Efficient extraction performance and mechanisms of Cd2+ and Pb2+ in water by novel dicationic ionic liquids.

Ten novel hydrophobic dicationic ionic liquids (DILs) were synthesized and applied for the extraction of heavy metals in aqueous solutions. Their physicochemical properties were measured at ambient temperature, and the leaching behaviors of the as-prepared DILs in water were assessed by TOC analysis. Metal extraction experiments were carried out to evaluate the extraction performances of the DILs. It was found that the extraction rates of up to 0.45 and 0.53 mg·(g·min)-1 were achieved with 100 mg DILs for 5 mL of 5 mg/L Cd2+ and Pb2+ solutions. Besides, the extraction efficiencies of Cd2+ and Pb2+ were respectively up to 95.48% and 98.46%, when the volumes of the simulated wastewater were expanded by a factor of 20 at a constant extraction phase ratio (1000 mg DILs for 50 mL of 5 mg/L Cd2+ or Pb2+ solutions). The reusability of the novel DILs was successfully proved by the back-extraction experiments with 0.5 M HNO3. Finally, taking Cd2+ extraction as an example, the extraction mechanism based on FTIR analysis and quantum chemical calculations showed that both S and O atoms in the anions of DILs had physical and quasi-chemical interactions with Cd2+, which were stronger than the electrostatic attraction.

Synthesis and Characterization of ABA-Type Triblock Copolymers Using Novel Bifunctional PS, PMMA, and PCL Macroinitiators Bearing p-xylene-bis(2-mercaptoethyloxy) Core.

Syntheses of novel bifunctional poly(methyl methacrylate) (PMMA)-, poly(styrene) (PS)-, and (poly ε-caprolactone) (PCL)-based atom transfer radical polymerization (ATRP) macroinitiators derived from p-xylene-bis(1-hydroxy-3-thia-propanoloxy) core were carried out to obtain ABA-type block copolymers. Firstly, a novel bifunctional ATRP initiator, 1,4-phenylenebis(methylene-thioethane-2,1-diyl)bis(2-bromo-2-methylpropanoat) (PXTBR), synthesized the reaction of p-xylene-bis(1-hydroxy-3-thia-propane) (PXTOH) with α-bromoisobutryl bromide. The PMMA and PS macroinitiators were prepared by ATRP of methyl methacrylate (MMA) and styrene (S) as monomers using (PXTBR) as the initiator and copper(I) bromide/N,N,N',N″,N″-pentamethyldiethylenetriamine (CuBr/PMDETA) as a catalyst system. Secondly, di(α-bromoester) end-functionalized PCL-based ATRP macronitiator (PXTPCLBr) was prepared by esterification of hydroxyl end groups of PCL-diol (PXTPCLOH) synthesized by Sn(Oct)2-catalyzed ring opening polymerization (ROP) of ε-CL in bulk using (PXTOH) as initiator. Finally, ABA-type block copolymers, PXT(PS-b-PMMA-b-PS), PXT(PMMA-b-PS-b-PMMA), PXT(PS-b-PCL-b-PS), and PXT(PMMA-b-PCL-b-PMMA), were synthesized by ATRP of MMA and S as monomers using PMMA-, PS-, and PCL-based macroinitiators in the presence of CuBr/PMDETA as the catalyst system in toluene or N,N-dimethylformamide (DMF) at different temperatures. In addition, the extraction abilities of PCL and PS were investigated under liquid-liquid phase conditions using heavy metal picrates (Ag+, Cd2+, Cu2+, Hg2+, Pb2+, and Zn2+) as substrates and measuring with UV-Vis the amounts of picrate in the 1,2-dichloroethane phase before and after treatment with the polymers. The extraction affinity of PXTPCL and PXTPS for Hg2+ was found to be highest in the liquid-liquid phase extraction experiments. Characterizations of the molecular structures for synthesized novel initiators, macroinitiators, and the block copolymers were made by spectroscopic (FT-IR, ESI-MS, 1H NMR, 13C NMR), DSC, TGA, chromatographic (GPC), and morphologic SEM.

Effect of the magnetic core in alginate/gum composite on adsorption of divalent copper, cadmium, and lead ions in the aqueous system.

