Cation Exchange Mechanism Research Articles

Experimental and molecular insights into ionic liquid-based recovery of valuable metals from spent lithium-ion batteries

A new type of collaborative extractants consisting of the ionic liquid (IL) 1-aminoprooyl-3-methylimidazolium bis((trifluoromethyl)sulfonyl)imide, ([APMIM][Tf2N]) and Cyanex 923 (C923) is first applied for selective extraction of valuable metals from spent lithium-ion batteries (LIBs). The one-stage extraction efficiencies of Co2+, Ni2+ and Mn2+ are up to 99.87 %, 97.74 %, 99.98 %, respectively, at the optimal conditions, and the high-purity Li+ was enriched at the raffinate. It is found that the extraction process follows the so-called “cation exchange mechanism”, and the molecular-level mechanism is revealed via quantum chemical (QC) calculations. The findings show that C923 plays the role of coordinating with metal ions, the cation of IL exchanges metal ions from the aqueous to organic phases, and the anion [Tf2N]- of IL can stabilize the complex species of metal ion-[Tf2N]--C923 in organic phase. This work provides new insights for the design of novel IL-based extractants for the recycling of spent LIBs.

Novel magnetic adsorbents based on oyster and clam shells for the removal of cadmium in soil

Magnetic adsorbents can effectively remove heavy metals from soil. However, the magnetization process may reduce availability of adsorption sites, making it challenging to balance magnetic and adsorption properties. In this study, oyster shell (OS) and clam shell (CS) material was magnetized by an improved chemical co-precipitation method. The organic matter in the shells was destroyed by calcination modification to expose new active sites, and calcinated ferro-magnetic adsorbent was produced with either ferrosodium EDTA (giving CEOS and CECS) or with iron citrate (for CCOS and CCCS). All four modified adsorbents reached adsorption equilibrium for Cd2+ in solution within 120 min, with maximum adsorption capacities ranging from 115.5 to 266.5 mg/g, giving high removal efficiencies for Cd2+. Adsorption by precipitation and cation exchange mechanisms was dominant, together contributing >60 % of all adsorption capacity, followed by complexation. When used for remediation of Cd-contaminated soil, CEOS demonstrated the best Cd removal efficiency, achieving removal rates of 46 % and 58 % for total and available Cd, respectively. This was mainly because CEOS had the highest magnetic recovery rate, of 98 %. CEOS maintained removal rates of 34 % for total Cd after regeneration and reuse three cycles, with recovery rates remaining above 90 %. Contaminated soil was treated with the novel adsorbents and in pot experiments with water spinach cultivation it was shown that both CEOS and CECS treatment significantly reduced Cd content (by up to 56 %). The magnetic adsorbents presented here demonstrate excellent performance to remove Cd from water and soil, and have promising application prospects.

Solvation Effect-Determined Mechanisms of Cation Exchange Reactions for Efficient Multicomponent Nanocatalysts.

Cation exchange (CE) reaction is a classical synthesis method for creating complex structures. A lock of study on intrinsic mechanism limits its understanding and practical application. Using X-ray absorption spectroscopy, we observed that the evolution from Ru-Cl to Ru-O/OH occurs during the CE between K2RuCl6 and CoSn(OH)6 in aqueous solution, while CE between K2PtCl6 and CoSn(OH)6 is inhibited due to the failure of structural evolution from Pt-Cl to Pt-O/OH. Theoretical simulations imply that the interaction between Ru-O and CoSn(OH)6 with Co vacancy (CoVCoSn(OH)6) endows the electron transfer, as a result of strengthened adsorption on CoVCoSn(OH)6. Moreover, this mechanism is validated for CE between K2RuCl6 and ASn(OH)6 (A = Mg, Ca, Mn, Co, Cu, Zn), and CE between K2PdCl6/Na3RhCl6/K2IrCl6 and CoSn(OH)6. Impressively, the Pt-free CoRuSn(OH)x produced via CE displays a mass activity and a power density of 15.0 A mgRu-1 and 11.6 W mgRu-1, respectively, for anion exchange membrane fuel cell (AEMFC) exceeding the values of commercial PtRu/C (11.8 A mgRu+Pt-1 and 9.0 W mgRu+Pt-1). This work, for the first time, reveals the intrinsic mechanism of CE as structural evolution of target ion breaking through the traditional classic etch-adsorption mechanism and will promote fundamental research and practical application in various fields.

