Extraction and preconcentration of toxic metal ions from aqueous solution using benzothiazole-based chelating resins

Polystyrene-divinylbenzene resin (PS-DVB) was functionalized with a benzothiazole group. PS-DVB with amino group was initially prepared by nitration and reduction reactions and subsequently treated with ethyl 2-benzothiazolylacetate (BA) to obtain the chelating resin with an amide linkage (BA-PS-DVB). Meanwhile, the amino-PS-DVB was diazotized and coupled with BA to obtain the chelating resin with an azo linkage (azo-BA-PS-DVB). The resins were characterized by elemental analysis and infrared spectroscopy and evaluated for their extraction of Cd(II), Cu(II) and Pb(II) ions in water before their determinations by flame atomic absorption spectrometry (FAAS). Extraction conditions were optimized for batch method such as the pH of the solution, the extraction time and the adsorption isotherm. The optimum pH for the extraction of Cd(II), Cu(II) and Pb(II) are 8.0, 7.0 and 6.0, respectively, while the equilibrium time of all ions was reached within 10-20 min. The adsorption behavior of all the metal ions followed the Langmuir adsorption isotherm. In the column method, the optimum flow rates of metal sorption onto BA-PS-DVB and azo-BA-PS-DVB columns were 2.5 and 4.0 mL min^− 1. Metal ions sorbed onto columns were eluted by 0.5 to 2.0 M HNO₃. The preconcentration factors of Cd(II) and Cu(II) on azo-BA-PS-DVB and Cu(II) on BA-PS-DVB were 50, 50, and 20, respectively. The present column method gave acceptable validation results: 71.2 and 74.0% recovery for Cd(II) and Cu(II) and an overall relative standard deviation (R.S.D) less than 10% (n = 15). The proposed method was applicable for determining Cu(II) in drinking water.     

Solid-state compounds of 2-chlorobenzylidenepyruvate with some bivalent metal ions

Solid-state M-2-Cl-BP, where M stands for Mn, Fe, Co, Ni, Cu, Zn and Pb and 2-Cl-BP is 2-chlorobenzylidenepyruvate, have been synthesized. Thermogravimetry and derivative thermogravimetry (TG/DTG), simultaneous thermogravimetry and differential thermal analysis (TG-DTA), X-ray powder diffractometry, infrared spectroscopy, elemental analysis, and complexometry were used to characterize and to study the thermal behaviour of these compounds. The results led to information about the composition, dehydration, thermal stability and thermal decomposition of the isolated compounds.     

Solid-state compounds of 2-methoxybenzylidenepyruvate with some bivalent metal ions

Solid-state M-2-MeO-BP compounds, where M represents bivalent Mn, Fe, Co, Ni, Cu, Zn and 2-MeO-BP is 2-methoxybenzylidenepyruvate have been synthesized. Simultaneous thermogravimetry-differential thermal analysis (TG-DTA), differential scanning calorimetry (DSC), X-ray powder diffractometry, infrared spectroscopy, elemental analysis and complexometry were used to characterize and to study the thermal stability and thermal decomposition of these compounds. The results led to information about the composition, dehydration, crystallinity and thermal decomposition of the isolated compounds.     

Batch and column study: sorption of perfluorinated surfactants from water and cosolvent systems by Amberlite XAD resins

Amberlite XAD resins have been employed to a great extent as the sorbent for removing or concentrating organic compounds from different matrices. We present for the first time a systematic study on the sorption of perfluorochemical (PFC) surfactants, an emerging class of environmental contaminants, by XAD-7HP (moderately polar) and XAD-2 (nonpolar). The results show that XAD-7HP can strongly sorb PFCs at circumneutral pH; the isotherm-determined linear sorption coefficient can reach 10(6)L/kg. On the other hand, the sorption coefficient for XAD-2 was two orders of magnitude lower than that for XAD-7HP. PFC sorption on XAD-7HP increased with an increase of the perfluorocarbon chain length of PFC and a decrease of the solution pH, indicating the importance of hydrophobic and electrostatic effects. The sorption coefficient for XAD-7HP reduced markedly with increasing fraction of the organic cosolvent (methanol) in the water-cosolvent mixture; however, the trend could not be predicted by a log-linear cosolvency model. Furthermore, the statistical analysis of column test results showed that after regeneration XAD-7HP can be used at least eight times without significant loss of performance. Finally, the experimental results imply that XAD-7HP sorption of shorter-chained PFCs (≤5 perfluorinated carbons) from water can be thermodynamically favorable.     