The change of composition of an adsorbent material has been widely used as a method to increase its adsorption capacity, particularly concerning adsorbents made of polysaccharides. Introducing magnetic adsorbents into contaminated water treatment systems is a highly promising strategy, as it promotes the metal ions removal from water. Considering this, gum Arabic (GA) was associated with alginate (Alg), when magnetite nanoparticles were present or absent, to produce beads that were utilised to take up Cu(II), Cd(II), and Pb(II) from aqueous solution. After a complete characterisation (for which Fourier transform infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy, and swelling were used), the adsorption properties were established using batch and column tests. The magnetic beads (MAlg/GA) demonstrated improved adsorption in comparison with the beads made without magnetite (Alg/GA) under the same conditions. In normal adsorption conditions (pH 6.0, 25 °C, 2.5 g L-1 of adsorbent dosage), the highest uptake capacities recorded for the MAlg/GA beads were: for Cu(II), 1.33 mmol g-1; Cd(II), 1.59 mmol g-1; and for Pb(II), 1.43 mmol g-1. The pseudo-second-order kinetics and Langmuir isotherm models provided good fits for the adsorption of these metals. Overall, ion exchange and physical forces led to the uptake of these metals by both Alg/GA and MAlg/GA; moreover, the functional groups on the beads played crucial roles as binding sites. Additionally, it was observed that flow rates of >2 mL min-1 did not produce noticeable changes in uptake levels over the same flow period. It was found that the efficient eluting agent was HNO3 (0.2 M). In some cases, the metals were not removed fully from the used beads during the first five cycles of regeneration and reuse. The results of this investigation show that these beads are efficient adsorbents for the removal of metal ions from spiked well water samples.

Acid resistant functionalised magnetic nanoparticles for radionuclide and heavy metal adsorption.

Coating superparamagnetic iron oxide NPs with SiO2 has been established in order to confer stability in acidic media. Acid stability tests were carried out between pH 1 and pH 7 to determine the effectiveness of the SiO2 passivating layer to protect the magnetic Fe3O4 core. Transmission Electron Microscopy (TEM) and zeta potential measurements have shown that uncoated Fe3O4 NPs exhibit rapid agglomeration and dissolution when exposed to acidic media, moving from a zeta potential of - 26 mV to a zeta potential of + 3 mV. In contrast, the SiO2 coating of the Fe3O4 NPs shows a very high degree of stability for over 14 months and the zeta potential of these NPs remained at ∼- 39 mV throughout the acid exposure and they showed no loss in magnetisaton. Due to the use of these NPs as a potential tool for heavy metal extraction, the stability of the surface functionalisation (in this case a phosphate complex) was also assessed. With a constant zeta potential of ∼ - 29 mV for POx-SiO2@Fe3O4 NP complex, the phosphate functionality was shown to be highly stable in the acidic conditions simulating the environment of certain nuclear wastes. ATR-FTIR was conducted after acid exposure confirming that the phosphate complex on the surface of the NPs remained present. Finally, preliminary sorption experiments were carried out with Pb(II), where the NP complexes shown complete removal of the heavy metals at pH 3 and pH 5.

Salicylaldehyde derivative of nano-chitosan as an efficient adsorbent for lead(II), copper(II), and cadmium(II) ions.

In this study, a biodegradable natural polymer chitosan was modified with salicylaldehyde to prepare salicylaldehyde functionalized chitosan nanoparticles (N-Ch-Sal). The N-Ch-Sal was characterized by atomic force microscopy (AFM), scanning electron microscopy-energy-dispersive X-ray (SEM-EDX), Fourier transform infrared spectroscopy (FT-IR) and thermogravimetric analysis (TGA). The salicylaldehyde functionalized chitosan nanoparticles (N-Ch-Sal) (~80 nm) were then used for the adsorption of three heavy metals viz., Cu(II), Cd(II) and Pb(II) ions. The above-mentioned techniques were also employed for evaluation of changes in N-Ch-Sal after metal adsorption. The parameters affecting the adsorption of metal ions including pH, contact time, amount of adsorbent, initial metal ion concentration and the effect of interfering ions, were studied thoroughly and optimized. The concentration of metal ions remaining in the aqueous system after adsorption experiments was analyzed by ICP-MS. At optimal conditions, sorption capacity of Pb(II) ion was found to be highest i.e., 123.67 followed by Cu(II) (84.60) and Cd(II) (63.71 mg/g). The adsorption process followed the pseudo-second-order kinetic model and fitted well with the Langmuir adsorption isotherm. The adsorption method was applied to a real tap water sample for the quantification and removal of Pb(II) ions. The concentration of Pb(II) ions in the tested sample was 4.88 ppb.

Solvent Bar Micro-Extraction of Heavy Metals from Natural Water Samples Using 3-Hydroxy-2-Naphthoate-Based Ionic Liquids.

