Biosorption of copper (II) and lead (II) from aqueous solutions by nonliving green algae Cladophora fascicularis: Equilibrium, kinetics and environmental effects

Biosorption of Cu²⁺ and Pb²⁺ by Cladop- hora fascicularis was investigated as a function of initial pH, initial heavy metal concentrations, temperature and other co-existing ions. Adsorption equilibriums were well described by Langmuir and Freundlich isotherm models. The maximum adsorption capacities were 1.61 mmol/g for Cu²⁺ and 0.96 mmol/g for Pb²⁺ at 298 K and pH 5.0. The adsorption processes were endothermic and biosorption heats calculated by the Langmuir constant b were 39.0 and 29.6 kJ/mol for Cu²⁺ and Pb²⁺, respectively. The biosorption kinetics followed the pseudo-second order model. No significant effect on the uptake of Cu²⁺ and Pb²⁺ by co-existing cations and anions was observed, except EDTA. Desorption experiments indicated that Na₂EDTA was an efficient desorbent for the recovery of Cu²⁺ and Pb²⁺ from biomass. The results showed that Cladophora fascicularis was an effective and economical biosorbent material for the removal and recovery of heavy metal ions from wastewater.     

Heavy metal ions removal by nano-sized spherical polymer brushes

Nano-sized spherical polymer brushes(SPBs) consisting of both a polystyrene(PS) core and a brush shell of poly(acrylic acid)(PAA), poly(N-acrylcysteamine)(PSH), or poly(N-acrylcysteamine-co-acrylic acid)(P(SH-co-AA)), were prepared by photo-emulsion polymerization. The core-shell structure was observed by dynamic light scattering and transmission electron microscopy. Due to the strengthened Donnan effect, the PAA brush can adsorb heavy metal ions. Effects of the contact time, thickness of PAA brush and pH value on the adsorption results were investigated. Due to the coordination between the mercapto groups and heavy metal ions as well as the electrostatic interactions, SPBs with mercapto groups are capable to remove heavy metal ions selectively from aqueous solutions. The order of adsorption capacity of the heavy metal ions by SPBs with mercapto groups is: Hg2+ ≈ Au3+ Pb2+ Cu2+ Ni2+. The adsorbed heavy metal ions can be eluted from SPB by aqueous HCl solution, and the SPBs can be recovered. After three regenerations the recovered SPBs still maintain their adsorption capacity.     

Heavy Metal Removal from Synthetic Solutions with Magnetic Beads Under Magnetic Field

The aim of this study is to prepare magnetic beads which can be used for the removal of heavy metal ions from synthetic solutions. Magnetic poly(ethylene glycol dimethacrylate‐vinyl imidazole) [m‐poly(EGDMA‐VIM)] beads were produced by suspension polymerization in the presence of magnetite Fe₃O₄ nano‐powder. The specific surface area of the m‐poly(EGDMA‐VIM) beads was found to be 63.1 m²/g with a size range of 150–200 µm in diameter and the swelling ratio was 85%. The average Fe₃O₄ content of the resulting m‐poly(EGDMA‐VIM) beads was 12.4%. The maximum binding capacities of the m‐poly(EGDMA‐VIM) beads were 32.4 mg/g for Cu²⁺, 45.8 mg/g for Zn²⁺, 84.2 mg/g for Cd²⁺and 134.5 mg/g for Pb²⁺. The affinity order on mass basis is Pb²⁺>Cd²⁺>Zn²⁺>Cu²⁺. Equilibrium data agreed well with the Langmuir model. pH significantly affected the binding capacity of the magnetic beads. Binding of heavy metal ions from synthetic wastewater was also studied. The binding capacities were 26.2 mg/g for Cu²⁺, 33.7 mg/g for Zn²⁺, 54.7 mg/g for Cd²⁺ and 108.4 mg/g for Pb²⁺. The magnetic beads could be regenerated up to about 97% by treating with 0.1 M HNO₃. These features make m‐poly(EGDMA‐VIM) beads a potential candidate for support of heavy metal removal under magnetic field.     

