Simultaneous preconcentration of Cd(II), Cu(II) and Pb(II) on Nano-TiO2 modified with 2-mercaptobenzothiazole prior to flame atomic absorption spectrometric determination

Nano-TiO₂ modified with 2-mercaptobenzothiazole (MBT) was investigated as a new adsorbent for preconcentration of Cd(II), Cu(II) and Pb(II). The metal ions are adsorbed onto nano-TiO₂-MBT, eluted by nitric acid and determined by flame atomic absorption spectrometry. The parameters affecting the adsorption were investigated. Under optimized conditions, the calibration curves were linear in the range of 0.2–25.0, 0.2–20.0, and 3.0–70.0 ng mL⁻¹ for cadmium, copper and lead, respectively. The limits of detection for Cd(II), Cu(II) and Pb(II) were 0.12, 0.15 and 1.38 ng mL⁻¹, respectively. The method was applied to determination of Cd(II), Cu(II) and Pb(II) in water and ore samples.     

Flame atomic absorption spectrometric determination of Cd,Pb, and Cu in food samples after pre-concentration using 4-(2-thiazolylazo) resorcinol-modified activated carbon

This work aimed to develop a solid-phase extraction method using low-cost activated carbon produced from waste and modified with 4-(2-thiazolylazo) resorcinol for Cd(II), Pb(II), and Cu(II). The results showed that quantitative recovery of analytes was obtained at pH 6 with 3 M nitric acid as the eluent and a sample volume up to 1000 mL. The method was validated using certified reference material and addition-recovery tests. The limits of detection (LODs) for Pb(II), Cd(II), and Cu(II) were 2.03 μg L⁻¹, 0.15 μg L⁻¹, and 0.19 μg L⁻¹, respectively. The procedure was applied for determination of analytes in food samples.     

Nano-alumina coated with sodium dodecyl sulfate and modified with 4-(2-Pyridylazo) resorcinol for extraction of heavy metals in different matrixes

A green, novel and efficient solid phase extraction method based on the use of nano-alumina (nano-Al₂O₃) coated with sodium dodecyl sulfate (SDS) and modified with 4-(2-Pyridylazo) resorcinol (PAR) as a new adsorbent was developed for separation and preconcentration of trace amounts of Ni, Pb, Cu and Zn ions prior to determination by inductively coupled plasma-optical emission spectrometry (ICP-OES). Under the optimum conditions (eluent: HNO₃, 4.0 mL, 3.0 mol L⁻¹; adsorbent: 0.8 g of nano-Al₂O₃, 40 mg of SDS, 8.6 mg of PAR; and sample: pH 6, flow rate 2.0 mL min⁻¹), adsorption capacity of nano-Al₂O₃-SDS-PAR, enrichment factors and limits of detection for the analytes were 8.7–12.9 mg g⁻¹, 125–250, and 0.12–0.71 μg L⁻¹, respectively. The proposed method presented excellent repeatability with relative standard deviations less than 1.6% (n = 10), and calculated calibration curves gave good level of linearity with correlation coefficient values between 0.989 and 0.999. Finally, the feasibility of the method was evaluated by extraction and determination of Ni, Pb, Cu and Zn ions in rice seed, apple juice, coriander, lettuce and tap water samples.     

A novel agricultural waste based adsorbent for the removal of Pb(II) from aqueous solution: Kinetics,equilibrium and thermodynamic studies

Fig sawdust was used as a precursor for the production of activated carbon by chemical activation with H₃PO₄. The developed Fig sawdust activated carbon (FSAC) was used as a biosorbent for the removal of Pb(II) from aqueous solution. Highest adsorption of Pb(II) (95.8%) was found at pH 4. Equilibrium data fitted very well with the Langmuir isotherm model. Maximum adsorption capacity was determined 80.645 mg g⁻¹ at pH 4. Kinetic studies demonstrated that the adsorption followed a pseudo second order kinetics model. The negative value of ΔG° confirmed the feasibility and spontaneity of FSAC for Pb(II) adsorption.     

