Electrochemical methodology to study labile trace metal/natural organic matter complexation at low concentration levels in natural waters

A new electrochemical methodology to study labile trace metal/natural organic matter complexation at low concentration levels in natural waters is presented. This methodology consists of three steps: (i) an estimation of the complex diffusion coefficient (D_ML), (ii) determination at low pH of the total metal concentration initially present in the sample, (iii) a metal titration at the desired pH. The free and bound metal concentrations are determined for each point of the titration and modeled with the non-ideal competitive adsorption (NICA-Donnan) model in order to obtain the binding parameters. In this methodology, it is recommended to determine the hydrodynamic transport parameter, α, for each set of hydrodynamic conditions used in the voltammetric measurements.The methodology was tested using two fractions of natural organic matter (NOM) isolated from the Loire river, namely the hydrophobic organic matter (HPO) and the transphilic organic matter (TPI), and a well characterized fulvic acid (Laurentian fulvic acid, LFA). The complex diffusion coefficients obtained at pH 5 were 0.4 ± 0.2 for Pb and Cu/HPO, 1.8 ± 0.2 for Pb/TPI and (0.612 ± 0.009) × 10⁻¹⁰ m² s⁻¹ for Pb/LFA. NICA-Donnan parameters for lead binding were obtained for the HPO and TPI fractions. The new lead/LFA results were successfully predicted using parameters derived in our previous work.     

Use of a NICA-Donnan approach for analysis of proton binding to a lignocellulosic substrate extracted from wheat bran

The acid-base properties of a lignocellulosic substrate extracted from wheat bran have been investigated. The lignocellulosic substrate was first studied by use of FTIR, XPS, and solid-state 13C NMR to characterize the surface-active groups. Major contributions arise from the presence of carboxylic and phenolic sites. The former are associated with long-chain fatty acids and the latter are constituent units of lignin. All ionizable sites were quantified by use of the Ca-acetate method and by potentiometric titrations in non-aqueous media. Results were compared with those from conductimetric titrations in water and in the presence of barium ions. Protometric titration curves for the lignocellulosic substrate were obtained at several ionic strengths. Data were also treated with the NICA-Donnan model to determine the intrinsic ionization parameters.     

Adsorption of Cu(II) and Ni(II) on solid humic acid from the Azraq area, Jordan

Isotherms of adsorption of Cu(II) and Ni(II) onto solid Azraq humic acid (AZHA) were studied at different pH (2.0-3.7) values and 0.1 M NaClO4 ionic strength. The Langmuir monolayer adsorption capacity was found to range from 0.1 to 1.0 mmol metal ion/g AZHA, where Cu(II) has higher adsorptivity than Ni(II). The previously reported NICA-Donnan parameters for sorption of Cu(II) on HA fit the amount of Cu(bound) determined in the present study at pH 3.7 but underestimates those at pH values of 3.0, 2.4, and 2.0. The contribution of low affinity sites to binding of metal ions increases with decreasing pH and increasing metal ion loading. The aggregation of HA, which is facilitated by decreasing pH and increasing metal loading, may increase the ability of low-affinity sites to encapsulate metal ions. The binding of Ni(II) to HA exhibits less heterogeneity and less multidentism than that of Cu(II). AZHA loaded with Cu(II) and Ni(II) was found to be insoluble in water with no measurable amount of desorbed metal ions.     

Synthesis and characterization of nano-composite ion-exchanger; its adsorption behavior

A novel organic-inorganic nanocomposite cation-exchanger has been synthesized via sol-gel method. It was characterized on the basis of FTIR, XRD, SEM, TEM, AFM and Raman studies. The structural studies reveal semi-crystalline nature of the material with the particle size ranging from 1-5 nm. Physiochemical properties such as ion-exchange capacity, chemical and thermal stability of composite material have also been determined. Bifunctional behavior of the material has been indicated by its pH titrations curves. The nanocomposite material exhibits improved thermal stability, higher ion-exchange capacity and better selectivity for toxic heavy metals. The ion-exchange material shows an ion-exchange capacity of 1.8 meq g(-1) for Na(+) ions. Sorption behavior of metal ions on the material was studied in different solvents. The cation exchanger was found to be selective for Pb(II), Hg(II) and Zr(IV) ions. The limit of detection (LOD) and the limit of quantification (LOQ) for Pb(II) ion was found to be 0.85 and 2.85 μg L(-1). Analytically important separations of heavy metal ions in synthetic mixtures as well as industrial effluents and natural water were achieved with the exchanger. The practical utility of polyanilineZr(IV)sulphosalicylate cation exchanger has been established for the analysis and recovery of heavy metal ions in environmental samples.     

