Electrochemical DNAzyme sensor for lead based on amplification of DNA-Au bio-bar codes

An electrochemical DNAzyme sensor for sensitive and selective detection of lead ion (Pb(2+)) has been developed, taking advantage of catalytic reactions of a DNAzyme upon its binding to Pb(2+) and the use of DNA-Au bio-bar codes to achieve signal enhancement. A specific DNAzyme for Pb(2+) is immobilized onto an Au electrode surface via a thiol-Au interaction. The DNAzyme hybridizes to a specially designed complementary substrate strand that has an overhang, which in turn hybridizes to the DNA-Au bio-bar code (short oligonucleotides attached to 13 nm gold nanoparticles). A redox mediator, Ru(NH3)6(3+), which can bind to the anionic phosphate of DNA through electrostatic interactions, serves as the electrochemical signal transducer. Upon binding of Pb(2+) to the DNAzyme, the DNAzyme catalyzes the hydrolytic cleavage of the substrate, resulting in the removal of the substrate strand along with the DNA bio-bar code and the bound Ru(NH3)6(3+) from the Au electrode surface. The release of Ru(NH3)6(3+) results in lower electrochemical signal of Ru(NH3)6(3+) confined on the electrode surface. Differential pulse voltammetry (DPV) signals of Ru(NH3)6(3+) provides quantitative measures of the concentrations of Pb(2+), with a linear calibration ranging from 5 nM to 0.1 microM. Because each nanoparticle carries a large number of DNA strands that bind to the signal transducer molecule Ru(NH3)6(3+), the use of DNA-Au bio-bar codes enhances the detection sensitivity by five times, enabling the detection of Pb(2+) at a very low level (1 nM). The DPV signal response of the DNAzyme sensor is negligible for other divalent metal ions, indicating that the sensor is highly selective for Pb(2+). Although this DNAzyme sensor is demonstrated for the detection of Pb(2+), it has the potential to serve as a general platform for design sensors for other small molecules and heavy metal ions.     

Graphene-DNAzyme based biosensor for amplified fluorescence "turn-on" detection of Pb2+ with a high selectivity

On the basis of the remarkable difference in affinity of graphene (GO) with ssDNA containing a different number of bases in length, we for the first time report a GO-DNAzyme based biosensor for amplified fluorescence "turn-on" detection of Pb(2+). A FAM-labeled DNAzyme-substrate hybrid acted as both a molecular recognition module and signal reporter and GO as a superquencher. By taking advantage of the super fluorescence quenching efficiency of GO, our proposed biosensor exhibits a high sensitivity toward the target with a detection limit of 300 pM for Pb(2+), which is lower than previously reported for catalytic beacons. Moreover, with the choice of a classic Pb(2+)-dependent GR-5 DNAzyme instead of 8-17 DNAzyme as the catalytic unit, the newly designed sensing system also shows an obviously improved selectivity than previously reported methods. Moreover, the sensing system was used for the determination of Pb(2+) in river water samples with satisfying results.     

Amplified surface plasmon resonance and electrochemical detection of Pb2+ ions using the Pb2+-dependent DNAzyme and hemin/G-quadruplex as a label

The hemin/G-quadruplex nanostructure and the Pb(2+)-dependent DNAzyme are implemented to develop sensitive surface plasmon resonance (SPR) and electrochemical sensing platforms for Pb(2+) ions. A complex consisting of the Pb(2+)-dependent DNAzyme sequence and a ribonuclease-containing nucleic acid sequence (corresponding to the substrate of the DNAzyme) linked to a G-rich domain, which is "caged" in the complex structure, is assembled on Au-coated glass surfaces or Au electrodes. In the presence of Pb(2+) ions, the Pb(2+)-dependent DNAzyme cleaves the substrate, leading to the separation of the complex and to the self-assembly of the hemin/G-quadruplex on the Au support. In one sensing platform, the Pb(2+) ions are analyzed by following the dielectric changes at the surface as a result of the formation of the hemin/G-quadruplex label using SPR. This sensing platform is further amplified by the immobilization of the sensing complex on Au NPs (13 nm) and using the electronic coupling between the NPs and the surface plasmon wave as an amplification mechanism. This method enables the sensing of Pb(2+) ions with a detection limit that corresponds to 5 fM. The second sensing platform implements the resulting hemin/G-quadruplex as an electrocatalytic label that catalyzes the electrochemical reduction of H(2)O(2). This method enables the detection of Pb(2+) with a detection limit of 1 pM. Both sensing platforms reveal selectivity toward the detection of Pb(2+) ions.     