Solvation Effect‐Determined Mechanisms of Cation Exchange Reactions for Efficient Multicomponent Nanocatalysts

Cation exchange (CE) reaction is a classical synthesis method for creating complex structures. A lock of study on intrinsic mechanism limits its understanding and practical application. Using X‐ray absorption spectroscopy, we observed that the evolution from Ru−Cl to Ru−O/OH occurs during the CE between K2RuCl6 and CoSn(OH)6 in aqueous solution, while CE between K2PtCl6 and CoSn(OH)6 is inhibited due to the failure of structural evolution from Pt−Cl to Pt−O/OH. Theoretical simulations imply that the interaction between Ru−O and CoSn(OH)6 with Co vacancy (CoVCoSn(OH)6) endows the electron transfer, as a result of strengthened adsorption on CoVCoSn(OH)6. Moreover, this mechanism is validated for CE between K2RuCl6 and ASn(OH)6 (A = Mg, Ca, Mn, Co, Cu, Zn), and CE between K2PdCl6/Na3RhCl6/K2IrCl6 and CoSn(OH)6. Impressively, the Pt‐free CoRuSn(OH)x produced via CE displays a mass activity and a power density of 15.0 A mgRu−1 and 11.6 W mgRu−1, respectively, for anion exchange membrane fuel cell (AEMFC) exceeding the values of commercial PtRu/C (11.8 A mgRu+Pt−1 and 9.0 W mgRu+Pt−1). This work, for the first time, reveals the intrinsic mechanism of CE as structural evolution of target ion breaking through the traditional classic etch‐adsorption mechanism and will promote fundamental research and practical application in various fields.

A novel extraction process for efficient recovery of rare earth elements from the leaching liquor of ion-adsorption type rare earth ore using unsaponified N, N-di(2-ethylhexyl)-diglycolamic acid

There are still challenges in the recovery of rare earth elements (REEs) from leaching liquor of ion-adsorption type rare earth ore. In this paper, unsaponified N, N-di(2-ethylhexyl)-diglycolamic acid (HDEHDGA) was used to develop a green extraction process for efficient separation and enrichment of REEs. The cation exchange mechanism of RE(III) extraction was proposed by slope analysis and FT-IR spectra. HDEHDGA exhibited excellent extraction performances, such as short equilibrium time, high selectivity towards RE(III) and easy stripping by 0.5 mol/L HCl solution. REEs was enriched from 287.5 mg/L to 63.30 g/L by five-stage counter-current extraction and three-stage counter-current stripping using unsaponified HDEHDGA. The enrichment factor reached 220, and the proportion of REEs was increased from 80.76 wt% to 98.82 %. The loss of REEs was controlled below 2.14 wt%. This extraction strategy helps to improve the REEs recovery and avoid ammonia–nitrogen wastewater, which demonstrates its application potential in the ion-adsorption type rare earth ore.

Highly selective extraction of aluminum from chloride and sulfate solutions using a mixture of alkoxycarboxylic acid and tributyl phosphate

Four different solvent extraction systems are compared for aluminum (Al) separation in the presence of alkali metals, alkaline-earth metals, and transition metals. The octoxyacetic acid (OOA acid) is utilized as an Al extraction reagent for the first time, exhibiting high selectivity for Al. The impacts of the concentration of extractants, the equilibrium pH of the aqueous phase, and the concentration of phase modifier were studied systemically. The results indicate that the Al extraction efficiency using OOA/TBP (tributyl phosphate) system could reach 98.9 ± 0.63 % via a single-step solvent extraction process while maintaining negligible extraction for the other metal ions at the pH value of ∼ 4.2. Meanwhile, the separation factors (β) of Al over magnesium, calcium, manganese, cobalt and nickel reach the maximum values (βAl/Mg = 285157, βAl/Ca = 18275, βAl/Mn = 19271, βAl/Co = 10814, βAl/Ni = 5969). Slope analysis and infrared spectroscopic characterization confirm that the extraction of Al by the OOA/TBP system follows the cation exchange mechanism. The OOA/TBP solvent extraction system is promising for the efficient separation of Al, with potential applications in a wide range of practical scenarios.