Complexes of diethylenetriaminepentaacetic acid as contrast agents in NMR imaging. Computer simulation of equilibria in human blood plasma

In magnetic resonance imaging (MRI), the degree of contrast can be improved by using suitable contrast agents. The diethylenetriaminepentaacetic acid (DTPA) complexes of paramagnetic ions have been proposed for this purpose. This paper deals with extensive simulations of the distribution of species in blood plasma when solutions of manganese(II), copper(II), iron(III) and gadolinium(III) ions (as their soluble salts and as DTPA complexes) are injected. The various interaction equilibria, for which formation constants are known, are considered in order to assess toxic side-effects associated with their use in MRI. The data obtained support from the thermodynamic point of view, the use of GdDTPA, and suggest that the administration of a slight excess of ligand would guarantee complete coordination of the toxic gadolinium ion, and only minor interaction with the metal ions naturally present in blood plasma.     

Quantitative Studies of Metal Ion Adsorption on a Chemically Modified Carbon Surface: Adsorption of Cd(II) and Hg(II) on Glutathione Modified Carbon

The adsorption behavior of model toxic metal cations namely Cd(II) and Hg(II) on carbon surfaces chemically modified by glutathione was investigated as a function of the concentration of Cd²⁺ and Hg²⁺ ions, time and the amount of modified carbon used. Square wave and linear sweep anodic stripping voltammetry was used to monitor the uptake of Cd(II) and Hg(II) ions respectively. Kinetic and adsorption isotherm studies reveal that both Cd(II) and Hg(II) ions undergo similar large adsorption with the modified glutathione carbon material (Glu‐carbon).     

Metal Ions Binding to Natural Organic Matter Extracted from Wheat Bran: Application of the Surface Complexation Model

Ions binding to solid organic matter was investigated in this study. A simple surface complexation model, the diffuse double-layer model, was used to describe Pb(II), Cd(II), Zn(II), and Ni(II) binding to a lignocellulosic substrate extracted from wheat bran. The lignocellulosic substrate was represented by two acid sites: a low-pH ("carboxylic") site and a high-pH ("phenolic") site, the phenolic-type sites contributing significantly to the binding behavior, even at relatively low pH. By using the previously determined concentrations of sites and acidity constants, the surface complexation model was applied to Pb, Cd, Zn, and Ni binding as a function of pH in a 0.1 M NaNO(3) medium. The model fits were good over a wide range of pH (2相似文献   

Studying the sorption kinetics on peat ions of iron(III) and copper(II) from wastewater

The sorption kinetics on the peat of copper(II) and iron(III) ions from model solutions are studied. The sorption process takes place quickly and is almost complete after 20 minutes. Based on the processing of the experimental absorption curves of the equations of chemical kinetics and diffusion it is established that the sorption process is in the diffusion mode. The stage of the chemical interaction of the metal ions with the functional groups of peat also contributes to the overall speed of the process. The efficiency of the sorption process is determined and the possibility of Using peat as a sorbent for purifying wastewater from the copper( II) and iron(III) ions at industrial sites is shown.     

Removal of lead and cadmium ions from aqueous solution by adsorption onto micro-particles of dry plants

In the present work, Pb(II) and Cd(II) ion adsorption onto inert organic matter (IOM) obtained from ground dried plants: Euphorbia echinus, Launea arborescens, Senecio anthophorbium growing in semi-arid zones of Morocco and Carpobrotus edulis as the Mediterranean plant has been studied. A suspension of plant deroed micro-particles adsorbs lead and cadmium present as ionic species, with a higher affinity for Pb(II). The kinetics and the maximum capacity adsorption depend on the type of plant as well as on the metal ions (atomic weight, ionic radius and electronegativity). The adsorption process is affected by various parameters such as contact time, solution volume to mass of plant particles ratio (m/V), particle size, solution pH and metal concentration. A dose of 25 g/l of adsorbent was optimal to obtain maximum adsorption of both metal ions. The maximum metal uptake was obtained with particles of organic matter of <50 microm. As to classical ionic adsorption phenomena, the adsorption of both metal ions increases with the increase of the initial concentration in the solution. For the two metal cations, the uptake efficiency of the studied plants ranged from: C. edulis>E. echinus>S. anthophorbium>L. arborescens, however, the differences are rather small. Two different waste water types (domestic and industrial) were tested and good results were obtained for removal of Pb(II) and Cd(II) at more than 90%. The removal of the metal and mineral ions waste water was observed for PO(4)(3-) at 88%, for NO(3)(-) at 96.5% and for metal ions (Pb(II), Cd(II), Cu(II) and Zn(II)) at about 100%, using IOM as absorbent.     