DNAzyme-based colorimetric sensing of lead (Pb(2+)) using unmodified gold nanoparticle probes

Novel functional oligonucleotides, especially DNAzymes with RNA-cleavage activity, have been intensively studied due to their potential applications in therapeutics and sensors. Taking advantage of the high specificity of 17E DNAzyme for Pb(2+), highly sensitive and selective fluorescent, electrochemical and colorimetric sensors have been developed for Pb(2+). In this work, we report a simple, sensitive and label-free 17E DNAzyme-based sensor for Pb(2+) detection using unmodified gold nanoparticles (GNPs) based on the fact that unfolded single-stranded DNA could be adsorbed on the citrate protected GNPs while double-stranded DNA could not. By our method the substrate cleavage by the 17E DNAzyme in the presence of Pb(2+) could be monitored by color change of GNPs, thereby Pb(2+) detection was realized. The detection of Pb(2+) could be realized within 20?min, with a detection limit of 500?nM. The selectivity of our sensor has been investigated by challenging the sensing system with other divalent metal ions. Since common steps such as modification and separation could be successfully avoided, the sensor developed here could provide a simple, cost-effective yet rapid and sensitive measurement tool for Pb(2+) detection and may prove useful in the development of sensors for clinical toxicology and environmental monitoring in the future.     

Impedimetric immobilized DNA-based sensor for simultaneous detection of Pb2+, Ag+, and Hg2+

An unlabeled immobilized DNA-based sensor was reported for simultaneous detection of Pb(2+), Ag(+), and Hg(2+) by electrochemical impedance spectroscopy (EIS) with [Fe(CN)(6)](4-/3-) as redox probe, which consisted of three interaction sections: Pb(2+) interaction with G-rich DNA strands to form G-quadruplex, Ag(+) interaction with C-C mismatch to form C-Ag(+)-C complex, and Hg(2+) interaction with T-T mismatch to form T-Hg(2+)-T complex. Circular dichroism (CD) and UV-vis spectra indicated that the interactions between DNA and Pb(2+), Ag(+), or Hg(2+) occurred. Upon DNA interaction with Pb(2+), Ag(+), and Hg(2+), respectively, a decreased charge transfer resistance (R(CT)) was obtained. Taking advantage of the R(CT) difference (ΔR(CT)), Pb(2+), Ag(+), and Hg(2+) were selectively detected with the detection limit of 10 pM, 10 nM, and 0.1 nM, respectively. To simultaneously (or parallel) detect the three metal ions coexisting in a sample, EDTA was applied to mask Pb(2+) and Hg(2+) for detecting Ag(+); cysteine was applied to mask Ag(+) and Hg(2+) for detecting Pb(2+), and the mixture of G-rich and C-rich DNA strands were applied to mask Pb(2+) and Ag(+) for detecting Hg(2+). Finally, the simple and cost-effective sensor could be successfully applied for simultaneously detecting Pb(2+), Ag(+), and Hg(2+) in calf serum and lake water.     

