Synthesis of 2,3-dihydroxynaphthalene-functionalized Amberlite XAD-4 resin: Applications for the separation and preconcentration of trace metal ions prior to their determination by inductively coupled plasma atomic emission spectrometry

A simple, sensitive column solid-phase extraction procedure for separation and preconcentration of Cu(II), Ni(II), Co(II), and Cd(II) in spiked and natural water samples using 2,3-dihydroxynaphthalene-functionalized Amberlite XAD-4 (XAD-4-DHN) chelating resin prior to their determination by inductively coupled plasma atomic emission spectrometry was discussed. The optimum experimental parameters such as pH, volume of sample and eluent, flow-rates of uptake and stripping, and sorption capacity of the chelating resin, were evaluated. The effect of the electrolytes and the cations on the preconcentration of metal ions was also investigated. The chelating resin could be reused for more than 20 cycles of sorption–desorption without any significant change (<1.0%). Recoveries obtained from this method range from 96 to 102% with R.S.D of 2.50 (n = 4). The detection limits for Cu(II), Ni(II), Co(II), and Cd(II) were found to be 1.9, 0.9, 1.2 µg, and 1.4 µg L^?1, respectively. The proposed method was applied for the determination of Cu(II), Ni(II), Co(II), and Cd(II) in spiked, tap water, and river water samples.     

Effect of Ca(II), Fe(II), and Fe(III) on Cu(II) adsorption by a polyvinylidene fluoride-based chelating membrane from Cu(II)–EDTA complex solution

A polyvinylidene fluoride-based membrane bearing the diethylenetriaminepentaacetic acid chelating group was employed to recover Cu(II) from the Cu(II)-ethylenediaminetetraacetic acid complex aqueous solution. Effects of Ca(II), Fe(II), and Fe(III) on Cu(II) uptake were investigated by static batch adsorption tests and dynamic adsorption filtration. Isotherms, kinetics, and breakthrough curves of Cu(II) uptakes in the presence of the three cations at concentrations of 1 mmol L^?1 were elucidated. The three cations showed a positive effect on the Cu(II) uptake; the stimulative roles were in the order of Fe(III) > Fe(II) > Ca(II). They did not alter the adsorption behavior of the membrane; adsorption isotherms and kinetics could be described by Langmuir and Lagergren second-order models, and Cu(II) adsorption was a spontaneous and exothermic process. The presence of Ca(II), Fe(II), and Fe(III) increased the sorption capacity of the membrane stack by 1.3, 1.9, and 3 times. Breakthrough time and the exhaustion time of membrane stacks were also extended.     

Microbial electrolysis cells with biocathodes and driven by microbial fuel cells for simultaneous enhanced Co(II) and Cu(II) removal

Cobalt and copper recovery from aqueous Co(II) and Cu(II) is one critical step for cobalt and copper wastewaters treatment. Previous tests have primarily examined Cu(II) and Co(II) removal in microbial electrolysis cells (MECs) with abiotic cathodes and driven by microbial fuel cell (MFCs). However, Cu(II) and Co(II) removal rates were still slow. Here we report MECs with biocathodes and driven by MFCs where enhanced removal rates of 6.0±0.2 mg?L⁻¹?h⁻¹ for Cu(II) at an initial concentration of 50 mg?L⁻¹ and 5.3±0.4 mg?L⁻¹ h⁻¹ for Co(II) at an initial 40 mg?L⁻¹ were achieved, 1.7 times and 3.3 times as high as those in MECs with abiotic cathodes and driven by MFCs. Species of Cu(II) was reduced to pure copper on the cathodes of MFCs whereas Co(II) was removed associated with microorganisms on the cathodes of the connected MECs. Higher Cu(II) concentrations and smaller working volumes in the cathode chambers of MFCs further improved removal rates of Cu(II) (115.7 mg?L⁻¹?h⁻¹) and Co(II) (6.4 mg?L⁻¹?h⁻¹) with concomitantly achieving hydrogen generation (0.05±0.00 mol?mol⁻¹ COD). Phylogenetic analysis on the biocathodes indicates Proteobacteria dominantly accounted for 67.9% of the total reads, followed by Firmicutes (14.0%), Bacteroidetes (6.1%), Tenericutes (2.5%), Lentisphaerae (1.4%), and Synergistetes (1.0%). This study provides a beneficial attempt to achieve simultaneous enhanced Cu(II) and Co(II) removal, and efficient Cu(II) and Co(II) wastewaters treatment without any external energy consumption.     