Novel dialkylphosphinic acid modified Merrifield resins: Synthesis, characterization, and their adsorption and separation behaviors for zirconium and hafnium

Deep separation of Zr and Hf has always been a great challenging due to their very similar physicochemical properties. In this study, we established a method to synthesize two novel extraction chromatographic resins which graft dialkylphosphinic acid groups through amide group. The dialkylphosphinic acid modified resins were characterized by FT-IR, EA, SEM-EDS, XPS, and BET. Their adsorption and separation behaviors for Zr and Hf were investigated, and the adsorption mechanism was studied. The Zr and Hf adsorption onto Mer-CON-POOH-272 and Mer-CON-POOH-HYY2 both fit pseudo-second order model and Langmuir isotherm model. Mer-CON-POOH-HYY2 has stronger affinity to Zr and Hf than Mer-CON-POOH-272. Mer-CON-POOH-272 has a theoretical maximum loading capacity of 5.663 mg·g−1 Zr and 11.111 mg·g−1 Hf, while Mer-CON-POOH-HYY2 has a higher theoretical maximum loading capacity of 8.376 mg·g−1 Zr and 13.157 mg·g−1 Hf. Dialkylphosphinic acids are the functional groups of Mer-CON-POOH-272 and Mer-CON-POOH-HYY2 that interact with Zr and Hf during adsorption. They adsorb Zr and Hf through cation exchange mechanism, which can be expressed as M(SO4)32– + 2HL ⇌ M(SO4)L2 +.2H+ + 2SO42-. With increasing H2SO4 concentration, the Zr and Hf extraction percentages and their separation efficiency reduce. The DFT calculation reveals that the adsorption process is accompanied by charge transfer. Adsorption occurs mainly at P = O and P-O positions. The affinity of the two resins for Hf is higher than that of Zr, which is the reason why the resin preferentially adsorbs Hf.

Influence of ionic liquid (R4PSCN) for selective separation and recovery of copper from spent Cu[sbnd]Cr catalyst leach liquor

Separation and recovery of copper (Cu) from sulphate mediated CuCr spent catalyst leach solution through solvent extraction approach has been systematically investigated. A number of Ionic Liquid (IL) and other conventional extractants were used while investigating the selectivity and efficient extraction tendency of either IL or extractants towards Cu(II). In context of copper extraction efficiency, the adopted organic reagents followed the descending order: R4PSCN > R4PD > R4PCy > Cyphos 101 > Aliquot 336 > D2EHPA > Cyanex 272. The extraction behavior of Cu(II) was established based on slope analysis method. From the results it was noticed that extraction occurs through a cation exchange mechanism with association of a mole of Cu(II) per mole of R4PSCN. The plot of log D vs. log [R4PSCN] yield a linear relationship with a slope close to 4 which is used to propose extraction reaction mechanism/ stoichiometry. The nature of complex between Cu(II) and IL was further examined using FTIR analysis of the loaded organic phase with the diluent. Mc-Cabe Thiele diagram was constructed to predict quantitative extraction of Cu(II) which revealed the need for two stages at aqueous to organic (A:O) phase volume ratio of =3:1. The stripping isotherm constructed at optimum NH4OH concentration (0.4 M) suggests the need for two stages at O:A phase volume ratio of = 2:1 for complete stripping of copper with regeneration of R4SCN for further use. Both isotherm conditions were validated by 6 cycles of counter current simulation (CCS) study for obtaining the desired amount of Cu(II) loaded R4SCN (during extraction) and/or stripped copper solution (during stripping). Overall copper enrichment was ∼6 fold leading to produce a copper(II) solution of 48 g/L from 6 g/L Cu(II). The stripped solution was subjected to crystallization study to produce copper sulphate crystals of high purity and was confirmed by XRD analysis of crystal phases.

Heavy Metal Detection and Removal by Composite Carbon Quantum Dots/Ionomer Membranes.

The combination of ion exchange membranes with carbon quantum dots (CQDs) is a promising field that could lead to significant advances in water treatment. Composite membranes formed by sulfonated poly(ether ether ketone) (SPEEK) with embedded CQDs were used for the detection and removal of heavy metal ions, such as lead and cadmium, from water. SPEEK is responsible for the capture of heavy metals based on the cation exchange mechanism, while CQDs detect their contamination by exhibiting changes in fluorescence. Water-insoluble "red" carbon quantum dots (rCQDs) were synthesized from p-phenylenediamine so that their photoluminescence was shifted from that of the polymer matrix. CQDs and the composites were characterized by several techniques: FTIR, Raman, UV/VIS, photoluminescence, XPS spectroscopies, and AFM microscopy. The heavy metal ion concentration was analyzed by inductively coupled plasma-optical emission spectroscopy (ICP-OES). The concentration ranges were 10.8-0.1 mM for Pb2+ and 10.0-0.27 mM for Cd2+. SPEEK/rCQDs showed a more pronounced turn-off effect for lead. The composite achieved 100% removal efficiency for lead and cadmium when the concentration was below a half of the ion exchange capacity of SPEEK. The regeneration of membranes in 1 M NaCl was also studied. A second order law was effective to describe the kinetics of the process.