Separation of humic acid with XAD resins

Summary Separation of humic acid with different XAD resins has been studied. The effect of pH on the adsorption of humic acid by XAD resins and effect of pH on the distribution coefficient constant in a system of XAD resin and humic acid solution are reported. The XAD-12 was found to be the most efficient resin to remove humic acid from a solution at pH 5.0.

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Zusammenfassung Die Abtrennung von Huminsäure mit verschiedenen XAD-Harzen (Amberliten) wurde untersucht. Über den Einfluß des pH auf die Adsorption der Huminsäure an XAD-Harzen und auf den Verteilungskoeffizienten in einem System aus XAD-Harz und Huminsäure-Lösung wurde berichtet. XAD-12 erwies sich als das am besten wirksame Harz, um Huminsäure bei pH 5 aus einer Lösung zu entfernen.

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This study was supported by Office of Water Research and Technology, U. S. Department of Interior.     

Preparation of some metal carbonyl cluster formyl compounds

The reduction of H₂Os₃(CO)₁₀S or HOs₃(CO)₁₀(O₂CMe) with KBH(OPr-i)₃ at low temperatures yields unstable formyl complexes which have been identified by ¹H NMR spectroscopy; at higher temperatures conversion into stable hydridoanions is observed.     

Retention of organic ligands on anionic and nonionic resins: Application to the separation and preconcentration of metal ions

Complexing resins obtained by retention of an organic compound on anionic and nonionic conventional exchangers have been reviewed. The influence of different parameters—nature of fixed ligand, kind and chemical form of the conventional resin, and pH of the aqueous solution—on characteristics and applications of this type of resin has been discussed. Results from the literature have been tabulated to simplify their presentation.     

Preparation and properties of some transition metal phosphorus trisulfide compounds

Transition metal phosphorus trisulfide compounds with the general formula MPS₃, with M = Mn, Fe, Ni, have been prepared by chemical vapor transport, vapor sublimation, and direct combination of the elements. Chemical transport is accomplished by using 75 Torr of chlorine gas as a transport agent and a temperature gradient of 750° → 690°C or 700° → 640°C. The structure of these three compounds, which belongs to the monoclinic space group $\text{C2}\text{m}$, is related to that of CdCl₂ with a distorted cubic close-packing of the sulfur atoms. Metal atoms and phosphorus-phosphorus pairs occupy the trigonally distorted octahedral holes in a ratio of 2:1 and are ordered throughout the structure. Magnetic susceptibility measurements indicate that all three compounds are antiferromagnetic. The paramagnetic moments indicate that the metal ions in each case exist in the divalent high-spin state.     

Thermal studies on 2,6-xylyliminodiacetato compounds of some transition metal ions

Some new 2,6-xylyliminodiacetato compounds of Mn(II), Fe(III), Ni(III), Zn(II) and Cd(II) have been prepared in aqueous media. The thermal behaviour of these compounds has been studied by TG, DTG, and DSC techniques. Heats of dehydration have been calculated from the DSC curves.     

Determination of metal ions by ion chromatography with precolumn electrochemical preconcentration

The determination of heavy metals in concentrations less than 10^-6 mol/L by ion chromatography with conductivity detection requires a preconcentration step. Therefore, a special electrochemical equipment and method was developed for the on-line preconcentration of the divalent metals Ni, Co, Zn and Cd and their subsequent ion chromatographic determination. The loop of the injection valve of an ion chromatograph was replaced by an electrochemical flow-through-cell with a gold working electrode, a platinum auxiliary electrode and a silver/silver sulphate reference electrode. The preconcentration step consists of the deposition of the reduced metals on the electrode surface during a continuous pumping of the sample solution through the cell. After switching of the mobile phase through the cell, the analytes are injected after their reoxidation directly into the mobile phase. A new preconcentration step is simultaneously possible during the actual chromatographic run. An effective separation of the analytes from the matrix is also possible with the proposed system. A maximum of metal ion accumulation was obtained after 120 min in the galvanostatic mode on a gold tube electrode. The detection limits for Co(II), Ni(II), Zn(II) and Cd(II) were improved by a factor of 7.7, 10.4, 11.2, 14.0, respectively, and were in the 0.1 mol/L concentration range with a RSD of 2–6%. The accumulation of metal ions was disturbed in the presence of Cr(III).     

