Metal Ions In Aqueous Solution Research Articles

PE/PP fibrous adsorbents with bifunctional groups of tertiary amine and phosphate prepared by electron beam induced co-grafting for heavy metal adsorption of both cationic and anionic forms in acidic conditions.

A novel fabric adsorbent having bifunctional groups of tertiary amine and phosphate was prepared by co-graft polymerization of 2-diethylaminoethyl methacrylate (NMA) and 2-hydroxyethyl methacrylate phosphate (PMA) onto a polyethylene/polypropylene nonwoven fabric (PE/PP NF) under low-energy electron beam acceleration. The process involved pre-irradiating the fabric and immersing it in the comonomer solution for grafting. The kinetics of radiation-induced graft polymerization at a total dose of 100 kGy was investigated. For pre-irradiation at 100 kGy, the optimum condition offering highest degree of grafting was at 12 wt% of NMA, 8 wt% of PMA and 4 h of reaction time. The adsorption of anions using hydrogen chromate (HCrO4−) or Cr(VI) and cations using lead (Pb(II)), cadmium (Cd(II)) and copper (Cu(II)) in aqueous solution was carried out. The results demonstrated that the bifunctional adsorbent was able to adsorb both heavy metal anionic and cationic ions from water. The co-grafted adsorbents with tertiary amine and phosphate were able to adsorb 85% Cr(VI) anion and 29% Pb(II) cations from mixed Cr(VI) and Pb(II) solution at pH 3.0 and 71% Pb(II), 13% Cd(II) and 31 % Cu(II) from mixed Pb(II), Cd(II) and Cu(II) solution at pH 5.0. The unique achievement of this study is its hypothesis that a bifunctional adsorbent can be prepared from radiation-induced graft polymerization of two different monomers onto NF, along with proof that the prepared bifunctional adsorbent can actually absorb both cationic or anionic heavy metals forms. Additionally, the adsorbent's preparation offers a rapid and straightforward one-step grafting technique. Therefore, the new bifunctional adsorbents can remove heavy metal ions in aqueous solution, either in the cation or anion form, thus offering highly promising applications in industrial wastewater treatment.

Multifunctional carbon nanotube arrays on kapok-derived carbon microtube composites for efficient electromagnetic wave absorption and Cu(II) removal

To cope with different environments of application, electromagnetic wave absorption (EWA) materials with multifunctionality have attracted a wide range of interests. And excessive heavy metal ions in aqueous solutions seriously affect people’s health and pose a major challenge to environmental safety. In this study, carbon microtube/carbon nanotube (CMT/CNT) composites were fabricated via carbonization and chemical vapor deposition (CVD) methods. The CNT wrapped with cobalt nanoparticles were grown in situ on the CMT which derived from kapok fiber. By varying the concentration of cobalt precursors, the EWA and Cu(II) adsorption performances of CMT/CNT can be efficiently tuned. Optimizing the cobalt content to 2 wt% resulted in a minimum reflection loss (RL) of −66.14 dB at a matching thickness of 1.91 mm, with an effective absorption bandwidth (EAB) of 5.35 GHz. The adsorption capacity of Cu(II) by the CMT/CNT composite can reach 102.01 mg/g when the initial Cu(II) concentration is 500 mg/L. This research not only shows great promise for applications in the field of EWA materials but also holds significant potential for heavy metal ion removal and as a catalyst carrier, among other areas.

Polydopamine nanoparticles reinforced injectable hydrogels for the efficient adsorption and catalysis in the wastewater treatment

By in situ generation of hydrazone bonds, a composite hydrogel that combines poly(N-isopropylacrylamide) and carboxymethyl cellulose and is reinforced with PDA nanoparticles was successfully prepared for injectable use, and was employed to treat metal ions in aqueous solutions. The composite hydrogels presented desirable compressive strength and anti-fatigue performance. The adsorption capacities of Cu2+, Pb2+ and Cd2+ reached high values of 193.8, 168.8 and 112.6 mg/g, respectively, in a single-ion adsorption system, due to the plentiful adsorptive sites on the hydrogels. The adsorption kinetics followed the Pseudo-second-order model, while the adsorption isotherm adhered to the Langmuir model. Besides, the hydrogels showed slightly higher selectivity for Cu2+ in an adsorption system involving multiple ions, and exhibited good reusability, enabling it to be employed repeatedly as a recyclable adsorbent. The analysis of the mechanism indicated that ion exchange, electrostatic interaction, chemical adsorption and coordination effect might occurred between metal ions and functional groups in hydrogel matrix and PDA nanopartiles. Moreover, the Cu2+-adsorbed hydrogels could act as a scaffold for the on-site generation of Cu nanoparticles. With the Cu nanoparticles, the hydrogels showed catalytic activity of ∼ 80 % conversion of 4-nitrophenol (1 mmol) to 4-aminophenol in 30 min, validating the dual functional properties for both adsorption and catalytic purposes in the treatment of wastewater.

