Selective Transport of Cu(II) across a Polymer Inclusion Membrane with 1-Alkylimidazole from Nitrate Solutions

The selective transport of copper(II), zinc(II), cobalt(II), and nickel(II) ions from nitrate solutions across polymer inclusion membranes (PIMs), which consist of cellulose triacetate as polymeric support, o-nitrophenyl pentyl ether as plasticizer, and 1-alkylimidazole (alkyl from hexyl- to decyl) as ion carrier was reported. PIM was characterized by using atomic force microscopy (AFM) technique. The results show that Cu(II) can be separated very effectively from other transition metal cations as Zn(II), Co(II), and Ni(II) (at a concentration of 10^?3 mol/dm³ each). Alkyl substituents at position 1 of the imidazole ring have been found to affect the hydrophobic properties and initial flux of the transported metal ions. The efficiency of separation of metal ions by 1-alkylimidazole followed the sequence: Cu(II) > Zn(II) > Co(II) > Ni(II). The highest selectivity coefficient for Cu(II) was found with 1-hexylimidazole and its 1 mol/dm³ solution in PIM. Separation of the ions was more effective for the nitrates(V) than for chlorides.     

Silica functionalized by pyridinecarboximidamides as a novel sorbent of heavy metals ions

ABSTRACT

Two novel sorbents, obtained as a result of surface modification of silica gel for the Cu(II), Co(II) and Ni(II) removal from aqueous solutions were proposed. For the modification, 3-chloropropyltrimethoxysilane, N’-hydroxy-N,N-dioctylpyridine-3-carboximidamide and N’-hydroxy-N,N-dioctylpyridine-4-carboximidamides were used. A series of basic tests on the sorption of Cu(II), Co(II) and Ni(II) were carried out and the presented results indicated that the novel sorbents were able to remove all tested metals ions from the aqueous solutions, and the removal efficiency was dependent on the functionalised agent structure, dosage, metal ions concentration and pH. The Langmuir model also assumed that a monolayer sorption occurred.     

Preparation and Application of Inorganic Microballoons Membrane

Abstract

The primary emulsification to form the microballoons was studied. The effects of preparation conditions against the formation of microballoons were examined. The factors examined were metal species in the external aqueous phase, the concentrations of sodium silicate in the internal phase and Cyanex 923 as carrier. The particle size and shell thickness were found 10 µm and 2 µm, respectively. Since the penetration of metal species through the oil phase was promoted by the increase of carrier concentration. The formation of microballoons was completed in a short time of less than 30 min. The formation of microballoons of Co(II), Ni(II), Zn(II), Sr(II), and Cu(II) were used for removal of these metal ions.     

Synthesis,Characterization, and Applications of a New Chelating Resin Containing 4-2-(Thiazolylazo) Resorcinol (TAR)

A new phenol–formaldehyde based chelating resin containing 4-(2-thiazolylazo) resorcinol (TAR) functional groups has been synthesized and characterized by Fourier transform infrared spectroscopy and elemental analysis. Its adsorption behavior for Cu(II), Pb(II), Ni(II), Co(II), Cd(II), and Mn(II) has been investigated by batch and column experiments. The chelating resin is highly selective for Cu(II) in the pH range 2 ～ 3, whereas alkali metal and alkaline earth metal ions such as Na(I), Mg(II), and Ca(II) are not adsorbed even at pH 6. Quantitative recovery of most metal ions studied in this work except Co(II) is achieved by elution with 2M HNO₃ at a flow rate of 0.2 mL min^?1. A similar trend is observed for distribution coefficient values. The quantitative separations achieved on a mini-column of chelating resin include Cd(II) – Cu(II), Mn(II) – Pb(II), Co(II) – Cu(II), Mn(II) – Ni(II), and Mn(II) – Co(II) – Cu(II). The recovery of copper(II) is quantitative (98.0–99.0%) from test solutions (10–50 mg/L) by 1 mol/L HNO₃-0.01 mol/L EDTA. The chelating resin is stable in acidic solutions below 2.5 M HNO₃ or HCl as well as in alkaline solution below pH 11. The adsorption behavior of the resin towards Cu(II) was found to follow Langmuir isotherm and second order rate.     