High surface area-activated carbon from Glycyrrhiza glabra residue by ZnCl2 activation for removal of Pb(II) and Ni(II) from water samples

A high-surface-area activated carbon was prepared by chemical activation of Glycyrrhiza glabra residue with ZnCl₂ as active agent. Then, the adsorption behavior of Pb(II) and Ni(II) ion onto produced activated carbon has been studied. The experimental data were fitted to various isotherm models. According to Langmuir model, the maximum adsorption capacity of Pb(II) and Ni(II) ions were found to be 200 and 166.7 mg g⁻¹, respectively, at room temperature. Kinetic studies showed the adsorption process followed pseudo second-order rate model. High values of intra-particle rate constants calculated shows the high tendency of activated carbon for removal of Pb(II) and Ni(II) ions.     

Three-dimensional gold micro-/nanopore arrays containing 2-mercaptobenzothiazole molecular adapters allow sensitive and selective stripping voltammetric determination of trace mercury (II)

Three-dimensional (3D) gold micro-/nanopore arrays containing 2-mercaptobenzothiazole (MBT) adapters have been prepared and employed to improve the performance of the determination of trace mercury in solution using square wave anodic stripping voltammetry (SWASV). 3D gold micro-/nanopore arrays have an active surface area which is up to 4 and 15 times higher than a two-dimensional (2D) bowl-like structured microarrays and a flat solid gold electrode characterized by cyclic voltammetry, respectively. In this study, 3D MBT molecular adapters on the array surface greatly decreased the effect of capacitive current and enhanced the sensitivity and selectivity of the electrode. A limit of detection of 0.02 nM (which is well below the guideline given by the World Health Organization) and more importantly, a sensitivity of 1.85 μA nM^?1 was obtained using this system. Furthermore, excellent linear range (0.05–10 nM) and good repeatability (relative standard deviation of 2.10%) were obtained for Hg(II). Interference experiments were also investigated, and it was determined that Pb(II), Cd(II), Zn(II), Cu(II) and Ag(I) had little or no influence on the mercury signal.     

Lead ion and tetrabutylammonium bromide as inhibitors of the growth of spongy zinc in single flow zinc/nickel batteries

Lead ion and tetrabutylammonium bromide (TBAB) have been testified as inhibitors of spongy zinc electro-growth from flowing alkaline zincate solutions. To assess the efficacy of the two additives, current–time technique using potentiostatic electro-deposition, scanning electron microscopy and cycling test were undertaken. The results show that the growth of spongy zinc in flowing alkaline zincate solutions can be effectively inhibited by the addition of 10^?4 M Pb(II) or TBAB at the cathodic potential (η = ?100 mV), respectively. But, the dual addition of 10^?4 M Pb(II) and 5 × 10^?5 M TBAB produces more effective suppression on spongy zinc growth. Obvious synergistic effect of Pb(II) and TBAB on the inhibition of spongy zinc deposits is found. From the charge/discharge cycling tests of the single flow Zn–Ni test cells, it is shown that the rechargeability of Zn anode is highly improved by the mixed introduction of 10^?4 M Pb(II) and 5 × 10^?5 M TBAB.     

A lead(II)-orotate coordination polymer with a new coordination mode: Synthesis,structure and luminescent property

A lead(II) orotate complex [Pb(HOr)(H₂O)]_n (1), (H₃Or = orotic acid) was synthesized under hydrothermal condition and characterized by X-ray diffraction, IR, solid-state photoluminescence and thermogravimetric analysis. Lead atom in 1 is in a holodirected eight-coordinated polyhedron and the orotate ligand exhibits a new and unique hexametallic coordination mode. The lead complex shows a 6,6-connected (4⁸, 6⁶, 8)(4¹³, 6²) topology. The complex exhibits photoluminescence at 546 nm (λ_ex = 350 nm).     