Simulation of Magnetic Separation of Metal Ions in Aqueous Electrolytes

The magnetic separation of metal ions provides an alternative solution to traditional separation techniques such as pyrometallurgy, hydrometallurgy, biometallurgy or electrodialysis. Compared to traditional techniques that either use large amounts of chemicals (usually inorganic acids combined with reducing agent), produce large amounts of sludge as solid waste, consume a large amount of energy, or are difficult to separate ions of different charges [1], the magnetic separation of the metal ions can separate ions based on their magnetic susceptibility. This method is environmentally friendly [2] and consumes a small amount of energy (particularly when the system is designed using permanent magnets instead of electromagnets). The goal of this presentation is twofold. First, we derive the set of transport equations that need to be used to simulate the magnetic separation of metal ions in aqueous solutions. Then, we use these transport equations to simulate the magnetic separation process in various magnetic systems and predict the efficiency of magnetic separation of different systems.The mathematical model developed here is based on coupling the three-dimensional Navier-Stokes equations for flow transport with the drift (migration)-diffusion equations of ion transport [3] in the presence of magnetic field gradients. Both the drift-diffusion model and the Navier-Stokes equations include the magnetic force term as an additional driving force. By solving the entire system of equations self-consistently we analyze the effect of the diffusivity, concentration gradients, magnetic field gradients and fluid velocity over the capturing properties of the system. A detailed presentation of the mathematical model, underlying assumptions of the model, limiting cases, numerical implementation in three-dimensional structures, and simulations results will be presented at the meeting. In addition, we will present predictions for the magnetic separation of Li, Fe, Ni, Mn, and Co from the solution phase. Fortunately, these ions have significantly different magnetic susceptibility, which vary over more than 3 orders of magnitude, and which allows for the efficient extraction and separation of the elements from the solution and from each other.

Preparation and characterization of pyrimidine‐cored covalent organic frameworks for heavy metal removal

AbstractIn this work, two novel pyrimidine‐cored covalent organic frameworks TpTap‐COF and TpTan‐COF were synthesized for the first time and used for the adsorption of heavy metal ions in aqueous solution. Both COFs are nanofiber clusters with preferable crystallinity and thermal stability. The impact parameters such as pH value, shaking time, initial concentration, and temperature were studied by batch adsorption experiments in the multi‐metal ions system. The adsorption of six metal ions onto COFs follows the pseudo‐second‐order kinetic model and the Freundlich isotherm model, which is a chemical adsorption process that occurs on non‐uniform surfaces. The adsorption rate is determined by both film diffusion and intraparticle diffusion. Further research on the adsorption of copper ions onto COFs indicates the formation of metal complexes between O#N#N/O#O chelating sites in the COF skeleton and Cu ions through the sharing of lone pair electrons.

Versatile Solvatochromic fluorophores based on Schiff bases for colorimetric detection of metal ions