Stripping chronopotentiometric measurements of lead(II) and cadmium(II) in soils extracts and wastewaters using a bismuth film screen-printed electrode assembly

The key to remediative processes is the ability to measure toxic contaminants on-site using simple and cheap sensing devices, which are field-portable and can facilitate more rapid decision-making. A three-electrode configuration system has been fabricated using low-cost screen-printing (thick-film) technology and this coupled with a portable electrochemical instrument has provided a a relatively inexpensive on-site detector for trace levels of toxic metals. The carbon surface of the screen-printed working electrode is used as a substrate for in situ deposition of a metallic film of bismuth, which allows the electrochemical preconcentration of metal ions. Lead and cadmium were simultaneously detected using stripping chronopotentiometry at the bismuth film electrode. Detection limits of 8 and 10 ppb were obtained for cadmium(II) and lead(II), respectively, for a deposition time of 120 s. The developed method was applied to the determination of lead and cadmium in soils extracts and wastewaters obtained from polluted sites. For comparison purposes, a mercury film electrode and ICP-MS were also used for validation.     

Evaluating the mobility of toxic metals in untreated industrial wastewater sludge using a BCR sequential extraction procedure and a leaching test

The distribution and speciation of toxic metals in industrial wastewater sludge (IWS) was investigated. In this work, the modified BCR three-stage sequential extraction procedure was applied to the fractionation of Cr Pb Ni, and Cd in untreated industrial wastewater sludge from industrial sites in Hyderabad (Pakistan). The extracts were analyzed using electrothermal atomic absorption spectrometry. The procedure was evaluated using a certified reference material for soil mixed with sewage sludge BCR 483. The results from the partitioning study indicate that more easily mobilized forms (acid exchangeable) of Cd were dominant. The oxidizable fraction was dominant for all four toxic metals. Metal recovery was good, with <4% difference between the total metal recovered through the extractant steps and the total metal determined after microwave digestion. Lixiviation tests (DIN 38414-S4) were used to evaluate the leaching of toxic species from IWS, and it was observed that levels of leachable toxic metals were low compared to the amount of metal extracted in the exchangeable fraction of the BCR protocol.     

Highly efficient adsorption of Pb(II) by cubic nanocrystals in aqueous solution: Behavior and mechanism

As one of the most toxic heavy metal ions, lead pollution has become an urgent problem. Here, a cubic crystal nanoparticle (Prussian blue analogue, PBA), referred to as potassium manganese ferrocyanide (KMFC) was synthesized and used as a highly-effective sorbent for removing Pb(II) from aqueous solution. KMFC is a mesoporous material that has excellent ion exchange properties, which was confirmed by a series of characterizations. This paper investigated the adsorptive attributes of KMFC for lead ions in aqueous solution. The influences of temperature, contact time and pH on adsorption were studied in batch experiments. The KMFC possessed a robust adsorption capacity for resident lead ions in aqueous solution, which attained 1075.27 mg g⁻¹ at room temperature (25 °C), based on the Langmuir model, which was far higher than any previously reported values. The adsorption process was well fitted to a pseudo-second-order kinetic model, as well as Langmuir and Temkin isotherm models, and was endothermic and spontaneous on the basis of thermodynamic analysis. The adsorption of Pb(II) on the surface of KMFC started with electrostatic attraction, due to the electronegativity of KMFC. Further, ion exchange was the dominant mechanism in this adsorption process, which was confirmed by FTIR, XPS, and other supplementary experiments. The good chemisorption (K⁺ exchange) properties of KMFC suggested that it likely has excellent prospects in applications for heavy metal ions adsorption. This study not only provided a new perspective for the design and development of heavy metal sorbents but provided a deep insight into the mechanism of adsorption of heavy metal ions by PBA.     