DNA interaction and antimicrobial activity of novel tetradentate imino-oxalato mixed ligand metal complexes

Four novel DNA metalloinsertors having imino-oxalato mixed-ligands, of the composition [ML(ox)]Cl₂ (where M = Cu(II), Co(II), Ni(II) and Zn(II); ox = C₂O₄^2 − and L = N,N′-bis(4-chlorobenzylidene)benzene-1,2-diamine) were synthesized. They were fully characterized by microanalytical data, magnetic susceptibility values, molar conductivity measurements, UV–vis, IR, ¹H NMR, ¹³C NMR and EPR techniques. Their geometry was explored and found to have square-planar geometry. Electronic absorption spectroscopy, cyclic voltammetry and viscosity measurements indicate that these mixed-ligand complexes strongly bind to calf thymus DNA, presumably via an intercalation mechanism. Further, DNA cleavage efficacy of these complexes was investigated by gel electrophoresis. The complexes were found to promote the cleavage of pBR322 DNA in the presence of the reluctant, ascorbic acid. The ligand (L) and the mixed-ligand complexes were tested for their efficiency towards antimicrobial activity and their MIC data reveal that all the complexes have strong activity in comparison to the free ligand and standard drugs, ciprofloxacin and fluconazole.     

Chemically modified carbon nanotubes as efficient and selective sorbent for enrichment of trace amount of some metal ions

Multi-walled carbon nanotubes (MWCNT) was oxidized and chemically functionalized by 3-hydroxy-4-((3-silylpropylimino) methyl) phenol (HSPIMP) and characterized with FT-IR technique. This new sorbent was used for enrichment and preconcentration of Cu²⁺, Ni²⁺, Zn²⁺, Pb²⁺, Co²⁺, Fe³⁺ ions. Variables such as pH, amount of solid phase, eluting solution conditions (type, volume and concentrations) have significant effect on sorption and recoveries of analytes and the influence was optimized. At optimum value of conditions, the interference of other ions on understudy ions recoveries was investigated. The metal ions loaded on the solid phase via chelation with the new sorbent and subsequently efficiently eluted using 6 mL of 4 mol L^?1 HNO₃ solution. At each run, metal ions content was determined by flame atomic absorption spectrometry (FAAS). Relative standard deviation (N = 3) for determination of 0.2 μg mL^?1 of analytes was between 1.6 and 3.0%, while their detection limit was between 1.0 and 2.6 ng mL^?1 (3Sb, n = 10). The sorption capacity of HSPIMP–MWCNT for understudy ions was above 30 mg g^?1. The proposed method successfully applied for the extraction and determination of the understudy metal ions in different samples.     

Metal sorption on macroporous poly(GMA-co-EGDMA) modified with ethylene diamine

Two samples of macroporous crosslinked poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate), poly(GMA-co-EGDMA), with different porosity parameters were synthesized by suspension copolymerization and modified by ring-opening reaction of the pendant epoxy groups with ethylene diamine (EDA). The samples were characterized by mercury porosimetry, FT-IR spectroscopy and elemental analysis. The sorption rate of the modified copolymer, poly(GMA-co-EGDMA)-en for Cu(II) ions determined under non-competitive conditions was relatively rapid, i.e. the maximum capacity was reached within 30 min. Batch sorption capacities for Cu(II), Fe(II), Mn(II), Cd(II), Zn(II), Pb(II), Cr(III) and Pt(IV) ions were determined under non-competitive conditions in the pH range 1.25–5.5 at room temperature. The maximum sorption capacities of poly(GMA-co-EGDMA)-en under non-competitive conditions were 1.30 mmol/g for Pt(IV) at pH 5.5, 1.10 mmol/g for Cu(II) at pH 5.5, 1.06 mmol/g for Pb(II) at pH 1.25 and 0.67 mmol/g for Cd(II) ions at pH 5.5. The selectivity of poly(GMA-co-EGDMA)-en towards Cu(II), Co(II), Ni(II), Pb(II) and Pt(IV) ions was investigated under competitive conditions. Poly(GMA-co-EGDMA)-en showed high selectivity for Pt(IV) over Cu(II), Co(II), Ni(II) and Pb(II) ions at pH 2.1. At pH 5.5, the metal sorption capacities of poly(GMA-co-EGDMA)-en decreased in the order: Cu(II) > Co(II) > Pt(IV) ≈ Ni(II) > Pb(II). Regeneration of the Cu(II), Ni(II) and Pb(II) loaded poly(GMA-co-EGDMA)-en with 2 M H₂SO₄ showed that the polymer can be reused in several sorption/desorption cycles.     