Determination of metal ions by ion chromatography with precolumn electrochemical preconcentration

The determination of heavy metals in concentrations less than 10(-6) mol/L by ion chromatography with conductivity detection requires a preconcentration step. Therefore, a special electrochemical equipment and method was developed for the on-line preconcentration of the divalent metals Ni, Co, Zn and Cd and their subsequent ion chromatographic determination. The loop of the injection valve of an ion chromatograph was replaced by an electrochemical flow-through-cell with a gold working electrode, a platinum auxiliary electrode and a silver/silver sulphate reference electrode. The preconcentration step consists of the deposition of the reduced metals on the electrode surface during a continuous pumping of the sample solution through the cell. After switching of the mobile phase through the cell, the analytes are injected after their reoxidation directly into the mobile phase. A new preconcentration step is simultaneously possible during the actual chromatographic run. An effective separation of the analytes from the matrix is also possible with the proposed system. A maximum of metal ion accumulation was obtained after 120 min in the galvanostatic mode on a gold tube electrode. The detection limits for Co(II), Ni(II), Zn(II) and Cd(II) were improved by a factor of 7.7, 10.4, 11.2, 14.0, respectively, and were in the 0.1 micromol/L concentration range with a RSD of 2-6%. The accumulation of metal ions was disturbed in the presence of Cr(III).     

Determination of heavy metal ions in environmental samples employing preconcentration on novel resins of polyurethane foam linked with o-Aminophenol or o-Hydroxyphenylazonaphthol

o-Aminophenol (AP) and its azo derivative with ß-Naphthol(Naph) is bonded to polyurethane foam (BPUF) and used as solid phase extractor of nickel, cadmium and zinc ions in aqueous solutions prior to their atomic absorption spectrometric determinations. The novel resins of polyurethane foam were characterised by density, elemental analysis, IR spectra and chemical stability. The parameters including pH, sample volume, matrix effects were investigated. The relative standard deviation (RSD) of the combined method of sample treatment, preconcentration and determination with atomic absorption spectrometry is generally lower than 10%. The limit of detection was found between 0.06 and 0.22?µg?L^?1. The procedure was used for determination of analyte ions in natural water samples, apple leaves and fish liver.     

Synthesis of some antipyrinylazo and thiazolylazo compounds with pentan-2,4-dione and their reactions with metal ions

The reagents were synthesized by using pentan-2,4-dione as the coupling component with diazotized 4-aminoantipyrine or 2-aminothiazole. Two kinds of azo compounds were obtained under different conditions: 1-(4-antipyrinylazo)-1-(4-antipyrinylhydrazino)propan-2-one (Azonol A-1) and 3-(4-antipyrinylazo)pentan-2,4-dione (Azonol A-2) from 4-aminoantipyrine, and 1-(2-thiazolylazo)-1-(2-thiazolylhydrazino)propan-2-one (TAA-1) and 3-(2-thiazolylazo)pentan-2,4-dione (TAA-2) from 2-aminothiazole. The structure of Azonol A-1 was determined by single-crystal x-ray crystallography. The reactions of these reagents with various metal ions were examined. Azonol A-1 and TAA-1 form metal chelates at low pH values. Azonol A-1 is useful as a metallochromic indicator in titrations of bismuth with EDTA at pH 0.5–2, and as a spectrophotometric reagent for copper (II) (0.2–1.5 mg l^?1) at pH 0.3–1.2.     