Ion-exchange of Pb2+, Cu2+, Zn2+, Cd2+, and Ni2+ ions from aqueous solution by Lewatit CNP 80

Removal of trace amounts of heavy metals can be achieved by means of selective ion-exchange processes. The newly developed resins offered a high resin capacity and faster sorption kinetics for the metal ions such as Pb(2+), Cu(2+), Zn(2+), Cd(2+), and Ni(2+) ions. In the present study, the removal of Pb(2+), Cu(2+), Zn(2+), Cd(2+), and Ni(2+) ions from aqueous solutions was investigated. Experimental investigations were undertaken using the ion-exchange resin Lewatit CNP 80 (weakly acidic) and were compared with Lewatit TP 207 (weakly acidic and chelating). The optimum pH range for the ion-exchange of the above mentioned metal ions on Lewatit CNP 80 and Lewatit TP 207 were 7.0-9.0 and 4.5-5.5, respectively. The influence of pH, contact time, metal concentration and amount of ion-exchanger on the removal process was investigated. For investigations of the exchange equilibrium, different amounts of resin were contacted with a fixed volume of Pb(2+), Cu(2+), Zn(2+), Cd(2+), and Ni(2+) ion containing solution. The obtained sorption affinity sequence in the presented work was Ni(2+)>Cu(2+)>Cd(2+)>Zn(2+)>Pb(2+). The metal ion concentrations were measured by AAS methods. The distribution coefficient values for metal ions of 10(-3)M initial concentration at 0.1mol/L ionic strength show that the Lewatit CNP 80 was more selective for Ni(2+), Cu(2+) than it was for Cd(2+), Zn(2+) and Pb(2+). Langmuir isotherm was applicable to the ion-exchange process and its contents were calculated. The uptake of metal ions by the ion-exchange resins was reversible and thus has good potential for the removal of Pb(2+), Cu(2+), Zn(2+), Cd(2+), and Ni(2+) from aqueous solutions. The amount of sorbed metal ion per gram dry were calculated as 4.1, 4.6, 4.7, 4.8, and 4.7mequiv./g dry resin for Pb(2+), Cu(2+), Zn(2+), Cd(2+), and Ni(2+), respectively. Selectivity increased in the series: Cd(2+)>Pb(2+)>Cu(2+)>Ni(2+)>Zn(2+). The results obtained showed that Lewatit CNP 80 weakly acidic resin had shown better performance than Lewatit TP 207 resin for the removal of metals. The change of the ionic strength of the solution exerts a slight influence on the removal of Pb(2+), Cu(2+), Zn(2+), Cd(2+), and Ni(2+). The presence of low ionic strength or low concentration of NaNO(3) does not have a significant effect on the ion-exchange of these metals by the resins. We conclude that Lewatit CNP 80 can be used for the efficient removal of Pb(2+), Cu(2+), Zn(2+), Cd(2+), and Ni(2+) from aqueous solutions.     

Feasibility of using natural fishbone apatite as a substitute for hydroxyapatite in remediating aqueous heavy metals.

Fishbone, a natural, apatite rich substance, was examined for suitability as a substitute for hydroxyapatite in the sequestering of aqueous divalent heavy metal ions. The fishbone exhibited lower metal removal capacity than pure hydroxyapatite, due primarily to its purity ( approximately 70% apatite equivalent). In other ways the fishbone behaves in a similar manner as pure hydroxyapatite in the sequestration process. It was observed that it can remove all Pb(2+), Cu(2+), Cd(2+) and Ni(2+) to below detectable levels as measured by inductively coupled plasma atomic absorption, and the rate of reaction with either Zn(2+), Ni(2+), or Pb(2+) was also found to be similar to hydroxyapatite. Also, a two level, three variable full factorial design was performed for the Pb/apatite reaction and both apatites performed similarly. The main difference, besides capacity, was on exposure to high (2.4 mM) Pb concentrations. The fishbone removed less of the Pb(2+) than capacity correction predicted.     