Effect of core-shell reversal on the structural,magnetic and adsorptive properties of Fe2O3-GO nanocomposites

Effect of core-shell reversal on the nanocomposites of graphene oxide (GO) and ferric oxide (Fe₂O₃) was studied. Fe₂O₃@GO core-shell nanosheets were synthesized by sonication method, while the GO@Fe₂O₃ core-shell nanospheres by employing N,N′-dicyclohexylcarbodimide as the binding agent for the wrapping of GO sheets on pre-formed Fe₂O₃ nanoparticles (NPs). The phase composition, crystallinity and morphology of the nanocomposites were characterized by FT-IR, TEM, SEM-EDS, VSM, BET surface area study and XRD techniques. The saturation magnetization (M_s) was 1.25 and 0.51 emu g⁻¹ for GO@Fe₂O₃ and Fe₂O₃@GO respectively owing to the dependence of magnetic properties on the reversal of core-shell. BET analysis revealed the surface area of 100.32 m² g⁻¹ and 45.69 m² g⁻¹ for GO@Fe₂O₃ and Fe₂O₃@GO nanocomposites respectively. The fabricated nanocomposites were analyzed as adsorbents for the uptake of Pb (II) ions. The impact of various factors affecting adsorption process such as pH, adsorbent dose, contact time, temperature and metal ion concentration was also investigated. GO@Fe₂O₃ core-shell nanospheres showed a higher adsorption capacity for Pb (II) ions as compared to Fe₂O₃@GO core-shell nanosheet with the maximum adsorption capacities (q_m) of 303.0 and 125.0 mg g⁻¹ respectively. The equilibrium data was estimated by Freundlich, Langmuir, D-R and Temkin isotherm models. Thermodynamic analysis confirmed the spontaneous and exothermic nature of the adsorption process. The adsorption kinetics was significantly fitted to pseudo-second order model. The results confirmed that core-shell reversal can significantly alter the adsorptive properties of Fe₂O₃-GO nanocomposite     

Separation and determination of cadmium in water by foam column prior to inductively coupled plasma optical emission spectrometry

The sorption profile of cadmium (II) ions from aqueous iodide media onto procaine hydrochloride (PQ⁺·Cl⁻) treated polyurethane foams (PUFs) solid sorbent was studied. PQ⁺·Cl⁻ treated PUFs solid sorbent was found suitable and fast for Cd²⁺ uptake as [CdI4]_aq²⁻. Thus, removal of Cd²⁺ at trace levels by the sorbent packed columns was achieved. The sorbed Cd²⁺ species onto packed column were recovered with HNO₃ (10.0 mL, 1.0 mol L⁻¹) prior determination by inductively coupled plasma-optical emission spectrometry (ICP-OES). Plot of Cd²⁺ ions concentration was linear in the range 0.05–15 μg L⁻¹. The limits of detection and quantification of Cd²⁺ were found 0.01 μg L⁻¹ and 0.033 μg L⁻¹, respectively. Such limits could be improved to lower values by retention of Cd²⁺ species from large sample volumes of the aqueous phase at the optimized conditions. The relative standard deviation of the packed column for the extraction and recovery of standard aqueous solutions (0.1 L) containing 1.0 and 5.0 μg L⁻¹ (n = 3) of Cd²⁺ ions at flow rate of 5.0 mL min⁻¹ were 1.98 and 2.9%, respectively. The method was validated by analysis of Cd in certified reference materials (CRMs) IAEA-Soil-7 and TMDW water and wastewater samples.     