Pore-functionalized polymer membranes for preconcentration of heavy metal ions

Functionalized membranes containing carboxylate, phosphate and sulfonate groups were prepared by UV-initiator induced graft polymerization of the functional monomer (acrylic acid, ethylene glycol methacrylate phosphate (EGMP) and 2-acrylamido-2-methyl-1-propane sulfonic acid) with a crosslinker (methylenebisacrylamide) in the pores of poly(propylene) host membranes. The functionalized membranes thus obtained were characterized by gravimetry, FTIR spectroscopy, radiotracers and scanning electron microscopy for the degree of grafting and water uptake, presence of functional groups, ion-exchange capacity, and physical structure of the membranes, respectively. The uptakes of Cs⁺, Ag⁺, Sr²⁺, Cd²⁺, Hg²⁺, Zn²⁺, Eu³⁺, Am³⁺, Hf⁴⁺ and Pu⁴⁺ ions in the functionalized membranes were studied as a function of acidity of the equilibrating aqueous solution. Among the functionalized membranes prepared in the present work, the EGMP-grafted membrane (with phosphate groups) showed acid concentration dependent selectivity towards multivalent metal ions like Eu³⁺, Am³⁺, Hf⁴⁺ and Pu⁴⁺. The solvent extraction studies of EGMP monomer in methyl isobutyl ketone (MIBK) solvent indicated that divalent and trivalent metal ions form complexes with EGMP in 1:2 proportion, but the distribution coefficients of trivalent metal ions were significantly higher that for the divalent ions. The uptakes of Eu³⁺ ions in monomeric EGMP (dissolved in MIBK) and polymeric EGMP (in the forms of crosslinked gel and membrane) were studied as a function of concentration of H⁺ ions in the equilibrating solution. This study indicated that polymeric EGMP has better binding ability towards Eu³⁺ as compared to monomeric EGMP. The variation of distribution coefficients of Eu³⁺/Am³⁺ in gel and membrane as a function of H⁺ ion concentration in the equilibrating aqueous solution indicated that ionic species held in the membrane and gel were not same. These results indicated that proximity of functional groups (phosphate) plays an important role in metal ion binding with polymeric EGMP.     

Adsorption behaviour of metal ions on hydroximate resins

Some new chelating ion-exchange resins containing a hydroxamic acid moiety attached to a divinylbenzene styrene (DVBS) copolymer, i.e. glycine hydroximate in DVBS (GH-DVBS). anthranilic acid hydroximate in DVBS (AAHDVBS), malonic acid dihydroximate in DVBS (MAH-DVBS) and iminodiacetic acid dihydroximate in DVBS (IDAAH-DVBS). have been synthesized and their various physicochemical characteristics studied. The degree of retention of metal ions by the resins at equilibrium has been determined in terms of the molar distribution coefficient (k(d)). In general, the resins having a dihydroximate moiety are found to be more efficient compared to monohydroximate resins. However, it is of interest to note that the monohydroximate derivative of amino acid (GH-DVBS) showed better metal retention capability than the dihydroximate of carboxylic acid (MAH-DVBS). The selectivity of the resins for transition and highly charged metal ions is quite high compared to that for alkaline earth metals. All the synthesized resins can be utilized for the separation of a mixture of metal ions because the differences in the distribution coefficient values are large enough to permit good separations on columns. However, the GH-DVBS resin was tried for the separation of copper cobalt and copper nickel mixtures at pH 5.5 using the column mode of operation.     

Reactions of 2,5-pyrroledicarboxaldehyde with some metal ions

The coordination chemistry of the recently synthesized 2,5-pyrroledicarboxaldehyde has been investigated. The ligand reacts with metal ions only in basic media in which the pyrrole nitrogen is deprotonated. In the ionic form the ligand is bidentate using the pyrrolate nitrogen and an oxygen of one of the two aldehyde groups. The results of the reactions of the dialdehyde with Ni(II), Cu(II), Co(II), CO(III), Fe(III), Pd(II) and Pt(II) are reported.     

Solid phase extraction and preconcentration of some metal ions using Schiff base immobilised silica gel followed by ICP-OES

ABSTRACT

In this study, a simple and efficient solid phase extraction procedure was developed for simultaneous separation and preconcentration of Ba, Cd, Co, Cu, Mn and Ni. The methodology was based on preconcentration of the target analytes on N,N’-bis(4-methoxysalicylidene)-1,3-propanediamine modified silica gel prior to inductively coupled plasma optic emission spectrometry detection. The experimental conditions were as follows: pH of sample 5.00; sample and eluent flow rates 3 mL min^?1; sample volume 25 mL; eluent 0.5 mol L^?1 HNO₃; eluent volume 3.0 mL. Preconcentration factor was achieved as 33.3 for Ba, Co, Mn; 83.3 for Cd, Ni; 166.7 for Cu. Limits of detection were found as 0.33, 0.26, 0.27, 0.36, 0.27 and 0.19 µg L^?1 for Ba, Cd, Co, Cu, Mn and Ni, respectively. The relative standard deviations of 2.6–3.8% were obtained via nine parallel analyses. The suggested procedure was successfully validated by the analysis of TMDA-53.3 Lake Ontario water and ERM-CA022a soft drinking water certified reference materials and applied to various natural water samples.     