Factors influencing the removal of divalent cations by hydroxyapatite

The effect of pH, contact time, initial metal concentration and presence of common competing cations, on hydroxyapatite (HAP) sorption properties towards Pb(2+), Cd(2+), Zn(2+), and Sr(2+) ions was studied and compared using a batch technique. The results strongly indicated the difference between the sorption mechanism of Pb(2+) and other investigated cations: the removal of Pb(2+) was pH-independent and almost complete in the entire pH range (3-12), while the sorption of Cd(2+), Zn(2+) and Sr(2+) generally increased with an increase of pH; the contact time required for attaining equilibrium was 30 min for Pb(2+) versus 24h needed for other cations; maximum sorption capacity of HAP sample was found to be an order of magnitude higher for Pb(2+) (3.263 mmol/g), than for Cd(2+) (0.601 mmol/g), Zn(2+) (0.574 mmol/g) and Sr(2+) (0.257 mmol/g); the selectivity of HAP was found to decrease in the order Pb(2+)>Cd(2+)>Zn(2+)>Sr(2+) while a decrease of pH(PZC), in respect to the value obtained in inert electrolyte, followed the order Cd(2+)>Zn(2+)>Pb(2+)>Sr(2+); neither of investigated competing cations (Ca(2+), Mg(2+), Na(+) and K(+)) influenced Pb(2+) immobilization whereas the sorption of other cations was reduced in the presence of Ca(2+), in the order Sr(2+)>Cd(2+)>or=Zn(2+). The pseudo-second order kinetic model and Langmuir isotherm have been proposed for modeling kinetic and equilibrium data, respectively. The sorption of all examined metals was followed by Ca(2+) release from the HAP crystal lattice and pH decrease. The ion exchange and specific cation sorption mechanisms were anticipated for Cd(2+), Zn(2+) and Sr(2+), while dissolution of HAP followed by precipitation of hydroxypyromorphite (Pb(10)(PO(4))(6)(OH)(2)) was found to be the main operating mechanism for Pb(2+) immobilization by HAP, with the contribution of specific cation sorption.     

Simultaneous preconcentration and determination of copper, nickel, cobalt and lead ions content by flame atomic absorption spectrometry

A sensitive and simple method for the simultaneous preconcentration of nutritionally important minerals in real samples has been reported. The method is based on the formation of metal complexes by 4,6-dihydroxy-2-mercaptopyrimidine (DHMP) loaded on activated carbon. The metals content on the complexes are then eluted using 5 mL 2M HNO(3) in acetone, which are detected by AAS at resonance line. In this procedure, minerals such as Cu, Ni, Pb and Co could be analyzed in one run by caring out the simultaneous separation and quantification of them. At optimum condition the response are linear over concentration range of 0.04-1.1 microg mL(-1) for Ni(2+) and 0.04-1.0 microg mL(-1) for Cu(2+), Pb(2+) and Co(2+). The detection limits of each element are expressed as the amount of analytes in ng mL(-1) giving a signal to noise ratio of 3 are equal to 3.5, 3.4, 2.9 and 8.4 for Ni(2+), Co(2+), Cu(2+) and Pb(2+). The sorption capacity was determined by saturating 0.5 g solid phase. The loading capacity are 0.54, 0.53, 0.63 and 0.45 mg g(-1) for Ni(2+), Co(2+), Cu(2+) and Pb(2+). The ability of method for repeatable recovery of trace ion are 99.0, 98.9, 99.2 and 98.8 with R.S.D. of 1.4, 1.3, 1.2 and 1.4 for Ni(2+), Co(2+), Cu(2+) and Pb(2+). The low detection limits of these elements in this technique make it a superior alternative to UV-vis and in several applications, also an alternative to ICP-MS techniques. The method has been successfully applied for these metals content evaluation in some real samples including natural water, leaves of spinach and cow liver.     