Adsorption of Pb(II) and Ni(II) From Aqueous Solution by a High-Capacity Industrial Sewage Sludge-Based Adsorbent

In the present study, adsorption of Ni(II) and Pb(II) from aqueous solution was investigated using activated carbon synthesized with industrial wastewater sludge. The synthesized adsorbent was analyzed using nitrogen adsorption–desorption and Fourier transfer infrared (FTIR) techniques. Batch adsorption mode was used to evaluate the effect of solution pH, contact time, adsorbent dose, initial metal ion concentration, and temperature on the adsorption capacity of the synthesized adsorbent. The kinetic data were analyzed using different kinetic models. The pseudo-second-order equation gave the best fit to the experimental data for both metal ions. The equilibrium isotherm data were analyzed using the Langmuir, Freundlich, and Dubinin–Radushkevich (D–R) isotherm models. The results showed that the data obtained for the Ni(II) and Pb(II) adsorption are in good agreement with the Langmuir model. The Langmuir mono-layer maximum adsorption capacities for Ni(II) and Pb(II) ions were estimated to be 74.06 and 88.76 mg g^?1 at 25°C, respectively. In addition, the thermodynamic studies proved that the adsorption process of both metals could be considered endothermic.     

Raman microscopic studies of the liquid-liquid interface between an organic layer and an aqueous solution containing metal ions

Raman microscopic studies of liquid-liquid interfaces between an organic layer and aqueous solutions of metal ions containing extractants are described for the first time. Using a specially constructed cell, the observation of third-phase formation which hinders the mass transfer of metals from the aqueous to the organic layers has been monitored and the spectra discussed in terms of the processes involved and the molecular interactions. The system selected for study was tri-n-butylphosphate-odourless kerosene with zirconium(IV) in aqueous nitric acid solution, a model of an industrial process for nuclear fuels reprocessing. Particulate matter at the interface between the organic and aqueous layers was identified spectroscopically as a carbonate from wash solutions used in neutralisation of the aqueous acid component.     

Selective adsorption, pre-concentration and matrix elimination for the determination of Pb(II), Cd(II), Hg(II) and Cr(III) using 1,5,9,13-tetrathiacyclohexadecane-3,11-diol anchored poly (p-chloromethylstyrene-ethyleneglycoldimethacrylate) microbeads

Poly(p-chloromethylstyrene-ethyleneglycoldimethacrylate) polymeric microbeads, poly(p-CMS-EGDMA), were synthesized and 1,5,9,13-tetrathiacyclohexadecane-3,11-diol (S4HD) was attached chemically onto the polymeric microbeads. Characterization of all microbeads was done by Fourier transform-infrared spectrometry (FT-IR) and elemental analyzer. The amount of attached 1,5,9,13-tetrathiacyclohexadecane-3,11-diol to the polymer was found to be 2.23 mmol g⁻¹ polymers. The ligand attached microbeads, poly(p-CMS-EGDMA-S4HD), were used to examine the adsorption capacity of Pb(II), Cd(II), Hg(II) and Cr(II) ions for recovery, pre-concentration and the matrix elimination by changing the pH and the initial metal ion concentrations and also adsorption kinetics of the studied metal ions was determined. Pre-concentration factors for the studied toxic metal ions were found to be more than 500-fold and recovery was between 92 and 106%. In the drinking, lake, tap and sea-water samples from water lands, ultra-trace toxic metal ion concentrations were determined easily by using ligand modified microbeads after pre-concentration because of the high pre-concentration factor and easily matrix elimination using ligand modified microbeads. Reference sea-water material was used for the validation of the method and it was found that recovery, pre-concentration and the matrix elimination were performed perfectly. For the desorption of the toxic metal ions, 3 M HCl containing 0.8 M thiourea was used and desorption ratio was obtained more than 96%.     