Removal of Cd(II), Cu(II), and Pb(II) by adsorption onto natural clay: a kinetic and thermodynamic study

In this work, we study the elimination of three bivalent metal ions (Cd²⁺, Cu²⁺, and Pb²⁺) by adsorption onto natural illitic clay (AM) collected from Marrakech region in Morocco. The characterization of the adsorbent was carried out by X-ray fluorescence, Fourier transform infrared spectroscopy and X-ray diffraction. The influence of physicochemical parameters on the clay adsorption capacity for ions Cd²⁺, Cu²⁺, and Pb²⁺, namely the adsorbent dose, the contact time, the initial pH imposed on the aqueous solution, the initial concentration of the metal solution and the temperature, was studied. The adsorption process is evaluated by different kinetic models such as the pseudo-first-order, pseudo-second-order, and Elovich. The adsorption mechanism was determined by the use of adsorption isotherms such as Langmuir, Freundlich, and Temkin models. Experiments have shown that heavy metals adsorption kinetics onto clay follows the same order, the pseudo-second order. The isotherms of adsorption of metal cations by AM clay are satisfactorily described by the Langmuir model and the maximum adsorption capacities obtained from the natural clay, using the Langmuir isotherm model equation, are 5.25, 13.41, and 15.90 mg/g, respectively for Cd(II), Cu(II), and Pb(II) ions. Adsorption of heavy metals on clay is a spontaneous and endothermic process characterized by a disorder of the medium. The values of ΔH are greater than 40 kJ/mol, which means that the interactions between clay and heavy metals are chemical in nature.     

CC Bonding of Graphene Oxide on 4‐Aminophenyl Modified Gold Electrodes towards Simultaneous Detection of Heavy Metal Ions

This paper studied the electrochemical sensors based on C? C bonding of graphene oxide (GO) on π‐conjugated aromatic group modified gold electrodes for simultaneous detection of heavy metal ions. For comparison, another sensing interface Au‐Ph‐NH‐CO‐GO, in which GO was modified to Au‐Ph‐NH₂ interfaces by amide bonding. On the basis of the principle of heavy metal ions complexation with oxygenated species on GO, the fabricated sensing interfaces were used for the simultaneous determination of Pb²⁺, Cu²⁺ and Hg²⁺. The performance of two sensing interfaces for simultaneous detection of three metal ions was compared. Au‐Ph‐GO sensing interface demonstrated higher sensitivity and better repeatability than Au‐Ph‐NH‐CO‐GO sensing interface.     

Cysteine functionalized poly(hydroxyethyl methacrylate) monolith for heavy metal removal

The aim of this study was to investigate the performance of monoliths composed of hydroxyethyl methacrylate (HEMA) to which N-methacryloyl-(L)-cysteine methyl ester (MAC) was polymerized for removal of heavy metal ions. Poly(HEMA-MAC) monolith was produced by bulk polymerization. Poly(HEMA-MAC) monolith was characterized by FTIR and scanning electron microscopy (SEM). The poly(HEMA-MAC) monolith with a swelling ratio of 89%, and containing 69.4 μmol MAC/g were used in the adsorption studies. Adsorption capacity of the monolith for the metal ions, i.e., Cu²⁺, Cd²⁺, Zn²⁺, Hg²⁺, and Pb²⁺ were investigated in aqueous media containing different amounts of the ions (10–750 mg/L) and at different pH values (3.0–7.0). The maximum adsorption capacities of the poly(HEMA-MAC) monolith were 68.2 mg/g for Zn²⁺, 129.2 mg/g for Cu²⁺, 245.8 mg/g for Pb²⁺, 270.2 mg/g for Hg²⁺, and 284.0 mg/g for Cd²⁺. pH significantly affected the adsorption capacity of MAC incorporated monolith. The competitive adsorption capacities were 587 μmol/g for Zn²⁺, 1646 μmol/g for Cu²⁺, 687 μmol/g for Pb²⁺, 929 μmol/g for Hg²⁺, and 1993 μmol/g for Cd²⁺. The chelating monolith exhibited the following metal ion affinity sequence on molar basis: Cd²⁺ > Cu²⁺ > Hg²⁺ > Pb²⁺ > Zn²⁺. The formation constants of MAC–metal ion complexes have been investigated applying the method of Ruzic. The calculated values of stability constants were 5.28 × 10⁴ L/mol for Cd²⁺, 4.16 × 10⁴ L/mol for Cu²⁺, 2.27 × 10⁴ L/mol for Hg²⁺, 1.98 × 10⁴ L/mol for Pb²⁺, and 1.25 × 10⁴ L/mol for Zn²⁺. Stability constants were increased with increasing binding affinity. The chelating monoliths can be easily regenerated by 0.1 M HNO₃ with higher effectiveness. These features make poly(HEMA-MAC) monolith a potential adsorbent for heavy metal removal.     