Manipulation of intraparticle charge delocalization by selective complexation of transition-metal ions with histidine moieties

Ruthenium nanoparticles were cofunctionalized with pyrene and histidine moieties through Ru═carbene π bonds. The selective complexation of the histidine moiety with transition-metal ions led to a marked diminishment of the emission peak at 490 nm which arose from the nanoparticle-bridged pyrene moieties that behaved analogously to pyrene dimers with a conjugated spacer. This is accounted for by the polarization of the core electrons by the added positive charge that impacted the intraparticle charge delocalization between the particle-bound pyrene moieties. This electronic interaction was likely facilitated by the π interactions between the metal ions and the imidazole ring as well as by the conjugated molecular backbone that linked the imidazole ring to the nanoparticle cores. Within the present experimental context, of all the metal ions tested, the impacts were much more drastic with Pb(2+), Co(2+), and Hg(2+) than with Li(+), K(+), Rb(+), Mg(2+), Ca(2+), and Zn(2+) ions, with the most sensitive variation observed with Pb(2+). This is ascribed to the enhanced π interactions of the histidine moiety with the Pb(2+), Co(2+), and Hg(2+) ions because of their capability of donating d electrons, a behavior consistent with prior studies based on conventional histidine-metal ion complexes.     

Fluorescence detection of lead(II) ions through their induced catalytic activity of DNAzymes

We have developed a fluorescence approach for the highly selective and sensitive detection of Pb(2+) ions using AGRO100, a G-quadruplex DNAzyme. The sensing strategy is based on Pb(2+) ions inducing increased DNAzyme activity of AGRO100 in the presence of hemin, which acts as a cofactor to catalyze H(2)O(2)-mediated oxidation of Amplex UltraRed (AUR). A test of eight aptamers of various sequences for the detection of Pb(2+) ions revealed that AGRO100 performed the best in terms of sensitivity. The AGRO100-AUR probe exhibited high selectivity (>100-fold) toward Pb(2+) ions over other tested metal ions. The fluorescence intensity (excitation/emission maxima, ca. 561/592 nm) of the AUR product was proportional to the concentration of Pb(2+) ions over the range 0-1000 nM, with a linear correlation (R(2) = 0.98). For 5 mM Tris-acetate (pH 7.4) solutions in the presence and absence of 100 mM NaCl, the AGRO100-AUR probe provided limits of detection (signal-to-noise ratio = 3) for Pb(2+) ions of 1.0 and 0.4 nM, respectively. We validated the practicality of the use of the AGRO100-AUR probe for the determination of the concentrations of Pb(2+) ions in soil samples. This approach allows the determination of the concentrations of Pb(2+) ions with simplicity, selectivity, and sensitivity.     

Biosorption of heavy metals from aqueous solutions by chemically modified orange peel

Equilibrium, thermodynamic and kinetic studies were carried out for the biosorption of Pb(2+), Cd(2+) and Ni(2+) ions from aqueous solution using the grafted copolymerization-modified orange peel (OPAA). Langmuir and Freundlich isotherm models were applied to describe the biosorption of the metal ions onto OPAA. The influences of pH and contact time of solution on the biosorption were studied. Langmuir model fitted the equilibrium data better than the Freundlich isotherm. According to the Langmuir equation, the maximum uptake capacities for Pb(2+), Cd(2+) and Ni(2+) ions were 476.1, 293.3 and 162.6 mg g(-1), respectively. Compared with the unmodified orange peel, the biosorption capacity of the modified biomass increased 4.2-, 4.6- and 16.5-fold for Pb(2+), Cd(2+) and Ni(2+), respectively. The kinetics for Pb(2+), Cd(2+) and Ni(2+) ions biosorption followed the pseudo-second-order kinetics. The free energy changes (ΔG°) for Pb(2+), Cd(2+) and Ni(2+) ions biosorption process were found to be -3.77, -4.99 and -4.22 kJ mol(-1), respectively, which indicates the spontaneous nature of biosorption process. FTIR demonstrated that carboxyl and hydroxyl groups were involved in the biosorption of the metal ions. Desorption of Pb(2+), Cd(2+) and Ni(2+) ions from the biosorbent was effectively achieved in a 0.05 mol L(-1) HCl solution.     