Green synthesis of ZnO and Co-ZnO using Brassica rapa leave’s extract and their activities as antioxidant agents,efficient adsorbents,and dye removal agents

The wastewater released from industries contains many harmful materials like organic dyes and toxic metal ions which badly affect our environment. Nanotechnology is one of the unique approaches to reducing these chemicals. In current research work monometallic ZnO and Co-ZnO bimetallic NPs were synthesized from Brassica rapa leave’s extract and then these were employed for the elimination of methylene blue (MB) and metal ions of Cu (II). Characterization was done by several analytical techniques such as EDX, FTIR, UV–Visible spectroscopy, SEM and XRD. The average diameter of ZnO and Co-ZnO BMNPs was found to be 32.94 nm and 13.82 nm assessed by XRD analysis. The SEM investigation revealed that the produced NPs had a spherical shape. Three distinct methods have opted to determine the antioxidant potential of synthesized NPs. Different factors like pH, contact time, NPs conc., dye conc. and temperature were studied for the elimination of dye while for the eradication of Cu (II) ions; pH, contact time, NPs conc. and adsorbate doses were studied. Adsorption isotherm and kinetic studies were employed for MB and Cu (II) ions elimination while thermodynamic studies were also done for the elimination of MB.     

Adsorption properties of HKUST-1 toward hydrogen and other small molecules monitored by IR

Among microporous systems metal organic frameworks are considered promising materials for molecular adsorption. In this contribution infrared spectroscopy is successfully applied to highlight the positive role played by coordinatively unsaturated Cu2+ ions in HKUST-1, acting as specific interaction sites. A properly activated material, obtained after solvent removal, is characterized by a high fraction of coordinatively unsaturated Cu2+ ions acting as preferential adsorption sites that show specific activities towards some of the most common gaseous species (NO, CO2, CO, N2 and H2). From a temperature dependent IR study, it has been estimated that the H2 adsorption energy is as high as 10 kJ mol(-1). A very complex spectral evolution has been observed upon lowering the temperature. A further peculiarity of this material is the fact that it promotes ortho-para conversion of the adsorbed H2 species.     

Binding and chemical fractionation of heavy metals in typical peat matter

Laboratory batch studies were conducted to evaluate the binding capacity and the mobility of metal species bound to typical humus peat matter. The identification of phase composition of mineral fractions and functional groups in the organic matter was assessed. The results showed generally high, but different retention capacity and binding strength, suggesting distinct diversity in binding mechanisms, phases and chemical nature of binding sites, depending on the metal species and their input concentrations. In general, the binding capacity of peat for the metal ions studied follows the order: Cr(3+) > Cu(2+) > Zn(2+) > Cd(2+) and results in the decrease of pH in the same order, due to displacement of H(3)O(+) from the peat by metal ions. The highest metal enrichment occurs in fractions F1(EXC), F2(CARB), F4(MRO) and F5(OM) of different binding strength adequate to exchangeable, carbonatic, moderately reducible amorphous Fe-oxide and organic/ sulphidic fractions in soils and sediments. In relation to species distribution in peats, the prevailing part of Cr(3+) is strongly bound in oxidizable organic substrate, while Cu(2+) is highly enriched in the moderately reducible F4(MRO) and the most labile F2(EXC) fractions. Cd(2+) and Zn(2+) are predominantly bound in the labile F1(EXC) and F2(CARB) fractions. Diversity of the predominant binding phases for the studied metals suggests rather weak competition for binding sites between chromium and copper ions; the strongest competition between the sorbed metal ions is anticipated for F1(EXC) and F2(CARB) fractions.     

麦麸对重金属离子的吸附性能研究

以麦麸为天然吸附剂,从水溶液中去除重金属离子.实验表明,麦麸对重金属离子有优良的吸附性能.在约10min内达到吸附平衡,吸附容量分别为:Hg2 70mg/g、Pb2 63mg/g、Cd2 21mg/g、Cu2 15mg/g、Ni2 13mg/g及Cr3 9.3mg/g;吸附速率很快,并且对上述金属离子有良好的选择性.     

Structural characterization of Cu2+, Ni2+ and Zn2+ binding sites of model peptides associated with neurodegenerative diseases

Metal ions, especially redox active copper, are thought to play critical roles in neurodegenerative disorders. As a matter of fact, metal binding may result into severe conformational changes of proteins involved in neurodegeneration. The present review describes the interactions of metal ions with model peptides mimicking metal binding sites of such proteins, including the prion protein, the β-amyloid and the α-synuclein that have been related to the pathological onset of spongiform encephalopathies, Alzheimer's disease and Parkinson's disease, respectively. Using short protein fragments provides successful tools for characterizing the metal ion interaction with protein domains devoid of any defined secondary structure, and allows one to gain structural information on the metal ion binding properties of the corresponding proteins. Moreover, such an approach based on simplified models yields a multidimensional knowledge that would be never accessible for the natural systems, thus providing a significant and powerful tool for biochemical studies.