Scalp hair metal analysis in the assessment of the occupational exposure of arc welders

Eleven metals (Ca, Mg, Fe, Zn, Cu, Mn, Cd, Co, Cr, Ni and Pb) were estimated in hair samples of metal arc welders and a control group with the same socioeconomic background. Nitric acid–perchloric acid wet digestion procedure was adopted for the estimation of endogenous metal contents by ICP-AE technique. The study exhibited the following increasing order of the metal concentrations: Cd??1, dry weight, respectively. On average, the levels of Mn, Ni, Pb and Fe were found to be 1.5–2.4 times higher in the hair of welders compared with controls. Besides age and exposure which were strongly correlated, Cu–Mg, Mn–Mg, Ca–Co and Cd–Zn also showed significantly positive correlations. The identification of metal sources, done by cluster and principal component analyses, revealed four factors: age and exposure; Cu, Mg, Mn and Fe; Ca and Co; Cd, Zn, Ni and Pb. High levels of Fe were found to have a depleting impact on Co levels. The arc welders were feared to accumulate heavy metals in their bodies due to long-term endogenous exposure.     

Trace metal concentrations in cigarette brands commonly available in Turkey: relation with human health

In this study, the concentrations of Co, Ni, Fe, Cu, Mn, Pb, Cr, and Cd were determined in 15 cigarette brands from Turkey by flame atomic absorption spectrometry (FAAS). A wet digestion method was employed to cigarette samples. The mean values obtained for Co, Ni, Fe, Cu, Mn, Pb, Cr, and Cd were 1.2, 4.1, 134, 14, 66, 3.7, 5.0, and 1.1?µg?g^?1, respectively, i.e., in the order of Fe?>?Mn?>?Cu?>?Cr?>?Ni?>?Pb?>?Co?>?Cd. The results were compared with the literature values for other international cigarette brands.     

Removal of cadmium(II), lead(II), and chromium(VI) ions from aqueous solution using clay

Removal of cadmium(II), lead(II), and chromium(VI) from aqueous solution using clay, a naturally occurring low-cost adsorbent, under various conditions, such as contact time, initial concentration, temperature, and pH has been investigated. The sorption of these metals follows both Langmuir and Freundlich adsorption isotherms. The magnitude of Langmuir and Freundlich constants at 30°C for cadmium, lead, and chromium indicate good adsorption capacity. The kinetic rate constants (K _ad) indicate that the adsorption follows first order. The thermodynamic parameters: free energy change (ΔG ^o), enthalpy change (ΔH ^o), and entropy change (ΔS ^o) show that adsorption is an endothermic process and that adsorption is favored at high temperature. The results reveal that clay is a good adsorbent for the removal of these metals from wastewater.     

Availability of copper from phytoplankton and water for the bivalveMacoma balthica. II. Uptake and elimination from64Cu-labelled diatoms and water

The amount of copper taken up via algae and water byMacoma balthica from the Oosterschelde sea arm, S.W. Netherlands, was established using the radioisotope⁶⁴Cu. As far as we know, this isotope has never been used before in marine flod chain studies. As a model food source the marine diatomPhaeodactylum tricornutum was allowed to accumulate⁶⁴Cu for 1 d. These labelled algae were fed to the clams in the presence of the complexing agent EDTA (0.27mM). EDTA was added to prevent uptake of dissolved⁶⁴Cu that could be leaking from the labelled diatoms. In control experiments, unlabelled diatoms were fed toM. balthica in the presence of dissolved⁶⁴Cu (with and without EDTA) in order to assure a similar filtration activity. In repeated experiments with varying particulate/dissolved copper ratios, uptake through food always turned out to be at least as efficient as uptake from the water. It was concluded that Cu, associated with food, is well available for uptake byM. balthica.     