Cellulose/chitosan composites prepared in ethylene diamine/potassium thiocyanate for adsorption of heavy metal ions

Cellulose/chitosan composites were successfully prepared in a new and basic-based solvent system, ethylene diamine/potassium thiocyanate (EDA/KSCN), by dissolving cellulose and chitosan in 70/30 (w/w) EDA/KSCN at ?19 °C, and then coagulating in methanol. Wide angle X-ray diffraction studies revealed that the EDA/KSCN solvent system is capable of disrupting the hydrogen bonds in both cellulose and chitosan and increase the amorphous regions. Stability tests proved that the composites are stable in acidic aqueous solution due to the hydrogen bonds formed between cellulose and chitosan. This is the first time to dissolve chitosan in a basic-based solvent system and prepare cellulose/chitosan composites in a straightforward way. The adsorption of heavy metal ions (Cu²⁺, Cd²⁺, and Pb²⁺) onto the cellulose/chitosan composites was investigated. The adsorption capacity is highly dependent on pH and the maximum metal uptake was obtained at pH 5.0. Increasing initial metal concentration enhanced the diffusion of metal ions to the composite surface and therefore the metal removal efficiency. Higher percentage of chitosan in the composites also led to higher metal adsorption. The results indicated that the prepared cellulose/chitosan (1:1) composite can adsorb 0.53 mmol/g Cu²⁺, 0.28 mmol/g Cd²⁺ and 0.16 mmol/g Pb²⁺ ions at pH 5.0. The Freundlich model and the pseudo-second-order model were in good agreement with the adsorption isotherms and kinetics, respectively. X-ray photoelectron spectroscopy studies indicated that the binding of heavy metal ions is attributed to the nitrogen atoms of amino groups in chitosan. The composites can be reused for metal removal.     

Detection of Trace Heavy Metal Ions Using Carbon Nanotube‐ Modified Electrodes

A sensitive voltammetric method for detection of trace heavy metal ions using chemically modified carbon nanotubes (CNTs) electrode surfaces is described. The CNTs were covalently modified with cysteine prior to casting on electrode surfaces. Cysteine is an amino acid with high affinities towards some heavy metals. In this assay, heavy metals ions accumulated on the cysteine‐modified CNT electrode surfaces prior to being subjected to differential pulse anodic stripping voltammetry analysis. The resulting peak currents were linearly related to the concentrations of the metal ions. The method was optimized with respect to accumulation time, reduction time and reduction potential. The detection limits were found to be 1 ppb and 15 ppb for Pb²⁺ and Cu²⁺ respectively. The technique was used for the detection of Pb²⁺ and Cu²⁺ in spiked lake water. The average recoveries of Pb²⁺ and Cu²⁺ were 96.2% and 94.5% with relative standard deviations of 8.43% and 7.53% respectively. The potential for simultaneous detection of heavy metal ions by the modified CNTs was also demonstrated.     