Inhibitory effects of Cu,Zn, Ni and Co on nitrification and relevance of speciation

BACKGROUND: The speciation of metals is often overlooked in understanding their observed inhibitory effect in biological systems, in particular in nitrification systems. This study examines the effects of Cu, Zn, Ni and Co on a nitrifying sludge, where the aim is to relate inhibition to speciation. RESULTS: Nitrification inhibition was monitored by O₂ and CO₂ measurements, an approach rarely followed to date. The IC₅₀ value of each metal was expressed in terms of total, free and labile metal. Zn and Cu formed similar species, but had different free and labile fractions. Although free and labile fractions of Cu were much lower than the others, it was the most inhibitory metal. Ni and Co exhibited quite different inhibitory effects on nitrification despite the formation of similar metal species. Co was the least inhibitory metal and exhibited its effect very slowly. CONCLUSION: The study is among the few which examine inhibition and speciation of several metals in a comparative way. In the same nitrification medium each metal formed different species, which is a factor to be considered in interpretation of inhibition. The results may be projected to nitrifying systems to clarify the underlying factors in inhibition. Copyright © 2009 Society of Chemical Industry     

Solid Phase Extraction and Preconcentration of Trace Heavy Metal Ions in Natural Water with 2,2′‐Dithiobisaniline Modified Amberlite XAD‐2

Abstract

A solid phase extraction and preconcentration methodology utilizing a new chelating resin is described for the separation of Cd, Ni, Co, Cu, and Zn. The chelating resin matrix was prepared by covalently linking 2,2′‐dithiobisaniline synthesized from 2‐aminothiophenol with the benzene ring of polystyrene‐divinylbenzene resin Amberlite XAD‐2 through a –N?N– group. Its adsorption and preconcentration behavior for Cd, Ni, Co, Cu, and Zn in aqueous solution was studied using batch and column procedures in detail. The newly designed resin quantitatively adsorbs Cd, Ni, Co, Cu, and Zn above pH 5.0. Subsequent elution with 2 M HCl readily strips the sorbed metal ions from the resin. The sorption capacity is 360, 230, 170, 200, and 150 mol g^?1 for Cd, Ni, Co, Cu, and Zn, respectively. Their preconcentration factors are 80–200. The time for 80% sorption was less than 10 min for all five metal ions. The effects of electrolytes on the preconcentration were also investigated with the recoveries >95%. The procedure was validated by analysis of a standard reference river sediment material (GBW 08301 China). The developed method was successively utilized for the determination of Cd, Ni, Co, Cu, and Zn in tap water and river water by flame atomic absorption spectrometry (FAAS) after column SPE and preconcentration. The 3σ detection limits for these metal ions were found to be 0.10, 0.34, 0.42, 0.16, and 0.52 g L^?1, respectively. The relative standard deviation was <10% for the determination of 10 g each of Cd, Ni, Co, Cu, and Zn in a 100 mL water sample.     

Exploring process options to enhance metal dissolution in bioleaching of Indian Ocean nodules

Polymetallic Indian Ocean nodules offer a lucrative resource for valuable strategic metals such as Cu, Co and Ni. A novel bioleaching process using cell‐free spent growth medium from a fully‐grown culture of a marine organism isolated from the nodules (Bacillus M1) dissolved about 45% Co, and 25% Cu and Ni at a the pH of 8.2 in 4 h. To enhance metal dissolution, different modifications in the bioleaching process, such as increasing the pH of the spent growth medium, carrying out leaching in multiple steps, and introducing organic reductant in the leach pulp, were investigated in this study. Increasing the initial pH of the spent growth medium to above 12 resulted in a 25–30% increase in dissolution of Cu, Co and Ni. The pK_a value for the spent growth medium was observed to be in the range of 11.5–12.5. UV‐visible spectroscopy of the growth medium at pH values above 10.0 suggested a change in the structure of complexing phenolic substances present therein. A four‐step leaching process using the spent growth medium, each step lasting for about 4 h, was able to bring around 60% Cu and Ni and 85% Co in solution. About 85% Co, 90% Cu and 60% Ni were dissolved in two‐stage leaching, in which the bioleached residue was treated with the spent growth medium from Acidithiobacillus thiooxidans in the second cycle. The effects of concentration of starch (0.1–10%) as an organic reductant to the spent growth medium were also studied. The dissolution of Cu, Co and Ni stabilized at about 80–85% at a starch concentration of 3% and did not increase much thereafter. Copyright © 2004 Society of Chemical Industry     