Biosolids application affects the competitive sorption and lability of cadmium,copper, nickel,lead, and zinc in fluvial and calcareous soils

The objective of this research was to investigate the effects of biosolids on the competitive sorption and lability of the sorbed Cd, Cu, Ni, Pb, and Zn in fluvial and calcareous soils. Competitive sorption isotherms were developed, and the lability of these metals was estimated by DTPA extraction following their sorption. Sorption of all metals was higher in the fluvial than in the calcareous soil. Sorption of Cu and Pb was stronger than that of Cd, Ni, and Zn in all soils. Biosolids application (2.5%) reduced the sorption of all metals especially Cu and Pb (28–43%) in both soils (especially the calcareous soil) at the lower added metal concentrations (50 and 100 mg L^?1). However, it increased the sorption of all metals especially Pb and Cu in both soils (especially the calcareous soil; 15.5-fold for Cu) at the higher added concentrations (250 and 300 mg L^?1). Nickel showed the highest lability followed by Cd, Zn, and Pb in both soils. Biosolids increased the lability of the sorbed Ni in the fluvial soils at all added concentrations and the lability of Cd, Pb, and Zn at 50 mg L^?1, but decreased the lability of Cd, Pb, and Zn at 250 and 300 mg L^?1 in both soils. We conclude that at low loading rate (e.g., 50 mg L^?1) biosolids treatment might increase the lability and environmental risk of Cd, Cu, Pb, and Zn. However, at high loading rate (e.g., 300 mg L^?1) biosolids may be used as an immobilizing agent for Cd, Cu, Pb, Zn and mobilizing agent for Ni.     

Development and application of cross-linked polyethylenimine for trace metal and metalloid removal from mining and industrial wastewaters

Pollution of water bodies by trace metals is an established problem and several studies have been conducted to deal with it. South Africa is amongst those countries whose water systems are most affected as a result of intensive mining activities. This research was dedicated to the development of an insoluble chelating polymer for use as an adsorbent for abstraction of metal ions from mining and industrial wastewaters. Polyethylenimine (PEI), well known for its metal chelating potential, was cross-linked by epichlorohydrin (ECH) in order to convert it into a water-insoluble form for direct use as an adsorbent. The binding affinity of the cross-linked polyethylenimine (CPEI) to heavy metal ions was assessed as well as its ability to be regenerated for re-use. CPEI exhibited good complexation ability to metal ions with high affinity to Cr and most divalent metal ions. The observed order of complexation was: Cr?>?Zn>?Fe?>?Ni?>?Mn?>?Pb. On the other hand, it showed very poor ability to bind oxo-anions such as SeO₃ ^2? and AsO₂ ^? which has been attributed to the unavailability of suitable functional groups to interact with these ions.     

Lead(II) and cadmium(II) removal from aqueous solution using processed walnut shell: kinetic and equilibrium study

The biosorption potential of processed walnut shell for Pb(II) and Cd(II) ions from aqueous solutions was explored. The effects of pH, contact time, initial ion concentration, and amount of dried adsorbent were studied in batch experiments. The maximum adsorption was achieved within the pH range 4.0–6.0. The equilibrium data were well fitted by the Langmuir isotherm model. The maximum monolayer adsorption capacities were found to be 32?g?kg^?1 and 11.6?g?kg^?1 for Pb(II) and Cd(II) ions, respectively. Kinetic data were best described by the pseudo-second-order model. The structural features of the adsorbent were characterized by Fourier transform infrared spectroscopy, which confirmed the involvement of hydroxyl (–OH), carboxyl (–COO^–), and carbonyl (C=O) groups in metal sorption. This readily available adsorbent is efficient in the uptake of Pb(II) and Cd(II) ions from an aqueous solution and could be used for the treatment of wastewater streams bearing these metal ions.     