A POSS‐Phosphazene Based Porous Material for Adsorption of Metal Ions from Water

The development of adsorptive materials continues to be an important area of research for removal of heavy metal ions from waste water. The adsorption capacity can be modulated by both physical and chemical modification of the adsorbent. Herein, we combine the unique properties of polyhedral oligomeric silsesquioxane (POSS) and organocyclophosphazene as the building units to synthesize a hybrid porous material, abbreviated as PN‐POSS. The synthetic method follows a Heck reaction between hexa(4‐bromophenoxy)cyclotriphosphazene and octavinylsilsesquioxane (OVS). The Brunauer–Emmett–Teller (BET) analysis shows that the material possesses micro‐ and mesopores of 1.5 and 3.8 nm size and a surface area on the order of 500 m² g^?1. These attributes in combination with the donor ability of the phosphazene units qualify the material for high adsorption of Pb²⁺, Hg²⁺ and Cu²⁺ ions with maximal adsorption capacities on the order of 1326, 1927 and 2654 mg g^?1, respectively. The adsorbent exhibits a good regeneration performance and can be effectively used for water treatment.     

Synthesis of a Dithiocarbamate Chelate Resin and Its Oxidized form and Their Adsorption Properties for Heavy Metal Ions

A series of macroporous dithiocarbamate chelate resins, III and V, and an oxidized resin, VI, with high adsorption capacity were prepared. The influence of various reaction conditions of amination, dithiocarboxylation, and oxidation were examined. The structure and the conversion of functional groups of resins were confirmed by IR spectra and elemental analysis. The adsorption capacities of Resin II for Hg²⁺, Cu²⁺, Zn²⁺, and Cd²⁺ are 4.40, 2.44, 1.77, and 1.36 mmol/g, respectively. The adsorption capacities of Resins V and VI for Cu²⁺. Zn²⁺, Ni²⁺, Co³⁺, Ag⁺, Hg²⁺, Cd²⁺, Pb²⁺, and Au³⁺ are 4.07–0.51 and 3.81–0.59 meq ion/g, respectively. The adsorption rate and the influence of pH on the adsorption percentage of the resins for metal ions were examined. Noble metal, transitional metal, and heavy metal ions can be quantitatively adsorbed by the resins. The adsorbed Cu²⁺, Pb²⁺, Cd²⁺, Co³⁺, and Ni²⁺ can be quantitatively eluted with 5N HNO₃, and the presence of large amounts of Ca²⁺, Mg²⁺, Fe³⁺, and Al³⁺ did not interfere.     

Crayfish Shell Waste as Safe Biosorbent for Removal of Cu2+ and Pb2+ from Synthetic Wastewater

Crayfish shell is an abundant natural waste and is also a potential biosorbent for pollutants, especially, heavy metals. In this study, the safety of the use of crayfish shell as a biosorbent was first assessed by release experiments involving primary heavy metal ions, such as Cu²⁺, Zn²⁺, and Cr³⁺, in aqueous solution under different environmental conditions. The release concentrations of heavy metals were dependent on pH, ionic strength, and humic acid; and the maximum release concentrations of heavy metals were still lower than the national standard. Specifically, Cu²⁺ and Pb²⁺ removal by crayfish shell in synthetic wastewater was investigated. The removal process involved biosorption, precipitation, and complexation, and the results indicate that crayfish shell is an excellent biosorbent for Cu²⁺ and Pb²⁺ removal. The precipitation step is particularly dependent on Ca species, pH, and temperature. The maximum removal capacities of Pb²⁺ and Cu²⁺ were 676.20 and 119.98 mg/g, respectively. The related precipitates and the generated complex products include Cu₂CO₃(OH)₂, Ca₂CuO₃, CuCO₃, Pb₂CO₃(OH)₂, CaPb₃O₄, and PbCO₃.     