Understanding the Role of Ligand Structure on Extraction of Neptunium by N-Pivot Tripodal Diglycolamides in an Ionic Liquid

ABSTRACT The extraction of Np4+ was studied by a series of N-pivot tripodal diglycolamides, with varying substituents (alkyl groups with varying branching and chain length) and varying spacer length, dissolved in an ionic liquid, i.e. [C4mim][Tf2N]. Out of a series of four ligands, L I (propylene spacer) and L II (ethylene spacer) differ only in the spacer length connecting the three diglycolamide units with the tripodal N platform. While L II – L IV have the same spacer length (ethylene spacer), but L II has a hydrogen atom, L III has methyl group, and L IV has isopropyl group as a substituent at the amidic N atom close to the central N atom. A reversal extraction mechanism of Np4+ was observed when the spacer chain length reduced from a propylene group in L I to an ethylene group in L II – L IV . While a cation-exchange mechanism was observed in case of L I , a solvation extraction mechanism was seen for the other three ligands with the extracted species being Np(NO3)2(L)2+ for L I , and [Np(NO3)4·L] for L II – L IV . The extraction efficiencies of Np4+ with L II – L IV were significantly affected by the nature of the alkyl substituents and follow the order: L II > L III > L IV . This trend in the extraction pattern affirms that the alkyl substitution at the amidic N atom creates steric strain in the ligand while complexing with the metal ion.

Constructing hydroxyoxime-functionalized ionic liquid [BHIB][NTf2] for the separation of Mo(VI) from U(VI)

We describe here a hydroxyoxime-functionalized ionic liquid, 1-butyl-3-(4-hydroxy-3-((hydroxyimino)methyl)benzyl)-1H-imidazol-3-ium bis((trifluoromethyl)sulfonyl)amide ([BHIB][NTf2]), for the isolation and purification of 99Mo from 235U. This material exhibits remarkable extraction efficiency for Mo(VI) from 0.1 to 2 M HNO3 and can effectively distinguish Mo(VI) from U(VI). The attained highest separation factor (SF) of Mo(VI) over U(VI) exceeds 104, thus setting a new record for their separation. Additionally, the extracted Mo(VI) can be efficiently recovered using either NH4OH or the mixture of NH4OH and (NH4)2CO3. This excellent extraction performance is sustained even after five cycles. The extraction efficiency remains stable following exposure to 150 kGy gamma irradiation, thus providing robust experimental support for potential engineering applications. Slope analysis and EXAFS results indicate that [BHIB][NTf2] forms a 2:1 complex with Mo(VI) during the extraction process primarily driven by a cation exchange mechanism. When one equivalent of Mo(VI) migrates from the aqueous phase to the organic phase, each of two equivalents [BHIB][NTf2] remove one of H+ and migrate to the aqueous phase to maintain charge balance. This investigation introduces a highly efficient and environmentally benign method for separation, alongside providing novel insights into ligand design for the efficacious differentiation of Mo(VI) and U(VI) under HNO3 conditions, potentially streamlining current methodologies.

Retention mechanisms of amitriptyline and its impurities on amide, amino, diol, and silica columns in hydrophilic interaction liquid chromatography.

Hydrophilic interaction liquid chromatography (HILIC) has been widely applied to challenging analysis in biomedical and pharmaceutical fields, bridging the gap between normal-phase high-performance liquid chromatography and reversed-phase high-performance liquid chromatography (RP-HPLC). This paper comprehensively explores the retention mechanisms of amitriptyline and its impurities A, B, C, D, F, and G on amide, amino, diol, and silica columns. Dual HILIC/RP-HPLC retention mechanisms were developed, and transitional points between HILIC and RP-HPLC mechanisms were calculated on amide, diol, and silica columns. Adsorption and partition contributions to overall retention mechanisms were evaluated using Python software in HILIC and RP-HPLC regions. The cation exchange mechanism dominates overall retention for ionized analytes in the silica column (R2>0.995), whereas the retention of ionized analytes increases with pH. Impacts of acetonitrile content, buffer ionic strength, and pH, along with their interactions on the retention of ionized analytes in the silica column, were determined using the chemometric approach. Acetonitrile content showed the most significant impact on the retention mechanisms. These findings highlight that a detailed investigation into retention mechanisms provides notable insights into factors influencing analyte retention and separation, promising valuable guidance for future analysis.