Remobilization of selected metal ions from Nile sediment (Egypt) according to sequential extraction and metal–EDTA complex

River sediments are basic components of our environment, providing nutrients for living organisms and serving as sinks for deleterious chemical species. The metal contents may be remobilized and released back into waters with changes in environmental conditions, thus affecting living organisms and human activities. This paper aims to determine the effect of a synthetic anthropogenic chelating agent (EDTA) as industrial discharges on the remobilization of several metals (Cu, Zn, Cd, and Pb) in River Nile sediments (at Aswan and Mansoura cities) under different concentrations and pH values, and to investigate the influence of metal–EDTA complexes on this remobilization. For these purposes, sequential extraction and experiments on the effect of pH and metal EDTA complex were carried out on the two representative sediment samples south and north of the River Nile in Egypt. The results of sequential extraction show that most of metal contents present in the residual form (Cu, 11.36–72.34%; Pb, 29.64–66.67%; and Zn, 43.76–50.09% at Aswan and Mansoura, respectively). Non-residual fractions which may be available for the remobilization by EDTA represented anthropogenic (industrial, agriculture, and domestic discharges) and lithiopogenic (metals bound to Fe and Mn oxides) sources. A clear increase was detected for Cu and Zn remobilization from the increase in EDTA concentrations, in contrast, Cd independent of the EDTA concentration and slight influence on Pb content. The remobilization of metals as a function of pH exhibited. The metals were greatly remobilized under the complexing action of EDTA, showing that some of these elements were adsorbed on the sediments. The remobilization rate of metals was dependent upon the added metal–EDTA complex (with the exchange rate being in the order Ca–EDTA>Zn–EDTA>Cd–EDTA>Cu–EDTA>Pb–EDTA), due to the stability constant of the metal–EDTA complex. The results of these experiments showed that heavy metals are greatly remobilized under the complexing action of EDTA when it is present in excess, so all precautions should be taken to prevent any wastewater containing EDTA or any chelating agents discharging directly or indirectly via the River Nile stream because most EDTA remains in the aquatic phase. The ability of this portion to remobilize metals from sediments should be taken into account.     

Bioaccumulation of heavy metals in Octopus vulgaris from coastal waters of Alexandria (Eastern Mediterranean)

Heavy metal concentrations (Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn) were determined in various tissues (hepatopancreas, branchial hearts, salivary gland, gills, genital tract, mantle, arms and skin) of Octopus vulgaris collected from three different contaminated sites in front of Alexandria (Egypt) during 2000. All collected tissues displayed high enrichment factors when compared to ambient levels. Heavy metal concentrations in most tissues displayed significant differences among sites, sizes and sex. This study suggests that hepatopancreas, and to a lesser extent branchial hearts, are better indicators of chronic Cu, Fe, Zn and Cd contamination than edible tissues. The enrichment factor (EF) for heavy metals in the hepatopancreas and in edible tissues allowed discriminating our samples into three main groups; (1) EF?>?55 (Cu), (2) EF ranging from 15 to 7.5 (Fe, Cd and Zn) and (3) EF?相似文献   

Synthesis,structural elucidation,electro-chemical behaviour and fungitoxic activity of transition metal(II) mixed-ligand complexes with some Schiff bases