Chitosan modified with Reactive Blue 2 dye on adsorption equilibrium of Cu(II) and Ni(II) ions

This study aimed at immobilizing Reactive Blue 2 (RB 2) dye in chitosan microspheres through nucleophilic substitution reaction. The adsorbent chemical modification was confirmed by Raman spectroscopy and thermogravimetric analysis. This adsorption study was carried out with Cu(II) and Ni(II) ions and indicated a pH dependence, while the maximum adsorption occurred around pH 7.0 and 8.5, respectively. The pseudo second-order kinetic model resulted in the best fit with experimental data obtained from Cu(II) (R = 0.997) and Ni(II) (R = 0.995), also providing a rate constant, k₂, of 4.85 × 10⁻⁴ and 3.81 × 10⁻⁴ g (mg min)⁻¹, respectively, thus suggesting that adsorption rate of metal ions by chitosan-RB 2 depends on the concentration of ions on adsorbent surface, as well as on their concentration at equilibrium. The Langmuir and Freundlich isotherm models were employed in the analysis of the experimental data for the adsorption, in the form of linearized equations. Langmuir model resulted in the best fit for both metals and maximum adsorption was 57.0 mg g⁻¹ (0.90 mmol g⁻¹) for Cu(II) and 11.2 mg g⁻¹ (0.19 mmol g⁻¹) for Ni(II). The Cu(II) and Ni(II) ions were desorbed from chitosan-RB 2 with aqueous solutions of EDTA and H₂SO₄, respectively.     

Influence of anion induced proton abstraction on Cu(II) adsorption by alginic acid

Alginic acid (AA) synthesized by acidification of commercial sodium alginate was investigated for its Cu(II) adsorption efficiency in the presence of different counter ions. The results of batch adsorption studies indicated an adsorption of 169.86 mg/g of Cu(II) by AA in the presence of acetate ions, however, it significantly decreased in the presence of chloride (126.36 mg/g), sulphate (115.24 mg/g) and nitrate (113.28 mg/g) as counter ions. This can be accounted to the tendency of conjugate base (anion) to abstract proton from AA, which determines the extent of deprotonation of carboxylic acid. The FTIR and TGA/DTA studies support the difference in the coordination of carboxylate to Cu(II) in the presence of various counter anions. Acetate showed strong chelate coordination between Cu(II) and AA, whereas in the presence of Cl⁻, NO₃⁻ and SO₄^2 −, Cu(II) was complexed by weak bridging coordination with AA.     

Effect of Pb excess in sol–gel process on phase composition in PFN ceramics

Lead iron niobate Pb(Fe_0.5Nb_0.5)O₃ (PFN) precursors were prepared using sol–gel synthesis by mixing acetates Pb and Fe with Nb-ethylene glycol–tartarate (Pechini) complex at 80 °C and calcination of gels at 600 °C. Single pyrochlore phase with structure close to Pb₃Nb₄O₁₃ was formed in stoichiometric precursor and Pb₃Nb₄O₁₃ with small amount of perovskite phase Pb(Fe_0.5Nb_0.5)O₃ in nonstoichiometric precursor prepared with the excess of Pb in molar ratio (Pb:Fe:Nb = 1.2:0.5:0.5). Average particle sizes of PFN calcined powders were ～120 nm. The metastable pyrochlore phase was partially decomposed to perovskite phase at sintering temperature of 1150 °C for 2, 4 and 6 h. Excess of Pb caused increasing of the density (7.4 g/cm³) and content of the perovskite phase (～53 vol.%) in ceramics sintered for 4 h. In microstructures of PFN ceramics sintered at 1150 °C for different times, the bimodal grain size distribution was observed with small spherical grains of perovskite phase and larger octahedral grains, which represent the pyrochlore phase. Results of EDX analysis confirm that complex types of pyrochlore phases that differ in iron content were present in ceramics.     