Removal of heavy metal ions by biogenic hydroxyapatite: Morphology influence and mechanism study

Based on the synthesis of hydroxyapatite (HA) with different morphologies, such as nanorod-like, flower-like and sphere-like assembled HA nanorods, a new strategy has been developed for the removal of heavy metal ions such as Pb²⁺, Cu²⁺, Mn²⁺, Zn²⁺. The dependence of removal efficiency on the morphology and the suspended concentration of trapping agent, the removal time and selectivity were evaluated and discussed. The experimental results proved that the removal capacity of flower-like assembled HA nanorods (NAFL-HA) was the best, and the maximum removal ratio for Pb²⁺ ion was 99.97%. The mechanism of Pb²⁺ removal was studied in detail, noting that some metal ions were completely incorporated into hydroxyapatitie to produce Pb-HA. It reveals that the metal ions capture by HA is mainly controlled by sample surface adsorption and co-precipitation, which are directly controlled by sample morphology.     

Heavy metal adsorptivity of calcium-alginate-modified diethylenetriamine-silica gel and its application to a flow analytical system using flame atomic absorption spectrometry

This study aimed to evaluate the heavy metal adsorptivity of calcium-alginate-modified diethylenetriamine-silica gel (CaAD) and incorporate this biosorbent into a flow analytical system for heavy metal ions using flame atomic absorption spectrometry (FAAS). The biosorbent was synthesized by electrostatically coating calcium alginate onto diethylenetriamine (dien)-silica gel. Copper ion adsorption tests by a batch method showed that CaAD exhibited a higher adsorption rate compared with other biosorbents despite its low maximum adsorption capacity. Next, CaAD was packed into a 1 mL microcolumn, which was connected to a flow analytical system equipped with an FAAS instrument. The flow system quantitatively adsorbed heavy metals and enriched their concentrations. This quantitative adsorption was achieved for pH 3–4 solutions containing 1.0 × 10⁻⁶ M of heavy metal ions at a flow rate of 5.0 mL min⁻¹. Furthermore, the metal ions were successfully desorbed from CaAD at low nitric acid concentrations (0.05–0.15 M) than from the polyaminecarboxylic acid chelating resin (Chelex 100). Therefore, CaAD may be considered as a biosorbent that quickly adsorbs and easily desorbs analyte metal ions. In addition, the flow system enhanced the concentrations of heavy metals such as Cu²⁺, Zn²⁺, and Pb²⁺ by 50-fold. This new enrichment system successfully performed the separation and determination of Cu²⁺ (5.0 × 10⁻⁸ M) and Zn²⁺ (5.7 × 10⁻⁸ M) in a river water sample and Pb²⁺ (3.8 × 10⁻⁹ M) in a ground water sample.     

Selective Lead Adsorption by Recombinant Escherichia coli Displaying a Lead-Binding Peptide

A highly specific lead-binding peptide ThrAsnThrLeuSerAsnAsn was displayed on Escherichia coli, and lead adsorption characteristics of the recombinant bacteria were investigated. Cell surface-displayed peptide was expressed under the control of an arabinose promoter using outer membrane protein C (OmpC_t) as an anchoring motif. The optimal induction period and arabinose concentration for the expression of peptide-fused OmpC_t were determined to be 2 h and 0.001 g/L, respectively. Selective adsorption of Pb²⁺ onto recombinant cells was verified with individual or combinatory use of four metal ions, Pb²⁺, Ni²⁺, Co²⁺, and Cu²⁺; the amount of bound Pb²⁺ onto the biosorbents was significantly higher than the other metal ions. The adsorption isotherm of recombinant cells for Pb²⁺ followed the Langmuir isotherm with a maximum adsorption loading (q _max) of 526 μmol/g dry cell weight.     