The Schiff bases, potassium salt of salicylidene-β-alanine [KHL], bis(benzylidene)ethylenediamine [SB¹] and thiophene-o-carboxaldene-p-toluidine [SB²], and mixed-ligand complexes with Mn(II), Co(II), Ni(II), Cu(II), Zn(II), and Cd(II) have been prepared. They were characterized by elemental analyses, magnetic susceptibility measurements, thermogravimetric analyses (t.g.a.), infrared spectra and electronic spectra. The mixed-ligand complexes were found to have the general composition [M(L)(SB)(H₂O)]. All the mixed-ligand complexes were found to have six-coordinated octahedral geometry. The fungitoxic activity of the ligands, metal salts, control (DMSO), bavistin, emcarb, and mixed-ligand complexes were screened against Aspergillus niger, Fusarium oxysporum and Aspergillus flavus. All the mixed-ligand complexes show higher fungitoxic activity as compared to the Schiff bases, metal nitrate and control (dimethyl sulphoxide, DMSO), and moderate fungitoxic activity as compared to the fungicides (bavistin and emcarb).     

Toxic effect of transition metal complexes on Salmonella typhi,Escherichia coli and Serratia marcescens

The present article describes the synthesis, structural features and toxicological studies of the complexes of the type [M(L)(dipy-amine)(H₂O)] or [M(L)(bendan)(H₂O)] where M?=?Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II), H₂L?=?salicylidene-o-aminothiophenol, dipy-amine?=di(2-pyridyal)amine, or bendan?=?bis(benzylidene)1,8-diaminonaphthalene. The complexes have been characterized on the basis of elemental analyses, electronic spectra, magnetic measurement and thermogravimetric analyses. The nature of the bonding has been discussed on the basis of infrared spectral data. A thermal study of the complexes has been carried out to ascertain their thermal stability. Magnetic susceptibility measurements and electronic spectral data suggest a six-coordinated octahedral structure for these complexes. The complexes of Mn(II), Co(II), Ni(II), Cu(II) are paramagnetic, while Zn(II) and Cd(II) are diamagnetic in nature. The toxic effects of the investigated complexes were tested against three Gram-negative bacteria, Salmonella typhi, Escherichia coli and Serratia marcescens by the “Disc Diffusion Method”. It is observed that the complexes show higher toxic effects as compared to the ligands, metal salts and control (DMSO), but moderate toxic effects as compared to the standard drug (tetracycline) and the results are discussed.     

Sorption of cadmium(II) and copper(II) by soil humic acids: temperature effects and sorption heterogeneity

Sorption by humic acids is known to modify the bioavailability and toxicity of metals in soils and aquatic systems. The sorption of cadmium(II) and copper(II) to two soil humic acids was measured at pH 6.0 using ion-selective electrode potentiometric titration at different temperatures. Sorption reactions were studied with all components in aqueous solution, or with the humates in suspension. Adsorption reactions were described using a multiple site-binding model, and a model assuming a continuous log-normal distribution of adsorption constants. Adsorption of Cu²⁺ was more favourable than adsorption of Cd²⁺. The log-normal distribution model provided the closest fit to observations and allowed parameterisation of adsorption data using a mean adsorption constant (log K _μ). Sorption of Cd²⁺ to dissolved humic acids increased slightly in extent and sorption affinity with increasing temperature, but the effect was small (log K _μ 2.96–3.15). A slightly greater temperature effect occurred for sorption of Cd²⁺ to solid-phase humic acids (log K _μ 1.30–2.08). Sorption of copper(II) to both aqueous- and colloidal-phase humates showed more pronounced temperature dependence, with extent of sorption, and sorption affinity, increasing with increasing temperature (log K _μ 3.4–4.9 in solution and 1.4–4.5 in suspension). The weaker adsorption of Cd²⁺ than Cu²⁺, and smaller temperature effects for dissolved humates than suspended humates, suggested that the observed temperature effects had a kinetic, rather than thermodynamic, origin. For any metal-to-ligand ratio, free metal ion concentration, and by inference metal bioavailability, decreased with increasing temperature. The consistency of the data with kinetic rather than thermodynamic control of metal bioavailability suggests that equilibrium modelling approaches to estimating bioavailability may be insufficient.     