Thermal and electrical studies on quinoxaline compounds of some first row transition metal ions

The chloro and bromo compounds of quinoxaline with manganese(II), cobalt(II), nickel(II) and copper(II) have been prepared in ethanolic solution. The thermal behaviour of these compounds was studied by thermogravimetry (TG) and differential thermal analysis (DTA). The thermal decomposition studies show that the compounds dichlorobis(quinoxaline) cobalt(II), dibromobis(quinoxaline) cobalt(II) and dibromobis(quinoxaline) manganese(II) form intermediate compounds before the metal halide is produced. The other compounds undergo decomposition with loss of organic ligand and the formation of the metal halide. Electrical conductivities at room temperature range from 1.4 × 10⁻⁶ Ω⁻¹ m⁻¹ for MnCl₂Q to 2.3 × 10⁻³ Ω⁻¹ m⁻¹ for both CoCl₂Q₂ and CoBr₂Q₂. There appears to be a correlation between electrical conductivity and coordination number of the metal atom. From the temperature dependence of conductivity, information has been obtained for donor or acceptor ionization energies. Decomposition temperature, as electrically determined, is in good agreement with the TG method.     

On-line dialysis of some metal ions and metal complexes

The effect of ionic strength, pH and complexing ligands on the dialysis of metal ions, particularly zinc(II), through cellulose acetate membranes, was studied under flow conditions. The dialysis factor, which depends on both the mass transfer and the membrane permeability, was found to be independence of ionic strength in the interaval 0.05–0.3 M and to increase only slightly with pH 4.6 and 7.0. Some common buffer constituents had no effect, but chloride and calcium ions affected the transfer rates. The rate of transfer of the ligands histidine, NTA and EDTA was of the same order of magnitude as that of the metal ions. The transfer rate of the Ni(II)-EDTA complex was the same as that of a mixture of Ni(II) and EDTA. Generally, addition of the chelating agents decreased the metal-ion transfer rates. Partition coefficients between the membrane polymer and the buffers were evaluated and compared with the dialysis factors and there were significant differences with regard to the range of variation, effect of concentration and pH-dependence. The time scale of uptake or release of metal ions by the polymer is much longer than that of a steady-state transfer in dialysis. Partition and dialysis may not be directly related to each other.     

Chemically-modified activated carbon with ethylenediamine for selective solid-phase extraction and preconcentration of metal ions

A new method that utilizes ethylenediamine-modified activated carbon (AC-EDA) as a solid-phase extractant has been developed for simultaneous preconcentration of trace Cr(III), Fe(III), Hg(II) and Pb(II) prior to the measurement by inductively coupled plasma optical emission spectrometry (ICP-OES). The new sorbent was prepared by oxidative surface modification. Experimental conditions for effective adsorption of trace levels of Cr(III), Fe(III), Hg(II) and Pb(II) were optimized with respect to different experimental parameters using batch and column procedures in detail. The optimum pH value for the separation of metal ions simultaneously on the new sorbent was 4.0. Complete elution of absorbed metal ions from the sorbent surface was carried out using 3.0 mL of 2% (%w/w) thiourea and 0.5 mol L⁻¹ HCl solution. Common coexisting ions did not interfere with the separation and determination of target metal ions. The maximum static adsorption capacity of the sorbent at optimum conditions was found to be 39.4, 28.9, 60.5 and 49.9 mg g⁻¹ for Cr(III), Fe(III), Hg(II) and Pb(II), respectively. The time for 94% adsorption of target metal ions was less than 2 min. The detection limits of the method was found to be 0.28, 0.22, 0.09 and 0.17 ng mL⁻¹ for Cr(III), Fe(III), Hg(II) and Pb(II), respectively. The precision (R.S.D.) of the method was lower 4.0% (n = 8). The prepared sorbent as solid-phase extractant was successfully applied for the preconcentration of trace Cr(III), Fe(III), Hg(II) and Pb(II) in natural and certified samples with satisfactory results.