Ultrafast Removal of Thorium and Uranium from Radioactive Waste and Groundwater Using Highly Efficient and Radiation-Resistant Functionalized Triptycene-Based Porous Organic Polymers.

Thorium (Th) and uranium (U) are important strategic resources in nuclear energy-based heavy industries such as energy and defense sectors that also generate significant radioactive waste in the process. The management of nuclear waste is therefore of paramount importance. Contamination of groundwater/surface water by Th/U is increasing at an alarming rate in certain geographical locations. This necessitates the development of strategic adsorbent materials with improved performance for capturing Th/U species from radioactive waste and groundwater. This report describes the design of a unique, robust, and radiation-resistant porous organic polymer (POP: TP-POP-SO3NH4), which demonstrates ultrafast removal of Th(IV) (<30 s)/U(VI) (<60 s) species present in simulated radioactive wastewater/groundwater samples. Thermal, chemical, and radiation stabilities of these POPs were studied in detail. The synthesized ammoniated POP revealed exceptional capture efficiency for trace-level Th (<4 ppb) and U (<3 ppb) metal ions through the cation-exchange mechanism. TP-POP-SO3NH4 shows a significant sorption capacity [Th (787 mg/g) and U (854 mg/g)] with an exceptionally high distribution coefficient (Kd) of 107 mL/g for Th. This work also demonstrates a facile protocol to convert a nonperforming POP, by simple chemical modifications, into a superfast adsorbent for efficient uptake/removal of U/Th.

Deep eutectic solvent‐assisted selective extraction of valuable metals from waste lithium‐ion batteries

AbstractA novel synergistic extractant consisting of a deep eutectic solvent (DES) and tri‐n‐butyl phosphate (TBP) is proposed for selective extraction of valuable metals from waste lithium‐ion batteries (LIBs). The extraction efficiencies of Ni2+, Co2+, and Mn2+ were 99.8%, 99.1%, and 95.9%, respectively, and high‐purity Li+ was enriched in the raffinate after the single‐stage extraction. Valuable metal salts, lithium carbonate (92.3 wt%) and cobalt oxalate (94.9 wt%), were obtained. The DES + TBP extractant retained its high extraction performance even after multiple regeneration cycles. The extraction process followed the so‐called “cation exchange mechanism” with thermodynamic properties of ΔH &lt; 0, ΔG &lt; 0, and ΔS &lt; 0. The molecular‐level extraction mechanism demonstrated that the extraction process was dominated by both electrostatic and coordination interactions between the metal ions and DES/TBP, based on quantum chemical calculations. This study aims to provide a new strategy for recycling valuable metals from waste LIBs.

Brine formation in cold desert, shallow groundwater systems: Antarctic Ca-Cl brine chemistry controlled by cation exchange, microclimate, and organic matter

Groundwater in the McMurdo Dry Valleys of Antarctica is commonly enriched in calcium and chloride, in contrast to surface and groundwater in temperate regions, where calcium chemistry is largely controlled by the dissolution of carbonates and sulfates. These Antarctic Ca-Cl brines have extremely low freezing points, which leads to moist soil conditions that persist unfrozen and resist evaporation, even in cold, arid conditions. Several hypotheses exist to explain these unusual excess-calcium solutions, including salt deliquescence and differential salt mobility and cation exchange. Although the cation exchange mechanism was shown to explain the chemistry of pore waters in permafrost cores from several meters depth, it has not been evaluated for near-surface groundwater and wetland features (water tracks) in which excess-calcium pore-water solutions are common. Here, we use soluble salt and exchangeable cation concentrations to determine whether excess calcium is present in water-track brines and if cation exchange could be responsible for calcium enrichment in these cold desert groundwaters. We show that calcium enrichment by cation exchange is not occurring universally across the McMurdo Dry Valleys. Instead, evidence of the present-day formation of Ca-Cl−rich brines by cation exchange is focused in a geographically specific location in Taylor Valley, with hydrological position, microclimate, soil depth, and organic matter influencing the spatial extent of cation exchange reactions. Up-valley sites may be too cold and dry for widespread exchange, and warm and wet coastal sites are interpreted to host sediments whose exchange reactions have already gone to completion. We argue that exchangeable cation ratios can be used as a signature of past freeze-concentration of brines and exchange reactions, and thus could be considered a geochemical proxy for past groundwater presence in planetary permafrost settings. Correlations between water-track organic matter, fine sediment concentration, and cation exchange capacity suggest that water tracks may be sites of enhanced biogeochemical cycling in cold desert soils and serve as a model for predicting how active layers in the Antarctic will participate in biogeochemical cycling during periods of future thaw.