Biosorption of heavy metal ions on immobilized white-rot fungus Trametes versicolor

Trametes versicolor mycelia were immobilized in carboxymethylcellulose, CMC, beads via entrapment, and the bead containing immobilized fungus spores were incubated at 30 degrees C for 3 days to attain uniform growth on the bead surface. After incubation, the live and heat inactivated immobilized fungus on the CMC beads were used for the biosorption of Cu(2+), Pb(2+) and Zn(2+) ions.Plain CMC beads were used as a control system. The biosorption of Cu(2+), Pb(2+) and Zn(2+) ions by the CMC and both live and inactivated immobilized preparations increased as the initial concentration of Cu(2+), Pb(2+) and Zn(2+) ions in the medium increased. The maximum biosorption capacities for both immobilized live and heat inactivated Trametes versicolor were 1.51 and 1.84mmol Cu(2+), 0.85 and 1.11mmol Pb(2+) and 1.33 and 1.67mmol Zn(2+) per g of dry biosorbents, respectively. Biosorption equilibrium was established in about 1.0h and the equilibrium was well described by Langmuir and Freundlich isotherms. A temperature change in the range of 15-45 degrees C did not affect the biosorption capacity. The affect of pH was also investigated and the maximum adsorption of Cu(2+), Pb(2+) and Zn(2+) ions on the CMC and both live and inactivated immobilized fungal biomass was observed between pH 4.0 and 6.0. The CMC beads with the immobilized fungus can be regenerated using 10mM HCl, with up to 97% recovery of the metal ions; the biosorbents reused up to five biosorption-desorption cycles without any major loss in the biosorption capacity.     

Competitive sorption and transport of Pb2+, Ni2+, Mn2+, and Zn2+ in lateritic soil columns

Knowledge of sorption and transport of heavy metals in soils in the presence of other metals is crucial for assessing the environmental risk of these metals. Competitive sorption and transport of four metals, Pb(2+), Ni(2+), Zn(2+), and Mn(2+), were investigated using multi-metal column experiments with lateritic soils obtained from a gold mine impacted by acid mine drainage. Based on Pb(2+) breakthrough time for single-metal system at a pH of approximately 5, the sorption capacity of Pb(2+) was estimated to be higher in lateritic soil than the other metals. For multi-metal systems, the estimated retardation factors for the metals from highest to lowest were: Pb(2+)>Zn(2+)～ Ni(2+)>Mn(2+), suggesting the mobility of metals through lateritic soil for a multi-metal system would be in the order of Mn(2+)>Ni(2+)～ Zn(2+)>Pb(2+). For binary and multi-metal systems, the estimated sorption capacities of individual metals were found to be lower than the sorption capacities in single metal system - indicating possible competition for sorption sites. Mass recoveries estimates showed that the sorption of metals was more reversible under competitive multi-metal systems than in single metal systems.     

Sorption properties of the activated carbon-zeolite composite prepared from coal fly ash for Ni(2+), Cu(2+), Cd(2+) and Pb(2+)

Composite materials of activated carbon and zeolite have been prepared successfully by activating coal fly ash (CFA) by fusion with NaOH at 750 degrees C in N(2) followed by hydrothermal treatments under various conditions. Uptake experiments for Ni(2+), Cu(2+), Cd(2+) and Pb(2+) were performed with the materials thus obtained from CFA. Of the various composite materials, that were obtained by hydrothermal treatment with NaOH solution (ca. 4M) at 80 degrees C (a composite of activated carbon and zeolite X/faujasite) proved to be the most suitable for the uptake of toxic metal ions. The relative selectivity of the present sorbents for the various ions was Pb(2+)>Cu(2+)>Cd(2+)>Ni(2+), with equilibrium uptake capacities of 2.65, 1.72, 1.44 and 1.20mmol/g, respectively. The sorption isotherm was a good fit to the Langmuir isotherm and the sorption is thought to progress mainly by ion exchange with Na(+). The overall reaction is pseudo-second order with rate constants of 0.14, 0.17, 0.21 and 0.20Lg/mmol min for the uptake of Pb(2+), Cu(2+), Cd(2+) and Ni(2+), respectively.     