Developments in the liquid micro-extraction of trace metals from aqueous phases have proven to be limited when extended from pure water to more complex and demanding matrices such as sea water or wastewater treatment effluents. To establish a system that works under such matrices, we successfully tested three task-specific ionic liquids, namely trihexyltetradecyl- phosphonium-, methyltrioctylphosphonium- and methyltrioctylammonium 3-hydroxy-2-naphthoate in two-phase solvent bar micro-extraction (SBME) experiments. We describe the influence of pH, organic additives, time, stirring rate and volume of ionic liquid for multi-elemental micro-extraction of Cu, Ag, Cd and Pb from various synthetic and natural aqueous feed solutions. Highest extraction for all metals was achieved at pH 8.0. Minimal leaching of the ionic liquids into the aqueous phase was demonstrated, with values < 30 mg L-1 DOC in all cases. Sample salinities of up to 60 g L-1 NaCl had a positive effect on the extraction of Cd, possibly due to an efficient extraction mechanism of the present chlorido complexes. In metal-spiked natural feed solutions, the selected SBME setups showed unchanged stability under all conditions tested. We could efficiently (≥85%) extract Cu and Ag from drinking water and achieved high efficacies for Ag and Cd from natural sea water and hypersaline water, respectively. The method presented here proves to be a useful tool for an efficient SBME of heavy metals from natural waters without the need to pretreat or modify the sample.

Novel 3-Hydroxy-2-Naphthoate-Based Task-Specific Ionic Liquids for an Efficient Extraction of Heavy Metals.

Ionic liquids (ILs) are per definition salts with melting points below 100°C and might be green alternatives for the extraction of heavy metals from aqueous solutions due to their favorable environmental and physico-chemical properties. Partial solution during extraction, so-called leaching, however, limits their applicability. The present study synthesizes three novel ammonium and phosphonium ILs based on 3-hydroxy-2-naphthoic acid-trihexyltetradecylphosphonium-([P66614]), methyltrioctylphosphonium-([P1888]), and methyltrioctylammonium 3-hydroxy-2-naphthoate ([N1888][HNA])-by a deprotonation-metathesis route. The aims were to improve stability during extraction while still achieving high selectivity toward heavy metal ions, as well as to study the impact of different alkyl chains and the central atom of the cation on physico-chemical properties, extraction efficacy, and leaching. Extraction capabilities for the seven heavy metals Ag, Cd, Co, Cu, Mn, Ni, and Pb were studied in pure water at pH 8.0. Further experiments were conducted in water containing 30 g L-1 NaCl to simulate a seawater matrix and/or 30 mg L-1 humic acids, as well as metal-spiked natural water samples. All three ILs showed extraction efficacies ≥90% for Cu and Pb after 24 h. Overall, extraction efficacies for Ag, Cd, Cu, and Pb were highest for drinking water samples. Ag and Cd extraction was increased by up to 41% in (hyper-) saline samples using IL [P66614][HNA] compared with pure water samples. Leaching values were reduced down to 0.07% loss of the applied IL, which can be attributed to the hydrophobic character of 3-hydroxy-2-naphthoate. Our results represent a positive development toward a greener extraction of heavy metals from natural waters.

Extraction of heavy metal (Ba, Sr) and high silica glass powder synthesis from waste CRT panel glasses by phase separation.

In this study, a novel process for the extraction of heavy metal Ba and Sr from waste CRT panel glass and synchronous preparation of high silica glass powder was developed by glass phase separation. CRT panel glass was first remelted with B2O3 under air atmosphere to produce alkali borosilicate glass. During the phase separation process, the glass separated into two interconnected phases which were B2O3-rich phase and SiO2-rich phase. Most of BaO, SrO and other metal oxides including Na2O, K2O, Al2O3 and CaO were mainly concentrated in the B2O3-rich phase. The interconnected B2O3-rich phase can be completely leached out by 5mol/L HNO3 at 90 ℃. The remaining SiO2-rich phase was porous glasses consisting almost entirely of silica. The maximum Ba and Sr removal rates were 98.84% and 99.38% and high silica glass powder (SiO2 purity > 90 wt%) was obtained by setting the temperature, B2O3 added amount and holding time at 1000-1100 ℃, 20-30% and 30 min, respectively. Thus this study developed an potential economical process for detoxification and reclamation of waste heavy metal glasses.

Comparison of three types of oil crop rotation systems for effective use and remediation of heavy metal contaminated agricultural soil.