In recent years, fluorescent probes have been extensively studied as powerful tools for the effective assessment of toxic metal ions due to their high sensitivity, selectivity, capability for real-time and non-invasive monitoring, and versatility. In this paper, novel fluorescent probes based on Schiff bases, namely 2-((1E,2E)-1-(6-chlorobenzo[d]thiazol-2-ylimino)-3-(4-(dimethylamino)phenyl)allyl)phenol (1) and 2-((1E,2E)-3-(4-(dimethylamino)phenyl)-1-(4-methylbenzo[d]thiazol-2-ylimino)allyl)phenol (2), were synthesized and characterized. The optical properties of these probes were examined across a spectrum of fourteen solvents with varying polarities, revealing significant solvatochromic effects on both absorption and fluorescence spectra. The analysis delineated a discernible difference in dipole moment between electronic ground and excited states, with molecules exhibiting enhanced stabilization in singlet excited states. Subsequently, a straightforward method was devised for the selective and sensitive detection of diverse metal ions in aqueous solutions, including K+, V3+, Cr3+, Fe3+, Co2+, Ni2+, Cu2+, Se6+, Cd2+, Ba2+, and Hg2+, through naked eye observation, UV–Visible, and fluorimetric measurements. Notably, the UV–Vis spectra of probes 1 and 2 manifested a significant red shift upon the addition of metal ions, indicative of potential ligand-to-metal charge-transfer (LMCT) phenomena, with the exception of Ni2+, Cu2+, and Se6+ions. The observed alterations in optical absorption and fluorescence emission contributed to the probes' heightened selectivity and sensitivity, obviating the necessity for sample pretreatment. Competitive assays underscored the probes' preference for Cr3+ and V3+ ions over other common metal ions. Furthermore, Job's plot analysis suggested a 1:1 ligand-to-metal molar ratio binding. The investigated Schiff bases exhibited elevated binding constants (Ka), low detection limits, and limits of quantification, alongside diminished fluorescence quantum yield. Leveraging fluorescence quenching, facile paper-based sensor strips coated with Schiff bases facilitated prompt, qualitative, and quantitative in situ detection of metal ions in aqueous solutions across a broad concentration spectrum, discernible to the naked eye under UV light.

Large-Scale Synthesis of High-Loading Single Metallic Atom Catalysts by a Metal Coordination Route.

Single atom catalyst (SAC) is one of the most efficient and versatile catalysts with well-defined active sites. However, its facile and large-scale preparation, the prerequisite of industrial applications, has been very challenging. This dilemma originatesfrom the Gibbs-Thomson effect, which renders it rather difficult to achieve high single atom loading (< 3 mol%). Further, most synthesizing procedures are quitecomplex, resulting in significant mass loss and thus low yields. Herein, a novel metal coordination route is developed to address these issues simultaneously, which is realized owing to the rapid complexation between ligands (e.g., biuret) and metal ions in aqueous solutions and subsequent in situ polymerization of the formed complexes to yield SACs. The whole preparation process involves only one heating step operated in air without any special protecting atmospheres, showing general applicability for diverse transition metals. Take Cu SAC for an example, a record yield of up to 3.565kg in one pot and an ultrahigh metal loading 16.03 mol% on carbon nitride (Cu/CN) are approached. The as-prepared SACs are demonstrated to possess high activity, outstanding selectivity, and robust cyclicity for CO2 photoreduction to HCOOH. This research explores a robust route toward cost-effective, massive production of SACs for potential industrial applications.

Chemical Synthesis of Bimetallic Ag/Co Nanoparticles for Colorimetric Detection of Cr3+ and Fe3+ and Its Catalytic Performance

Precious metal nanoparticles, especially Ag-based nanoparticles due to their strong surface plasma effect and excellent catalytic performance, have been widely applied in environmental remediation and detection of heavy metal ions in aqueous solution. In this study, first, bimetallic Ag/Co nanoparticles (Ag/Co NPs) modified by sodium citrate were synthesized by chemical reduction method. Second, bimetallic Ag/Co NPs were used as colorimetric probe for detecting [Formula: see text] and [Formula: see text] in aqueous solution simultaneously for the first time. The results showed that the probe had high specificity towards [Formula: see text] and [Formula: see text] among the tested metal ions. When [Formula: see text] was mixed with Ag/Co NPs, the solution quickly changed from yellow to pink, meanwhile, the UV–Vis absorption intensity declined at 400[Formula: see text]nm and a new prominent absorption band was formed at 530[Formula: see text]nm. While [Formula: see text] was mixed with Ag/Co NPs, the solution quickly changed from yellow to nearly colorless. The linear relationship between absorbance of bimetallic Ag/Co NPs at 400[Formula: see text]nm and −log of [Formula: see text] concentration is 1[Formula: see text]nM to 10[Formula: see text][Formula: see text]M, which [Formula: see text] and [Formula: see text]. The limit of detection (LOD) for this study was 1.14[Formula: see text]nM. Similar to [Formula: see text], the LOD for [Formula: see text] was calculated 16.3[Formula: see text][Formula: see text]M. In addition, the catalytic performance of bimetallic Ag/Co NPs was evaluated by methylene blue (MB) in the presence of H2O2. The catalytic degradation efficiency of bimetallic Ag/Co NPs was about 4.8 times greater than monometallic Ag NPs, confirming Ag and Co NPs had obviously synergistic effect. Therefore, this result made bimetallic Ag/Co NPs had potential application in the field of environmental remediation.