Sorption processes and XRD analysis of a natural zeolite exchanged with Pb(2+), Cd(2+) and Zn(2+) cations

In this study the Pb(2+), Cd(2+) and Zn(2+) adsorption capacity of a natural zeolite was evaluated in batch tests at a constant pH of 5.5 by polluting this mineral with solutions containing increasing concentrations of the three cations to obtain adsorption isotherms. In addition X-ray powder diffraction (XRD) was used to investigate the changes of zeolite structure caused by the exchange with cations of different ionic radius. The zeolite adsorption capacity for the three cations was Zn>Pb>Cd. Moreover a sequential extraction procedure [H(2)O, 0.05 M Ca(NO(3))(2) and 0.02 M EDTA] was applied to zeolite samples used in the adsorption experiments to determine the chemical form of the cations bound to the sorbent. Using this approach it was shown that low concentrations of Pb(2+), Cd(2+) and Zn(2+) were present as water-soluble and exchangeable fractions (<25% of the Me adsorbed), while EDTA extracted most of the adsorbed cations from the zeolite (>27% of the Me adsorbed). The XRD pattern of zeolite, analysed according to the Rietveld method, showed that the main mineralogical phase involved in the adsorption process was clinoptilolite. Besides structure information showed that the incorporation of Pb(2+), Cd(2+) and Zn(2+), into the zeolite frameworks changed slightly but appreciably the lattice parameters. XRD analysis also showed the occurrence of some isomorphic substitution phenomena where the Al(3+) ions of the clinoptilolite framework were replaced by exchanged Pb(2+) cations in the course of the ion exchange reaction. This mechanism was instead less evident in the patterns of the samples doped with Cd(2+) and Zn(2+) cations.     

Comparison of synthesis of chelating resin silica-gel-supported diethylenetriamine and its removal properties for transition metal ions

Four kinds of silica-gel (SG)-supported diethylenetriamine (DETA) chelating resins SG-DETA-1, SG-DETA-2, SG-DETA-3, and SG-DETA-4 were prepared by functionalization of silica-gel via so-called "heterogeneous-direct-amination" (hetero-DA), "homogeneous-direct-amination" (homo-DA), "heterogeneous end-group protection" (hetero-EGP), and "homogeneous end-group protection" (homo-EGP) routes, respectively. These functionalized reactions on silica-gel were confirmed through elemental analysis, infrared spectroscopy, X-ray diffractometry, porous analysis, and thermogravimetry. Element analysis revealed that the direct-amination routes and homogeneous condition were more beneficial than the corresponding end-group protection routes and heterogeneous condition to the syntheses of chelating resins with high N content. Several metal ions, such as Ag(+), Cu(2+), Ni(2+), Hg(2+), Zn(2+) and Pb(2+), were chosen as representatives to investigate the relationship between adsorption capacities and N content of ligands onto the surface of silica-gel. The experiments results showed that all resins, SG-DETA-1, SG-DETA-2, SG-DETA-3 and SG-DETA-4, had a better adsorption for Hg(2+) and Cu(2+) than others. One conclusion should be drawn from the above compared experiments, that is, higher N content of silica-gel resins does not ensure a higher utilization ratio of N.     