Biosorption of chromium(VI), nickel(II) and copper(II) ions from aqueous solutions using Pithophora algae

The biosorption of heavy metals is considered to be one of the best alternatives for the treatment of wastewater. The metal binding capacity of algae and acid-treated algae is investigated to find out the removal characteristics of Cr(VI), Ni(II) and Cu(II) ions from single metal solutions. Batch experiments are conducted and the study is extended to investigate the effect of pH, amount of adsorbent and adsorbate concentration on the extent of biosorption. The results indicate that the adsorption capacity of algae depends strongly on pH. The maximum adsorption of Cr(VI), Ni(II) and Cu(II) occurs at pH values of 2, 7 and 4.3, respectively. The adsorption process follows first-order kinetic equation. The data obtained are correlated with Freundlich and Langmuir adsorption isotherms.     

Solid phase extraction of trace metals from environmental samples using Amberlite XAD-7 loaded with 2-hydroxy-propiophenone-4-phenyl-3-thiosemicarbazone and determination by inductively coupled plasma–atomic emission spectrometry

A method for the solid phase extraction of trace metals, namely Co, Cu, Pb, Ni and Zn, from environmental and biological samples using column Amberlite XAD-7 loaded with 2-hydroxy-propiophenone-4-phenyl-3-thiosemicarbazone (HPPPTSC) and determination by inductively coupled spectrometry (ICP–AES) has been developed. The reagent has the capacity to form chelate complexes with the metals because of three binding sites in the reagent molecule. The optimum experimental conditions for the quantitative sorption of five metals, pH, effect of flow rate, concentration of eluent, sorption capacity and the effect of diverse ions on the preconcentration of analytes have been investigated. The sorption capacity of the resin has 83, 127, 35, 88 and 85?µmol?g^?1 for Co²⁺, Cu²⁺, Pb²⁺, Ni²⁺ and Zn²⁺, respectively. The preconcentration factors for Co²⁺, Cu²⁺, Pb²⁺, Ni²⁺ and Zn²⁺ were 100, 110, 120, 140 and 150, respectively. The accuracy of the proposed procedure was evaluated by standard reference materials. The achieved results were in good agreement with certified values. The proposed method was applied for the determination of trace metals in river water and plant leaves.     

Nickel and copper accumulation strategies in Odontarrhena obovata growing on copper smelter-influenced and non-influenced serpentine soils: a comparative field study

The present investigation is the first in situ comparative study for the identification of Ni and Cu accumulation strategies involved in Odontarrhena obovata (syn. Alyssum obovatum (C.A. Mey.) Turcz.) growing in Cu-rich smelter-influenced (CSI) and non-Cu-influenced (NCI) sites. The total and Na₂EDTA (disodium ethylenediaminetetraacetic acid)-extractable metal concentration in soils and plant tissues (roots, stem, leaves and flowers) were determined for CSI and NCI sites. High concentrations of total Ni, Cr, Co and Mg in the soil suggest serpentine nature of both the sites. In spite of high total and extractable Cu concentrations in CSI soil, majority of its accumulation was restricted to O. obovata roots showing its excluder response. Since the translocation and bioconcentration factors of Ni?>?1 and the foliar Ni concentration?>?1000 μg g^?1, it can be assumed that O. obovata has Ni hyperaccumulation potential for both the sites. No significant differences in chlorophyll content in O. obovata leaves were observed between studied sites, suggesting higher tolerance of this species under prolonged heavy metal stress. Furthermore, this species from CSI site demonstrated rather high viability under extreme technogenic conditions due to active formation of antioxidants such as ascorbate, free proline and protein thiols. The presence of Cu in higher concentration in serpentine soil does not exert detrimental effect on O. obovata and its Ni hyperaccumulation ability. Thus, O. obovata could act as a putative plant species for the remediation of Cu-rich/influenced serpentine soils without compromising its Ni content and vitality.