Phytoextraction of Au: Uptake,accumulation and cellular distribution in Medicago sativa and Brassica juncea

The influence of metal concentration, solution pH and exposure time on the phytoextraction (i.e. separation using vascular plants) of Au was investigated for the known metallophytes Brassica juncea (BJ) and Medicago sativa (MS). Metal uptake was inferred using Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES) and in vivo localisation and distribution using proton induced X-ray emission spectroscopy (μ-PIXE). MS roots accumulated a maximum of 287 mg Au g^?1 (dry biomass) and BJ roots a maximum of 227 mg Au g^?1 (dry biomass), both when exposed to a 10,000 ppm aqueous solution of KAuCl_4. MS was found to accumulate comparatively greater quantities of Au than BJ across higher substrate concentrations (40–10,000 ppm Au) whereas BJ was found to be a better accumulator of Au at lower concentrations (5–20 ppm Au). In general MS showed an increase in Au uptake with an increase in Au substrate concentration and the time exposed, whereas for BJ the maximum uptake was observed after 48 h of exposure at higher concentrations (100–10,000 ppm), and then decreased at longer exposure times. The uptake ratio (UR), defined as the ratio of Au concentration in plant tissues to the concentration in the substrate, increased with increasing concentration and exposure time, to a maximum of 995 for MS roots after 72 h exposure. Metal translocation from roots to shoots in BJ increased with increasing substrate concentration, however in the shoots, metal uptake increased from 24 to 48 h and then decreased at 72 h, indicating some threshold level had been reached and metal was then being excluded from the cells, possibly through the phloem to the Au solution. Elemental distribution maps of plant tissues measured using μ-PIXE, show Au present across the entire sample, ranging from the epidermis and cortex, with the greatest concentration occurring within the central stele. This result is suggestive of xylem loading. These results collectively suggest that the separation of Au using vascular plants for applications in mining (phytomining) and remediation (phytoremediation) are viable technologies.     

Studies on extraction and permeation of lanthanum(III) and cerium(III) using cyphos IL 104 as extractant and ion carrier

ABSTRACT

This work shows application of Cyphos IL 104 (trihexyl(tetradecyl)phosphonium bis(2,4,4-trimethylpentyl)phosphinate) as the extractant and the ion carrier of Ce(III) and La(III) from aqueous solutions through polymer inclusion membranes (PIM). These membranes were used for separation of Ce(III) from solution containing La(III), Cu(II), Co(II) and Ni(II). The best results of the separation process were obtained for PIM containing: 20.0 wt.% CTA, 55.0 wt.% NPOE and 25.0 wt.% Cyphos IL 104 at pH 3.8 into 1 M H₂SO₄. The separation coefficients were found in order of S _Ce/La < S _Ce/Cu < S _Ce/Co < S _Ce/Ni.     

Removal of metal ions from electrochemical decontamination solution using organic acids

Applicability of the organic acids and cyclodextrin (CD) for the removal of Fe, Co and Ni from the spent electro-decontamination solution was investigated. Oxalic acid showed the highest removal efficiency: 90% for 0.89 M Fe and 95% for 0.0089 M Co and Ni, respectively. The metal–oxalate precipitates were characterized by differential scanning calorimetry/thermogravimetry analysis (DSC/TGA), Fourier transform infrared (FTIR) and X-ray fluorescence (XRF). After thermal decomposition at >300°C, the metal–oxalate precipitates were transformed into metal oxides (Fe₂O₃, FeO, CoO and NiO) and pure metals (Co and Ni). The results imply that organic acids have a high potential for the removal of heavy metals from electro-decontamination solutions.     