Preparation of PSSS‐grafted polysulfone microfiltration membrane and its rejection and removal properties towards heavy metal ions

3‐Hydroxy‐N,N‐diethylaniline (HDEA) as a tertiary aromatic amine was introduced onto the surface of chloromethylated polysulfone (CMPSF) microfiltration membrane through modification reaction, resulting in the modified membrane PSF‐DEA. A redox surface‐initiating system (DEA/APS) was constituted by the bonded tertiary aromatic amine group DEA and ammonium persulfate (APS) in aqueous solution, and so, the free radicals formed on the membrane initiated sodium p‐styrenesulfonate (SSS) as an anionic monomer to produce graft polymerization, getting the grafting‐type composite microfiltration membrane, PSF‐g‐PSSS membrane. Subsequently, the adsorption property of PSF‐g‐PSSS membrane for three heavy metal ions, Pb²⁺, Zn²⁺, and Hg²⁺ ions, was fully examined, and the rejection performance of PSF‐g‐PSSS membrane towards the three heavy metal ions was emphatically evaluated via permeation experiments. The experimental results show that by the initiating of the surface‐initiating system of DEA/APS, the graft polymerization can smoothly be carried out under mild conditions. PSF‐g‐PSSS membrane as a functional microfiltration membrane has strong adsorption ability for heavy metal ions by right of strong electrostatic interaction (or ion exchange action) between the anionic sulfonate ions on the membrane and heavy metal ions. The order of adsorption capacity is Pb²⁺ > Zn²⁺ > Hg²⁺, and the adsorption capacity of Pb²⁺ ion gets up to 2.18 μmol/cm². As the volume of permeation solutions, in which the concentrations of the three metal ions are 0.2 mmol/L, are in a range of 50 to 70 mL, the rejection rate of PSF‐g‐PSSS membrane for the three heavy metal ions can reach a level of 95%, displaying a fine rejection and removing performance towards heavy metal ions.     

Chemically modified kapok fiber for fast adsorption of Pb2+, Cd2+, Cu2+ from aqueous solution

Kapok fiber, a natural hollow fiber with thin shell and large cavity, has rarely been used as adsorbent for heavy metal ions. In this paper, kapok fibers were modified with diethylenetriamine pentaacetic acid (DTPA) after hydrophilicity treatment. The adsorption behavior of the resultant kapok-DTPA influenced by pH, adsorption time and initial concentration of metal ion was investigated. The results demonstrate that adsorption equilibrium was reached within 2 min for Pb²⁺ and Cd²⁺. Adsorption kinetics showed that the adsorption rate was well fitted by pseudo-second-order rate model. The adsorption isotherms were studied, and the best fit was obtained in the Langmuir model. The maximum adsorption capacities of kapok-DTPA were 310.6 mg g^?1 for Pb²⁺, 163.7 mg g^?1 for Cd²⁺, 101.0 mg g^?1 for Cu²⁺, respectively. After eight desorption and re-adsorption loops, the lost adsorption capacities for Pb²⁺ and Cu²⁺ were less than 10 %. Because of the large specific area derived from the hollow fiber structure, kapok-DTPA exhibited much better adsorption capacity compared with many other reported adsorbents based on natural materials.     

Extraction of metal picrates by lipophilic hexamide and hexamine derivatives of azacrown [18]-N6

To determine the metal ion complexing ability of high molecular weight macrocyclic polyamines and polyamides, lipophilic derivatives of azacrown [18]-N₆ (hexacyclen) were prepared. Transition and heavy metal picrates, but not alkali and alkaline earth picrates, were extracted from water into chloroform and transported from water through chloroform into a second water phase by the hexa-4-dodecyloxybenzoyl and hexa-3,4-bis-dodecyloxybenzoyl amide derivatives1 and2 and by the hexa-4-dodecyloxybenzyl amine derivative3 of [18]-N₆ (hexacyclen). The relative amounts of picrates extracted by hexamine3 from a pH 5 aqueous solution were Cu²⁺Ag⁺Pb²⁺> Hg²⁺>Zn²⁺>Co²⁺>Ni²⁺Cd²⁺. Using a pH 7 receiving phase, none of the metal ions were transported rapidly through chloroform, and only Co²⁺, Cu²⁺, and Pb²⁺, were transported rapidly into a pH 11 aqueous phase. The hexamide2, but not hexamide1, extracted significant amounts of the picrates of Cu²⁺, Ag⁺, and Hg²⁺, and transported Cu²⁺ and Ag⁺ but not Hg²⁺.     