Reduction of precious metal ions in aqueous solutions by contact-electro-catalysis

Precious metals are core assets for the development of modern technologies in various fields. Their scarcity poses the question of their cost, life cycle and reuse. Recently, an emerging catalysis employing contact-electrification (CE) at water-solid interfaces to drive redox reaction, called contact-electro-catalysis (CEC), has been used to develop metal free mechano-catalytic methods to efficiently degrade refractory organic compounds, produce hydrogen peroxide, or leach metals from spent Li-Ion batteries. Here, we show ultrasonic CEC can successfully drive the reduction of Ag(ac), Rh3+, [PtCl4]2-, Ag+, Hg2+, Pd2+, [AuCl4]-, and Ir3+, in both anaerobic and aerobic conditions. The effect of oxygen on the reaction is studied by electron paramagnetic resonance (EPR) spectroscopy and ab-initio simulation. Combining measurements of charge transfers during water-solid CE, EPR spectroscopy and gold extraction experiments help show the link between CE and CEC. What’s more, this method based on water-solid CE is capable of extracting gold from synthetic solutions with concentrations ranging from as low as 0.196 ppm up to 196 ppm, reaching in 3 h extraction capacities ranging from 0.756 to 722.5 mg g−1 in 3 h. Finally, we showed CEC is employed to design a metal-free, selective, and recyclable catalytic gold extraction methods from e-waste aqueous leachates.

Adsorption Potential, Speciation Transformation, and Risk Assessment of Hg-, Cd-, and Pb-Contaminated Soils Using Biochar in Combination with Potassium Dihydrogen Phosphate.

The objective of this study is to develop a remediation technology for composited heavy metal-contaminated soil. Biochars (BC300, BC400, and BC500) derived from corn were combined with potassium dihydrogen phosphate (KH2PO4) to immobilize and remove heavy metal ions, including mercury (Hg2+), cadmium (Cd2+), and lead (Pb2+). The adsorption kinetics of metal ions in aqueous solutions with different concentrations was tested, and the fitting effects of the two models were compared. The findings demonstrate that the joint application of biochar and KH2PO4 could markedly enhance the immobilization efficacy of Pb2+, whereas the utilization of KH2PO4 on its own exhibited a more pronounced immobilization impact on Cd2+. Furthermore, the present study underscores the shortcomings of various remediation techniques that must be taken into account when addressing heavy metal-contaminated soils. It also emphasizes the value of comprehensive remediation techniques that integrate multiple remediation agents. This study offers a novel approach and methodology for addressing the intricate and evolving challenges posed by heavy metal contamination in soil. Its practical value and potential for application are significant.

Wood dimensional stability enhancement by multivalent metal-cation-induced lignocellulosic microfibrils crosslinking

Wood is a hygroscopic material that responds to the moisture changes of the surrounding environment through swelling and shrinkage, making it dimensionally unstable. Here, we introduce a facile metal-ion-modification (MIM) approach to enhance the dimensional stability of wood. The MIM process involved swelling the wood samples with aqueous metal ion solutions and drying. The high valent metal cations, such as Fe3+, Al3+, and Zr4+, interacted with the hydrophilic groups (e.g., OH, COOH) present in the wood fibers, limiting their access to water and moisture, thereby enhancing the wood's hydrophobicity and dimensional stability. Evaluation of three wood species, southern yellow pine, poplar, and red oak, revealed water contact angles of 120–130° after MIM, indicative of enhanced surface hydrophobicity. Fe3+ treatment decreased southern yellow pine's swelling ratio from 6 % to 4 %. Fe3+-treated wood exhibited tangential anti-swelling efficiencies ranging from 39.83 % to 57.14 % and radial anti-swelling efficiencies from 34.74 % to 48.33 %, varying across wood species. The enhancement of wood dimensional stability can be attributed to the formation of irreversible coordination bonds between metal cations and lignocellulosic microfibrils in the wood cell wall. These bonds prevent the microfibrils from slipping in response to moisture absorption and desorption.