Exploring Lower Limits of Plant Elemental Defense by Cobalt, Copper, Nickel, and Zinc

Elemental defense is a relatively newly recognized phenomenon in which plants use elements present in their tissue to reduce damage by herbivores or pathogens. In the present study, neonates of the generalist herbivore, Spodoptera exigua (Hübner) (Lepidoptera: Noctuidae), were fed artificial diets amended with varying concentrations of Co, Cu, Ni, and Zn that are hyperaccumulated by plants to determine minimum lethal concentrations (MLC) and minimum sublethal concentrations (MSC) for each metal. MLC values (dry mass) for Co (45 μg/g), Ni (230 μg/g), and Zn (280 μg/g) were below published minimum hyperaccumulator levels. MSC levels (dry mass) for Co (15 μg/g), Ni (140 μg/g), and Zn (200 μg/g) were at concentrations lower than published minimum accumulator levels. Furthermore, both MLC and MSC values for Zn were within normal tissue concentrations. These results indicate that elemental defense for Co, Ni, and Zn may be effective at concentrations lower than hyperaccumulator levels and so may be more widespread than previously believed.     

Study on Synthesis, Characterization, Thermal Stability and Conductivity Properties of a New Conjugated Oligoazomethine and some of its Metal Complexes

A novel azomethine oligomer of 2,3-bis[(2-hydroxyphenyl)methylene]diaminopyridine (HPMDAP) was first synthesized by oxidative polycondensation reaction using air and NaOCl as oxidative agents. Optimum reaction conditions for the oxidative polycondensation and the main parameters of the process were established. At optimum reaction conditions, the yield of the product was found to be 69%. Oligomeric complexes of 2,3-bis[(2-hydroxyphenyl)methylene]diaminopyridine with Cd(II), Co(II), Cu(II), Ni(II), Fe(II), Pb(II), Cr(III) and Zn(II) were successfully prepared. Structures of monomer, oligomer and some oligomer metal complexes obtained were confirmed by FT-IR, UV–vis, ¹H- and ¹³C-NMR and elemental analysis. Characterization was carried out by TG-DTA, size exclusion chromatography (SEC), magnetic moment and solubility tests. The ¹H- and ¹³C-NMR data showed that polymerization proceed by C–C coupling of ortho and para positions according to –OH group of HPMDAP. Elemental analysis of chelates suggests that the metal ligand ratio is about 1:2. Molecular weight distribution values of the products were determined by size exclusion chromatography (SEC). According to TG analyses, the carbonaceous residues of HPMDAP and OHPMDAP were found to be 34.94 and 29.36% at 1000 °C, respectively. Thermal analyses of Cd, Co, Cu, Ni, Fe, Pb, Cr and Zn oligomer–metal complexes were also investigated under N₂ atmosphere between 15 and 1000 °C. Electrical conductivities of OHPMDAP and its metal complexes were also measured with four probe technique.     

Polycyclic Aromatic Hydrocarbons,Heavy Metals,and Genotoxicity of the Suburban Soils from Guangzhou,China

During the past few decades, urban and suburban developments have grown at unprecedented rates and extents with unknown consequences for ecosystem function. The problem of soil pollution as a result of the accelerating development of Guangzhou in China is becoming great concerns. In the present study, gas chromatograph coupled mass spectrometry (GC-MS), inductively coupled plasma mass spectrometry (ICP-MS) and inductively coupled plasma atomic emission spectrometry (ICP-AES) were employed to determine the 16 US Environmental Protection Agency (EPA) priority polycyclic aromatic hydrocarbons (PAHs) and the heavy metals (As, Cr, Cu, Pb, Cd, Hg, and Se) of soils collected from suburban areas of Guangzhou. The genotoxicity of these soils was screened with micronucleus (MN) assay in Vicia faba root cells. The concentrations of the pollutants in the soils were (dried weight): ΣPAHs (230.6–1263 ng·g^?1), As (2282.6–36064 μg·kg^?1), Cr (7109–64699 μg·kg^?1), Cu (7047–56388 μg·kg^?1), Pb (9675.9–93739 μg·kg^?1), Cd (68.5–847.3 μg·kg^?1), Hg (85.4–549.2 μg·kg^?1), and Se (219.2–968 μg·kg^?1), which fell in the moderately polluted range. However, six out of nine soil-exposed groups had a significant increases of MN frequencies observed in the V. faba root cells compared with the negative group (P < 0.05, P < 0.01), indicating that they had potential genotoxic risks. Bringing together the chemical analyses with the biological effects observed in this study, the genotoxic response could at a certain degree be explained by both the soil PAHs and heavy metals. Our results suggested that apart from chemical analysis, bioassays like the MN assay of V. faba root cells should also be included in a battery of tests to assess the eco-environmental risks of urban and/or urbanization in the developing areas on the soils.     