Multiwalled carbon nanotube impregnated with bis(5-bromosalicylidene)-1,3-propandiamine for enrichment of Pb2+ ion

Multiwalled carbon nanotube impregnated by bis(5-bromosalicylidene)-1,3-propandiamine (BBSPN) was synthesized and applied as adsorbent for the enrichment of trace amount of Pb²⁺ ion subsequent their determination by flame atomic absorption spectroscopy (FAAS). The influences of the analytical parameters including pH, amount of ligand and adsorbent, type and condition of eluent and sample volume on the Pb²⁺ ion recoveries were investigated. The optimum pH value for the separation of Pb²⁺ ion on the new sorbent was 6 and the adsorbed Pb²⁺ ion could be completely eluted by using 5.0 mL of 2.0 mol L⁻¹ HNO₃ solutions with 0.015 g of ligand and 0.100 g of adsorbent. Common coexisting ions did not interfere with the separation and determination of target metal ions. The method has high sorption–preconcentration efficiency with relative standard deviation less than 4.0%, especially for lead determination in radish, vegetable, potato, tomato and cheeps.     

MLCT interaction in [Rh(II)2(CO3)4]4 −( x L)

Complexes of the type [Rh^II₂(CO₃)₄(H₂O)L]^n − with L = N-methylpyrazinium⁺ and 1-heptyl-4-(4-pyridinyl)pyridinium⁺ cations display intense long-wavelength (Rh(II) to L) MLCT absorptions. With L = H₂O, MLCT absorptions are not identified, but the photoreactivity of the complex in aqueous solution supports the assumption that (Rh(II) to CO₃^2 −) MLCT excited states are accessible. Upon irradiation with white light, Rh(II) is photooxidized while carbonate is reduced to CO. The efficiency of this photolysis is very low. However, the occurrence of this photoredox reaction is, nevertheless, of general interest with regard to the photochemical reduction of CO₂.     

Broadband dielectric spectroscopy of PbMg1/3Nb2/3O3–PbSc1/2Nb1/2O3 ceramics

Broadband dielectric spectroscopy results of various ordered and disordered (1 ? x)Pb(Mg_1/3Nb_2/3)O₃–(x)Pb(Sc_1/2Nb_1/2)O₃ (PMN–PSN) ceramics are investigated in the temperature range from 80 K to 300 K and frequency range from 20 Hz to 2 THz. Dielectric dispersion is very broad and in the ferroelectrics case (x = 1, 0.95) consists of two parts: low-frequency part caused by ferroelectric domains and higher frequency part caused by soft mode. The relaxational soft mode exhibits pronounced softening close to phase transition temperature, as it is typical for order–disorder phase transitions. By substituting Sc³⁺ by Mg²⁺ in PMN–PSN ceramics relaxation slows down, and for relaxors (x = 0.2) the most probable relaxation frequency decreases on cooling according to Vogel–Fulcher law.     

Chemistry of cement hydration in polymer-modified pastes containing lead compounds

The role of polymeric additives on the hydration process of cement pastes admixed with a lead compound (Pb₃O₄) was investigated. Three series of pastes were prepared: the reference series, mixing water with Ordinary Portland Cement (OPC), and two series in which whether a styrene–butadiene rubber latex or a superplasticiser based on acrylic-modified polymer was added to the pastes. For each series, 5 and 10 wt% of Pb were mixed with the pastes. Phase analysis and microstructural characterisation were carried out by means of X-ray powder diffraction and SEM–EDX. Thermogravimetric analysis was performed to monitor the hydration degree of the three pastes; indeed, quantitative determination of portlandite and calcite was performed.Dynamic leach tests were performed on solidified monoliths to evaluate the effective immobilisation of Pb₃O₄. After 384 h leaching, excellent results were obtained by pastes mixed with superplasticiser that showed a cumulative release of Pb equal to 0.62 mg/l for samples containing 5 wt% of Pb, and equal to 0.84 mg/l for samples bearing 10 wt% of Pb.