On-Line pH Measurement Cation Exchange Kinetics of Y3+-Exchanged Alginic Acid for Y2O3 Nanoparticles Synthesis.

A new sol-gel method that employs cation exchange from an aqueous metal ion solution with H+ ions of granulated alginic acid was developed for synthesizing high-purity Y2O3 nanoparticles. In this study, the cation exchange kinetics of H+~Y3+ in aqueous solution were analyzed using on-line pH technology and off-line inductively coupled plasma-atomic emission spectrometry (ICP-AES) analysis. Pseudo 2nd-order models were utilized to evaluate the parameters of the kinetics, suggesting that the concentration of H+~Y3+ involved in the cation exchange reaction was 1:1.733. Further, a comprehensive understanding of the Y-ALG calcination process was developed using thermo-gravimetric analysis, along with results obtained from differential scanning calorimetry (TGA/DSC). A detailed analysis of the XRD Rietveld refinement plots revealed that the crystallite sizes of Y2O3 nanoparticles were about 4 nm (500 °C) and 15 nm (800 °C), respectively. Differential pulse voltammetry (DPV) was employed to investigate the electrochemical oxidation of catechol. The oxidation peak currents of catechol at Y2O3 (500 °C)/GCE and Y2O3 (800 °C)/GCE showed two stages linear function of concentration (2.0~20.0 × 10-6 mol/L, 20.0~60.0 × 10-6 mol/L). The results indicated that the detection limits were equal to 2.4 × 10-7 mol/L (Y2O3 (500 °C)/GCE) and 7.8 × 10-7 mol/L (Y2O3 (800 °C)/GCE). The study not only provided a method to synthesize metal oxide, but also proposed a promising on-line pH model to study cation exchange kinetics.

Deep eutectic solvent assisted electrodialysis towards selective resource recovery from model spent batteries effluents

Critical minerals will remain major active ingredients to most battery technologies for decades and innovation to improve extractive operations during spent battery effluent recycling must be carried out. Although the recovery of metal-ions in aqueous solutions has been demonstrated with membrane systems, including electrodialysis, process intensification to increase the diffusion rate at the membrane/liquid interface must be achieved to improve recovery efficiency. This manuscript presents a unique approach to increase the rate of recovery and transfer of Li+ and Co2+ ions from a membrane bulk phase to an organic liquid phase by applying deep eutectic solvent (DES) instead of an aqueous solution as the permeate stream during electrodialysis. The DES, based on choline chloride and urea at a molar ratio of 1:2, is considered green and relatively non-toxic valuable for solvent extraction purpose. Here, electrodialysis tests were conducted with this solvent on the permeate side using commercial Neosepta and laboratory-made cobalt selective membranes. The DES significantly affected cobalt transport across the membranes and separation factor which increased from 247 to 516, leading to cobalt recovery as high as 66 %. Furthermore, the use of DES on the permeate side greatly improved the energy efficiency increasing the amount of recovered cobalt per Joule of energy by over 20 %.

Machine Learning Assisted Metal Oxide‐Bismuth Oxy Halide Nanocomposite for Electrochemical Sensing of Heavy Metals in Aqueous Media

AbstractHeavy metal in excess quantity is one of the major inorganic pollutants in water. It causes several hazards to human life and ecosystem. It exists in traces in most of the commonly available drinking water sources from lakes, ponds, wells, etc., However, their presence in treated water is relatively significant. As the treated water is primarily used for agricultural purposes, it is necessary to monitor and measure their concentration. This requires sensing of metals in aqueous medium with good sensitivity and stability. Recently, nanosensors coupled with electrochemical transducer is preferred for analyzing heavy metal in aqueous solutions. In this work, Silver oxide‐bismuth oxy bromide coated with nafion is proposed as an electrochemical sensor for detection of heavy metal ions in aqueous solution. Cyclic voltammetry (CV) behavior of the proposed electrode is observed in different electrolytes. Further, Differential Pulse Voltammetry (DPV) study shows that current increases with trace nickel and copper metal ions of different concentration. Further, machine learning (ML) algorithms such as Naïve Bayes, ANN, SVM and decision trees are employed for nickel ions to train the cyclic voltammetry data and evaluate its performance. Naïve Bayes algorithm provides the best accuracy of 93.2% among all the models.

Thermodynamics of Metal-Acetate Interactions.