Synthesis of 1,4,8,11‐tetraazacyclotetradecane monomer by addition of acryloyl chloride and its polymer for specific transition metal binding

1,4,8,11‐Tetraazacyclotetradecane (cyclam) was reacted with acryloyl chloride in a 1 : 2 molar ratio in dichloromethane in the presence of pyridine at 0°C. The modified cyclam was polymerized by adding an azobisisobutyronitrile initiator and irradiated with a UV lamp under reflux for 6 h. Precipitated cyclam containing polymer in the bulk structure was removed from the suspension by filtration. After washing and drying the final polymeric materials were used for transition metal ion adsorption and desorption studies. A Fourier transform IR spectrophotometer and thermogravimetric analyzer were used to characterize the polymeric structure. The affinity of the polymeric material for transition metal ions was used to test the adsorption–desorption of selected ions [Cu(II), Ni(II), Co(II), Cd(II), Pb(II)] from aqueous media containing different amounts of these metal ions (5–800 ppm) at different pH values (2.0–8.0). It was found that the adsorption rates were high and the adsorption equilibrium was reached in about 30 min. The uptake of the transition metal ions onto the polymer from solutions containing a single metal ion was 3.17 mmol/g for Cu(II), 0.98 mmol/g for Cd(II), 0.79 mmol/g for Co(II), 0.78 mmol/g for Ni(II), and 0.32 mmol/g for Pb(II). This polymer showed high affinity for Cu(II) compared to the other metal ions in the single ion solution and in the mixture of transition metal ions. The affinity order of the transition metal ions was Cu(II) ? Ni(II) > Cd(II) > Co(II) > Pb(II) for competitive adsorption. More than 95% of the adsorbed transition metal ions were desorbed in 2 h in a desorption medium containing 1.0M HNO₃. Poly(cyclam) was found to be suitable for repeated use of more than five cycles without a noticeable loss of adsorption capacity. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1406–1414, 2002     

The 2014 Murray Raney Award Lecture: Architecture and Preparation of Supported Nickel Catalysts

The so-called method of sequential co-precipitation allows the production of Ni or Co catalysts varying in metal content, metal dispersion, structure and texture. In this method at first the metal is precipitated and subsequently the support precursor or “stabilizer”. Deposition–precipitation of base metals (Ni, Co, Cu) starting from metal ammine complexes yields highly dispersed metals, uniformly distributed across the carrier surface.

     

Partial methane oxidation into synthesis gas over catalysts supported on meshed metallic materials

Comparative tests of metal catalysts (Pd, Ni, Co, and Cu on a metal gauze and FeCrAl alloy foil) obtained in two ways—thermochemical and electrochemical metal deposition—have been carried out in order to develop efficient catalysts supported on meshed metallic materials for partial methane oxidation into synthesis gas. The tests have been performed in the 680–1000°C range in a flow reactor (10 mm i.d.) with a catalyst in the form of a rolled metal gauze or FeCrAl foil mounted inside. The metallic supports (gauze and foil) with metals (Pd, Ni) supported on them are promising as catalysts for producing synthesis gas by partial methane oxidation in a narrow range of oxygen : methane molar ratios (O₂ : CH₄ = 0.45–0.55). An SEM examination of the catalyst surfaces has demonstrated that the thermochemical deposition of Group VIII metals yields a more branched active metal surface that ensures almost 100% methane conversion at a CO selectivity of >90% even at 900°C.     