Selecting suitable plants tolerant to heavy metals and producing products of economic value may be a key factor in promoting the practical application of phytoremediation polluted soils. The aim of this study is to further understand the utilization and remediation of seriously contaminated agricultural soil. In a one-year field experiment, we grew oilseed rape over the winter and then subsequently sunflowers, peanuts and sesame after the first harvest. This three rotation system produced high yields of dry biomass; the oilseed rape-sunflower, oilseed rape-peanut and oilseed rape-sesame rotation allowed us to extract 458.6, 285.7, and 134.5 g ha-1 of cadmium, and 1264.7, 1006.1, and 831.1 g ha-1 of lead from soil, respectively. The oilseed rape-sunflower rotation showed the highest phytoextraction efficiency (1.98%) for cadmium. Lead and cadmium in oils are consistent with standards after extraction with n-hexane. Following successive extractions with potassium tartrate, concentrations of lead and cadmium in oilseed rape and peanut seed meals were lower than levels currently permissible for feeds. Thus, this rotation system could be useful for local farmers as it would enable the generation of income during otherwise sparse phytoremediation periods.

Task-specific thioglycolate ionic liquids for heavy metal extraction: Synthesis, extraction efficacies and recycling properties.

Eight novel task-specific ionic liquids (TSILs) based on the thioglycolate anion designed for heavy metal extraction have been prepared and characterized by 1H and 13C NMR, UV-Vis, infrared, ESI-MS, conductivity, viscosity, density and thermal properties. Evaluation of their time-resolved extraction abilities towards cadmium(II) and copper(II) in aqueous solutions have been investigated where distribution ratios up to 1200 were observed. For elucidation of the IL extraction mode, crystals were grown where Cd(II) was converted with an excess of S-butyl thioglycolate. It was found by X-ray diffraction analysis that cadmium is coordinated by five oxygen and one sulfur donor atoms provided by two thioglycolate molecules and one water molecule. Leaching behavior of the hydrophobic ionic liquids into aqueous systems was studied by TOC (total dissolved organic carbon) measurements. Additionally, the immobilization on polypropylene was elucidated and revealed slower metal extraction rates and similar leaching behavior. Finally, recovery processes for cadmium and copper after extraction were performed and recyclability was successfully proven for both metals.

Heavy-metal extraction from sewage sludge using phosphorous-based salts: optimization process with Na2H2P2O7.

Land application is one of the important disposal alternatives for sewage sludge, but availability of potential toxic metals often restricts its uses. Three phosphorous-based salts (Na2H2P2O7, K4P2O7, KH2PO4) were studied as potential metal extractants. The conclusions of the research were that greater extractive efficiency is achieved through a 30-min process of vertical shaking with disodium diacid pyrophosphate - Na2H2P2O7 - at a concentration of 0.2 M at pH 2. Alternatively, the optimized process with oscillating shaking equipment would require 60 min. In both cases the average of set of extracted metals is around 50%. A second extraction process with potassium pyrophosphate - K4P2O7 at pH 6 achieved the reduction of further total amounts of metal, upper 65% with respect to the initial content. In this way the sludge could be used in land applications, with restrictions on each soil, according to the limit values specified in the future regulations.

Novel thiosalicylate-based ionic liquids for heavy metal extractions.

This study aims to develop novel ammonium and phosphonium ionic liquids (ILs) with thiosalicylate (TS) derivatives as anions and evaluate their extracting efficiencies towards heavy metals in aqueous solutions. Six ILs were synthesized, characterized, and investigated for their extracting efficacies for cadmium, copper, and zinc. Liquid-liquid extractions of Cu, Zn, or Cd with ILs after 1-24h using model solutions (pH 7; 0.1M CaCl2) were assessed using flame atomic absorption spectroscopy (F-AAS). Phosphonium-based ILs trihexyltetradecylphosphonium 2-(propylthio)benzoate [P66614][PTB] and 2-(benzylthio)benzoate [P66614][BTB] showed best extraction efficiency for copper and cadmium, respectively and zinc was extracted to a high degree by [P66614][BTB] exclusively.

Release of cadmium, copper and lead from urban soils of Copenhagen.

We studied the bonding and release kinetics of Cd, Cu and Pb from different soils in the older metropolitan area of Copenhagen. Total Cd, Cu and Pb concentrations were elevated 5-27 times in the urban soils compared to an agricultural reference soil, with Cd and Pb in mainly mobilisable pools and Cu in strongly bound pools. The soils were subjected to accelerated leaching studies in Ca(NO3)2 or HNO3 solutions resulting in release up to 78, 18 and 15% of total Cd, Cu and Pb soil concentrations over a period of 15 weeks. The relative initial Cd and Pb release rates increased 10 fold when pH decreased 2 and 3 units, respectively, while increases in Cu release rates were only seen at pH below 4. The total leachable Cu and Pb pools were higher in urban soils compared the agricultural reference soil but not for Cd.