Novel nanostructured dendrimer based on 1,3-bis(4,6-dichloro-1,3,5-triazine-2-yl)urea as an excellent adsorbent for Pb2+, Ni2+, Co2+ and Zn2+ metal ions

Human health is seriously harmed by the consumption of poor-quality water. Due to high toxicity and water solubility, heavy metals are present in wastewater discharged from numerous industries. In the environmental realm, metal-containing water must be treated before being released. A dendrimer is a superior adsorbent for the removal of heavy metal ions due to its nanostructure and hydrophilic end group. In this work, a novel triazine-based hydroxy-terminated dendrimer up to generation three is designed employing a carbamide core. The dendrimer's structure was explored using FT-IR and ¹H NMR studies. Full generation dendrimers UG1.0, UG2.0, and UG3.0 were utilized as an adsorbent for Pb²⁺, Ni²⁺, Co²⁺ and Zn²⁺ metal ion removal from water in a series of tests. The ability of dendrimers to uptake Pb²⁺, Ni²⁺, Co²⁺ and Zn²⁺ metal ions was investigated under various pH, time interval and dendrimer generation parameters. The presence of metal in the dendrimer was confirmed by FT-IR studies of dendrimer-metal complexes. The overall results show that Pb²⁺, Ni²⁺, Co²⁺ and Zn²⁺ metal ions uptake increases with the generation, time, and pH.     

Preparation of guanidinylated carboxymethyl chitosan and its application in the diffusive gradients in thin films (DGT) technique for measuring labile trace metals in water

ABSTRACT

Guanidinylated carboxymethyl chitosan (GCMCS) was prepared via the guanidinylation of carboxymethyl chitosan (CMCS). A device employing the diffusive gradients for thin films (DGT) technique was made using a GCMCS aqueous solution as the binding agent and a cellulose acetate dialysis membrane (CADM) as the diffusion phase to measure labile Cu²⁺, Pb²⁺ and Cd²⁺ in water. The percentage uptake (U%) values of labile Cu²⁺, Pb²⁺ and Cd²⁺ in a synthetic water sample were almost consistent with the theoretical values at 101.6 ± 2.8%, 104.6 ± 6.1% and 95.9 ± 4.4%, respectively. The optimum pH ranges for the measurement of labile Cu²⁺, Pb²⁺ and Cd²⁺ were 3.0–7.0, 3.0–7.0 and 4.0–8.0, respectively. The ionic strength mainly affected the diffusion of metal ions in the CADM. The diffusion rates decreased with increasing concentrations of NaNO₃ solutions. The application of GCMCS-DGT in natural water and industrial wastewater showed that dissolved organic carbon (DOC) only affects metal species, and the accurate determination of labile Cu²⁺, Pb²⁺ and Cd²⁺ can be achieved when the diffusion coefficients of these metal ions in the diffusion phase have been determined. GCMCS is suitable for DGT application as a chelating agent for metal ions.     

Colorimetric metal ion binding of catechol-based coatings inspired by melanin and molecular imprinting

Catechol-containing biomolecules and related synthetic materials are of interest for a broad range of applications. Our group has been interested in the potential of eumelanin, a catechol-containing biomaterial and the black-to-brown pigment in humans, and synthetic eumelanin analogues for water purification applications. In an attempt to apply the strategy of molecular imprinting towards lead-binding synthetic eumelanin coatings, we developed a PbO₂-mediated synthesis that was subsequently tested with a number of catechols in addition to the eumelanin and polydopamine monomers l-dopa and dopamine. Although this strategy did not provide significant improvements in affinity or selectivity, we found that the PbO₂-mediated oxidative polymerisation of 1,2-dihydroxybenzene generates a coating that darkens visibly upon binding Pb²⁺ and other metal ions. Oxidative polymerisation of catechol with sodium periodate also yields a coating with this colorimetric response. Of eight metal ions tested, the coatings are most responsive to Pb²⁺ and Cu²⁺, as analysed by quantitative colorimetry. With further optimisation, these coatings could prove useful for the colorimetric sensing of metal ions.