Kinetic and Equilibrium Modeling of Pb(II) and Co(II) Sorption onto Rose Waste Biomass

Abstract

An attempt was made to assess the biosorption potential of rose waste biomass for the removal of Pb(II) and Co(II) ions from synthetic effluents. Biosorption of heavy metal ions (>90%) reached equilibrium in 30 min. Maximum removal of Pb(II) and Co(II) occurred at pH 5 and 6 respectively. The biosorbent dose for efficient uptake of Pb(II) and Co(II) was 0.5 g/L for both metals. The biosorbent size affected the Pb(II) and Co(II) biosorption rate and capacity. Rose waste biomass was found effective for Pb(II) and Co(II) removal from synthetic effluents in the concentration range 10–640 mg/L. Equilibrium sorption studies showed that the extent of Pb(II) and Co(II) uptake by the rose waste biomass was better described by the Langmuir isotherm in comparison to the Freundlich model. The uptake capacities of the two metal ions were 156 and 27.15 mg/g for Pb(II) and Co(II) respectively.     

Decouple and compare the role of abiotic factors and developed iron and sulphur oxidizers for enhanced extraction of metals from television printed circuit boards

Chemical leaching agents were compared for metal extractions from selected e-waste. Effect of iron, sulphur oxidizers and the formulated consortium were investigated for metals extraction from television printed circuit boards. The consortium showed maximum metal leaching efficiency. The bioleaching profile was studied as a function of pH, redox potential, acid consumed and the amount of Cu, Zn and Ni extracted. At 10 g/L of e-waste, 90%, 93% and 87% of Cu, Zn and Ni were extracted within 96 h. Ethylene diamine tetra acetic and pyrite were found beneficial. Two-step process resulted in more metal extraction even at 100 g/L pulp density.     

Mechanistic study of active transport of copper (II) using LIX 54 across a liquid membrane

The present work describes the mechanism of active transport of copper(II) through an immobilized liquid membrane (ILM) containing LIX 54 (β‐diketone) dissolved in Iberfluid as mobile carrier. An uphill transport model has been described and equations have been derived taking into account aqueous boundary layer diffusion and liquid membrane diffusion as simultaneous controlling factors. In the present model, various cases were discussed using the carrier LIX 54 and different chemical species; the diffusional membrane resistance for lower and higher concentrations of extractant was evaluated. The diffusion coefficients were observed to decrease with increase in ­the extractant concentration, ranging from 4.1 × 10⁻³ to 1.65 × 10⁻² mol dm⁻³ Plotting [Cu]₀−[Cu]_t vs time resulted in a slope of [HR]₀A/2Δ_orgV taking into account the complex species, CuR₂, in the membrane. The mass transfer coefficient (Δ_org ⁻¹), the diffusion coefficient of the metal carrier species (D_org) and the thickness of the aqueous boundary layer were calculated from the proposed model for LIX 54. More than 90% of the Cu(II) could be separated using LIX 54 in the presence of various metals such as Ni, Co(II) and Zn. © 2000 Society of Chemical Industry     

Removal of divalent nickel from aqueous solution using blue-green marine algae: adsorption modeling and applicability of various isotherm models

Adsorption of Ni(II) onto blue-green marine algae (BGMA) is investigated under batch condition. Under optimum experimental conditions, the initial Ni(II) metal ion concentration is varied from 25 to 250 ppm and the maximum adsorption capacity of BGMA is found to be 42.056 mg/g. The optimum pH, biomass loading, and an agitation rate on maximum removal of Cu(II) ion are found to be 6, 2 g, and 120 rpm, respectively. 24 h of contact time is allowed to achieve equilibrium condition. All the experiments are carried out at room temperature. The equilibrium experimental data infer that the isotherm is L-shaped. It is the indication of no strong competition between solvent and Ni(II) to occupy the active sites of BGMA. Also, it indicates that the BGMA has a limited sorption capacity for adsorption of Ni(II). The experimental data are tested with various isotherm models; subsequently, the mechanism of adsorption is identified and the characteristic parameters for process design are established. Fritz–Schlunder-V isotherm model is highly significant in establishing the mechanism of adsorption of Ni(II) under the conditions employed in this investigation followed by Freundlich. The q_max of 41.89 mg/g obtained by this model indicates its relevance more precisely with experimental data.