Metal ions play crucial roles in protein- and ligand-mediated interactions. They not only act as catalysts to facilitate biological processes but are also important as protein structural elements. Accurately predicting metal ion interactions in computational studies has always been a challenge, and various methods have been suggested to improve these interactions. One such method is the 12-6-4 Lennard-Jones (LJ)-type nonbonded model. Using this model, it has been possible to successfully reproduce the experimental properties of metal ions in aqueous solution. The model includes induced dipole interactions typically ignored in the standard 12-6 LJ nonbonded model. In this we expand the applicability of this model to metal ion-carboxylate interactions. Using 12-6-4 parameters that reproduce the solvation free energies of the metal ions leads to an overestimation of metal ion-acetate interactions, thus, prompting us to fine-tune the model to specifically handle the latter. We also show that the standard 12-6 LJ model significantly falls short in reproducing the experimental binding free energy between acetate and 11 metal ions (Ni(II), Mg(II), Cu(II), Zn(II), Co(II), Cu(I), Fe(II), Mn(II), Cd(II), Ca(II), and Ag(I)). In this study, we describe optimized C4 parameters for the 12-6-4 LJ nonbonded model to be used with three widely employed water models (Transferable Intermolecular Potential with 3 Points (TIP3P), Simple Point Charge Extended (SPC/E), and Optimal Point Charge (OPC) water models). These parameters can accurately match the experimental binding free energy between 11 metal ions and acetate. These parameters can be applied to the study of metalloproteins and transition metal ion channels and transporters, as acetate serves as a representative of the negatively charged amino acid side chains from aspartate and glutamate.

A bifunctional fluorescent sensor based-on Pillar[5]arene for efficient detection of MnO4− as an oxidant and Hg2+ ion in aqueous media: Bio-imaging in living cells

The high amounts of oxidants and heavy metal ions caused undesirable health results and the detection of these ions gained increasing importance with new techniques. This paper focuses on a fluorescent macrocyclic sensor based on Pillar[5]arene and Bodipy (Bodipy-P[5]arene) for the recognition of oxidants and heavy metal ions in aqueous solution. After the characterization of the macrocyclic ligand, the spectroscopic measurements were carried out by Uv–vis and fluorescence spectroscopies. The bifunctional fluorescent macrocycle, Bodipy-P[5]arene, presents to a dual effect with fluorescence quenching response for fluorometrically recognizing MnO4- and Hg2+ ions. Bodipy-P[5]arene has low detection limits of MnO4- and Hg2+ such as 1.15 × 10-7 M and 8.12 × 10-7 M, respectively. Moreover, both Bodipy-P[5]arene can respectively detect the target ions in acidic and basic mediums and the macrocyclic ligand has short response times. In addition, the Bodipy-P[5]arene probe demonstrates low cellular toxicity and exceptional membrane permeability, making it a successful tool for fluorescently imaging Hg2+ and MnO4- ions within living HeLa cells.

KMnO4-activated spinach waste biochar: An efficient adsorbent for adsorption of heavy metal ions in aqueous solution

Developing advanced carbon materials by utilizing biomass waste has attracted much attention. Herein, a novel carbon adsorbent derived from Spinach waste was prepared by using pyrolysis procedure with KMnO4 as the activator. The preparation condition such as activator mass ratio (0–0.16) and activation temperature (200–800 °C) were comprehensively studied. The optimal sample (SBC-0.08–500) showed a 7.38-fold increase in specific surface area compared to the original biochar (SBC-500). Adsorption experiments revealed that SBC-0.08–500 had efficient removal capabilities for Cd(II), Pb(II), Cu(II), and Zn(II) ions. The maximum adsorption capacities for Cd(II), Pb(II), Cu(II), and Zn(II) ions at 298.15 K were 1.66, 2.88, 1.31, and 2.09 mmol∙g−1, respectively. Thermodynamic results indicated that the adsorption of Cd(II), Pb(II), and Zn(II) ions on SBC-0.08–500 was a spontaneous endothermic process. Additionally, SBC-0.08–500 had a high affinity for Pb(II) ions, making it a potential selective adsorbent for the removal of mixed heavy metal ions. The mechanism underlying the adsorption process was attributed to multiple interactions, including ion exchange, electrostatic interaction, and surface complexation. The as-prepared biochar by oxidative activation pyrolysis effectively solves the issues of subsequent chemical recycling and secondary pollution, thus providing greater potential for large-scale use.

