an excellent fluorescent chemosensor for Hg²⁺ in aqueous ethanol solution and with no fluorescent response toward other ions. The spectroscopic behavior of the sensor in living cells indicated that it can be used for the detection of Cu²⁺ and Hg²⁺ in environmental and biological systems. Mechanisms for the high selectivity of the sensor to Cu²⁺ and Hg²⁺ are discussed.     

Cerium Containing Al- and Zr-Pillared Clays: Promoting Effect of Cerium (III) Ions on Structural and Catalytic Properties

Ce³⁺ containing Al- and Zr-pillared clays were prepared by co-hydrolysis and co-intercalation methods, respectively. The materials were characterized by XRD, IR and near IR techniques. The expansion in the clay lattice as a result of pillaring was confirmed from X-ray diffraction study. The basal spacing for the pillared clay materials was observed typically in the range of 18–23 Å. The IR and near IR studies were employed to show the presence of acidic and non-acidic hydroxyl groups in the pillared clays. The IR peak at 3630 cm⁻¹ corresponding to the structural hydroxyl groups was more intense in pillared clays than in the parent clay. This peak is retained even after calcination at 500^∘C. Various overtone and combination bands were observed in the NIR range of 1200–2500 nm for the pillared clay materials. Pillaring with Al- and Zr-inorganic polycations enhanced the catalytic activity of the parent clays for dehydration of cyclohexanol. The presence of Ce³⁺ ions in the pillared clays was found to influence catalytic activity and stability of the Brønsted acidic sites. The stabilizing effect of cerium ion in the pillared clays is attributed to the competitive site occupancy and prevention of octahedral migration of the catalytically active protons.     

Study on Efficient Adsorption Mechanism of Pb2+ by Magnetic Coconut Biochar

Lead ion (Pb²⁺) in wastewater cannot be biodegraded and destroyed. It can easily be enriched in living organisms, which causes serious harm to the environment and human health. Among the existing treatment technologies, adsorption is a green and efficient way to treat heavy metal contamination. Novel KMnO₄-treated magnetic biochar (KFBC) was successfully synthesized by the addition of Fe(NO₃)₃ and KMnO₄ treatment during carbonization following Pb²⁺ adsorption. SEM-EDS, XPS, and ICP-OES were used to evaluate the KFBC and magnetic biochar (FBC) on the surface morphology, surface chemistry characteristics, surface functional groups, and Pb²⁺ adsorption behavior. The effects of pH on the Pb²⁺ solution, initial concentration of Pb²⁺, adsorption time, and influencing ions on the adsorption amount of Pb²⁺ were examined, and the adsorption mechanisms of FBC and KFBC on Pb²⁺ were investigated. The results showed that pH had a strong influence on the adsorption of KFBC and the optimum adsorption pH was 5. The saturation adsorption capacity fitted by the model was 170.668 mg/g. The successful loading of manganese oxides and the enhanced oxygen functional groups, as evidenced by XPS and FTIR data, improved KFBC for heavy metal adsorption. Mineral precipitation, functional group complexation, and π-electron interactions were the primary adsorption processes.     

The effect of cytosine on the two-step electroreduction of Zn ions in acetic buffers

Cytosine plays an important role in many biological processes since it constitutes the buildings blocks of DNA and RNA. A two-step reduction of Zn²⁺ ions at the dropping mercury electrode in acetic buffers at pH 4 and 5 in the presence of cytosine was examined. The measurements were performed using an impedance method in a wide potential and frequency ranges.The values of the standard rate constants k_s in the both studied system decrease from 3.8 × 10⁻³ to 2 × 10⁻³ cm s⁻¹ at pH 4 and from 5.1 × 10⁻³ to 2.5 × 10⁻³ cm s⁻¹ at pH 5. The values of the standard rate constants k_s1 characterizing the stage of the first electron transfer decrease similarly. However, the values of the standard rate constants k_s2 characterizing the stage of the second electron exchange decrease more markedly in the buffer at pH 4 than in the buffer at pH 5.     

Accumulation of Cu(II) cations in poly(3,4-ethylenedioxythiophene) films doped by hexacyanoferrate anions and its application in Cu-selective electrodes with PVC based membranes

Electrochemical properties of poly(3,4-ethylenedioxythiophene) doped with hexacyanoferrate(II,III) ions (PEDOT(HCF)) were studied in the presence of Cu²⁺ ions. Voltammetric and EDAX studies revealed retention of hexacyanoferrate anions in the polymer film and accumulation of Cu(II) cations, as well as formation of solid copper hexacyanoferrate near the polymer surface.Accumulation of Cu²⁺ ions was found to be advantageous from the point of view of PEDOT(HCF) applications as a solid contact (ion-to-electron transducer) in all-solid-state Cu²⁺-selective electrodes with solvent polymeric polyvinyl chloride (PVC) based membrane, containing Cu²⁺-selective ionophore. Binding of Cu²⁺ ions in the conducting polymer layer results in analyte ions flux into the transducer phase. Thus, pronounced enhancement of selectivity of the all-solid-state Cu²⁺-selective electrode or lower detection limit of the potentiometric response range was achieved, reaching under optimised conditions 10⁻⁷ M CuSO₄.     

A ratiometric fluorescent sensor for zinc(II) with high selectivity

Spectroscopic studies revealed that the compound [N,N′-di(quinoline-2-methylene) -1,2-phenylenediimine] (1) exhibited a rather high selectivity toward Zn²⁺ over other metal ions, even Cd²⁺. In acetonitrile, the red shift of fluorescent emission from 396 nm to 426 nm upon zinc binding is due to the formation of a 1:1 metal/ligand complex.