Heavy metal removal from aqueous solutions by activated phosphate rock

The use of natural adsorbent such as phosphate rock to replace expensive imported synthetic adsorbent is particularly appropriate for developing countries such as Tunisia. In this study, the removal characteristics of lead, cadmium, copper and zinc ions from aqueous solution by activated phosphate rock were investigated under various operating variables like contact time, solution pH, initial metal concentration and temperature. The kinetic and the sorption process of these metal ions were compared for phosphate rock (PR) and activated phosphate rock (APR). To accomplish this objective we have: (a) characterized both (PR) and (APR) using different techniques (XRD, IR) and analyses (EDAX, BET-N(2)); and, (b) qualified and quantified the interaction of Pb(2+), Cd(2+), Cu(2+) and Zn(2+) with these sorbents through batch experiments. Initial uptake of these metal ions increases with time up to 1h for (PR) and 2h for (APR), after then, it reaches equilibrium. The maximum sorption obtained for (PR) and (APR) is between pH 2 and 3 for Pb(2+) and 4 and 6 for Cd(2+), Cu(2+) and Zn(2+). The effect of temperature has been carried out at 10, 20 and 40 degrees C. The data obtained from sorption isotherms of metal ions at different temperatures fit to linear form of Langmuir sorption equation. The heat of sorption (DeltaH degrees), free energy (DeltaG degrees) and change in entropy (DeltaS degrees) were calculated. They show that sorption of Pb(2+), Cd(2+), Cu(2+) and Zn(2+) on (PR) and (APR) an endothermic process. These findings are significant for future using of (APR) for the removal of heavy metal ions from wastewater under realistic competitive conditions in terms of initial heavy metals, concentrations and pH.     

FTIR spectrophotometry, kinetics and adsorption isotherms modeling, ion exchange, and EDX analysis for understanding the mechanism of Cd(2+) and Pb(2+) removal by mango peel waste

Mango peel waste (MPW) was evaluated as a new sorbent for the removal of Cd(2+) and Pb(2+) from aqueous solution. The maximum sorption capacity of Cd(2+) and Pb(2+) was found to be 68.92 and 99.05mgg(-1), respectively. The kinetics of sorption of both metals was fast, reaching at equilibrium in 60min. Sorption kinetics and equilibria followed pseudo-second order and Langmuir adsorption isotherm models. FTIR analysis revealed that carboxyl and hydroxyl functional groups were mainly responsible for the sorption of Cd(2+) and Pb(2+). Chemical modification of MPW for blocking of carboxyl and hydroxyl groups showed that 72.46% and 76.26% removal of Cd(2+) and Pb(2+), respectively, was due to the involvement of carboxylic group, whereas 26.64% and 23.74% was due to the hydroxyl group. EDX analysis of MPW before and after metal sorption and release of cations (Ca(2+), Mg(2+), Na(+), K(+)) and proton H(+) from MPW with the corresponding uptake of Cd(2+) and Pb(2+) revealed that the main mechanism of sorption was ion exchange. The regeneration experiments showed that the MPW could be reused for five cycles without significant loss in its initial sorption capacity. The study points to the potential of new use of MPW as an effective sorbent for the removal of Cd(2+) and Pb(2+) from aqueous solution.     

Chitosan selectivity for removing cadmium (II), copper (II), and lead (II) from aqueous phase: pH and organic matter effect

The aim of this study was to investigate the selectivity of chitosan for cadmium, copper and lead in the presence and absence of natural organic matter (NOM) in different pH solutions. Adsorption isotherms of one and three adsorbates at initial concentration of 5-100mg/L were carried out in batch reactors at pH 4, 5, or 7 and 25 degrees C in reactive and clarified water. The chitosan employed had a MW of 107.8 x 10(3)g/mol and degree of acetylation (DA) of 33.7%. The chitosan adsorption capacity at pH 4 in reactive water was 0.036, 0.016, 0.010mmol/g for Pb(2+), Cd(2+), and Cu(2+), respectively, and it decreased for Pb(2+) and Cd(2+) in clarified water. Conversely, experiments carried out in clarified water showed that the cadmium adsorption capacity of chitosan was enhanced about three times by the presence of NOM at pH 7: an adsorption mechanism was proposed. Furthermore, it was found that the biosorbent selectivity, in both reactive and clarified water at pH 4, was as follows Cu(2+)>Cd(2+)>Pb(2+). Finally, the preliminary desorption experiments of Cd(2+) conducted at pH 2 and 3 reported 68 and 44.8% of metal desorbed, which indicated that the adsorption mechanism occurred by electrostatic interactions and covalent bonds.