Structure and size of complete hydration shells of metal ions and inorganic anions in aqueous solution.

The structures of nine hydrated metal ions in aqueous solution have been redetermined by large angle X-ray scattering to obtain experimental data of better quality than those reported 40-50 years ago. Accurate M-OI and M-(OI-H)⋯OII distances and M-OI(H)⋯OII bond angles are reported for the hydrated magnesium(II), aluminium(III), manganese(II), iron(II), iron(III), cobalt(II), nickel(II), copper(II) and zinc(II) ions; the subscripts I and II denote oxygen atoms in the first and second hydration sphere, respectively. Reported structures of hydrated metal ions in aqueous solution are summarized and evaluated with emphasis on a possible relationship between M-OI-OII bond angles and bonding character. Metal ions with high charge density have M-OI-OII bond angles close to 120°, indicative of a mainly electrostatic interaction with the oxygen atom in the water molecule in the first hydration shell. Metal ions forming bonds with a significant covalent contribution, as e.g. mercury(II) and tin(II), have M-OI-OII bond angles close to 109.5°. This implies that they bind to one of the free electron pairs in the water molecule. Comparison of M-O bond distances of hydrated metal ions in the solid state with one hydration shell, and in aqueous solution with in most cases at least two hydration shells, shows no significant differences. On the other hand, the X-O bond distance in hydrated oxoanions increases by ca. 0.02 Å in aqueous solution in comparison with the corresponding X-O distance in the solid state. A linear correlation is observed between volume, calculated from the van der Waals radius of the hydrated ion, and the ionic diffusion coefficient in aqueous solution. This correlation strongly indicates that monovalent metal ions, except lithium and silver(I), and singly-charged monovalent oxoanions have a single hydration shell. Divalent metal ions, bismuth(III) and the lanthanoid(III) and actinoid(III) ions have two hydration shells. Trivalent transition and tetravalent metal ions have two full hydration shells and portion of a third one. Doubly charged oxoanions have one well-defined hydration shell and an ill-defined second one.

Label-free impedimetric analysis of microplastics dispersed in aqueous media polluted by Pb2+ ions.

The rapid differentiation between polluted and unpolluted microplastics (MPs) is critical for tracking their presence in the environment and underpinning their potential risks to humans. However, the quantitative analysis of polluted microplastics on the field is limited by the lack of rapid methods that do not need optical analysis nor their capture onto sophisticated electrochemical sensor platforms. Herein, a simple analytical approach for MPs dispersed in aqueous media leveraging electrochemical impedance spectroscopy (EIS) analysis on screen-printed sensors is presented. This method is demonstrated by the EIS-based analysis of two standards of microplastics beads (MPs), one of polystyrene (PS) and one of polystyrene carboxylated (PS-COOH), when exposed to aqueous solutions containing Pb2+ ions. The adsorption of Pb2+ ions on the MPs was quantitatively determined by voltammetric analysis. EIS permitted to rapidly (about 2 minutes) differentiate clean MPs from the Pb2+ polluted ones. These results could constitute a first-step towards the realization of a portable impedimetric sensor for the quantification of microplastics polluted by metal ions in aqueous solutions.

Alkali activated winter melon peel as absorbent: Characterization and its adsorption performance for heavy metal ions in aqueous solutions

Agricultural waste winter melon peel was used as raw material as adsorbent material. In order to improve adsorption characteristic, this material modified with NaOH (AWMP). The AWMP was characterized by IR, XRD and XPS. The adsorption performance of AWMP on Cu (II) and Pb (II) in aqueous solution were investigated.The effects of the initial concentration of Cu(II) and Pb(II), contact time, solution pH, and temperature are studied in batch adsorption. The kinetics shows that the equilibrium reached in 60 min and the adsorption is favored above pH 5.0. The highest adsorption capacity for Langmuir isotherm for Cu(II) and Pb(II) onto AWMP was observed to be 197.8 mg/g and 188.8 mg/g respectively. Based on predicted and experimental values of equilibrium capacity, kinetic modeling demonstrated the suitability of the pseudo-second-order kinetic model. Finally, the regeneration of AWMP was also studied up to 10 cycles. Thus, AWMP showed excellent adsorption characteristics during the uptake of Cu(II) and Pb(II) from wastewater effluent and can be used as low-cost agricultural waste biomass as an adsorbent.