Facile green synthesis route for new ecofriendly photo catalyst for degradation acid red 8 dye and nitrogen recovery

This study novelty is that new photo catalyst prepared from sustainability low cost precursors. Dark red color hydrogel composites have been easily prepared from gelatin biopolymer using a simple sol–gel method. Gelatin doped by cobalt chloride, and silver nanoparticles (SNPs) in the presence of traces amount of sodium dodecyl sulfate surfactant and calcium chloride. Water-insoluble Gelatin composites are thermally stable photocatalysts for the degradation of toxic anionic acid red 8 dye. Promising photodynamic activity confirmed by fluorescence emission at λmax 650 nm. Optical absorption in Vis. light enhanced photo catalytic activity. Silver nanoparticles enhanced crystallinity, and improved optical properties and porosity. Dopants by CoCl2 and silver nanoparticles increased band gap of gelatin composites from (1.82 to 1.95) indicating interfacial charge separation. Low band gaps improved photo catalytic activity. Optical band gaps (Eg) lower than 2.0 eV indicates high catalytic activity in the photo degradation acid red 8 dye using Vis. light, wavelength 650 nm. Percent removal efficiency (%Re) of the dye at 500 ppm initial concentration, pH 1, contact time 30 min., and 0.20 g L−1 dose photo catalyst reached 95%. pH not affects removal efficiency. So, gelatin composites removed AR8 dye by photodegradation mechanism rather than adsorption due to photodynamic activity. Kinetics of photodegradation followed pseudo first order kinetic with rate constant k1 5.13 × 10−2 min.−1 Good electrical conductivity and magnetic properties (effective magnetic moment (µeff 4.11 B.M) improved dye degradation into simple inorganic species. Nutrients NH4+, and NO3− degradation products recovered by using alumina silicate clay via a cation exchange mechanism.

A high surface area mesoporous silica adsorbent for uranium uptake from lean uranium solutions: Template assisted preparation of mesoporous silica and its functionalization with iminodiacetic acid

The feasibility of uranium recovery from lean uranium solutions (like seawater) having extremely low concentrations has been explored using an iminodiacetic acid (ImDAc) modified mesoporous silica (MPS) adsorbent (MPS-ImDAc). Foremost, synthesis of the MPS, its chemical modification using ImDAc and characterization were emphasized. The MPS was prepared by a template assisted preparative route, and the incorporation of ImDAc moiety to the MPS was accomplished through chemical functionalization. Subsequently, the adsorption efficacy of the MPS-ImDAc has been investigated as a function of the pH of the aqueous medium, kinetics of adsorption, uranium loading to the adsorbent, and the effect of interfering elements. Zeta potential analyses were also conducted to investigate the role of ImDAc functional groups and charges at different pH values, and the study suggested that the negatively charged acetate moiety is likely responsible for adsorption above pH.The adsorption has been modeled using pseudo-first and second order kinetic and the Langmuir adsorption isotherm models. Superior adsorption of uranium above pH 4, based on cation exchange mechanism that leads to an adsorption capacity of approximately 110 mg/g was observed. Adsorption characteristics have been investigated from a synthetic seawater composition with all possible interfering elements, and the study confirmed that though sodium is significantly present in sea water, it has negligible adsorption to ImDAc and thus pose no competition to uranium adsorption. Small pore size and massive surface area of MPS in combination with uranium selective ImDAc functional group offer excellent uranium adsorption.

NdFeB magnet scrap valorization by leaching and recovery of rare earth metals by sorption on low-cost expanded clay

The search for new sources of rare earth metals (REM), such as neodymium and dysprosium, has ensued globally due to their strategic value for the sustainability of the energy sector. In this context, this work explored the potential of vermiculite as a sorbent for recovering rare earth cations from the leachate of end-of-life NdFeB magnets by kinetic, equilibrium, and desorption investigations. In which the REM uptake on vermiculite occurred by fast kinetics, and the significant sorbate-sorbate interactions at the equilibrium indicated that the REM sorption was a cooperative process; vermiculite sorbed the metals from the acid leachate in the following order: Fe(III) > Nd(III) > Zn(II) > Pr(III) > Co(II) > Dy(III) > Ni(II) > Al(III) > Mn(II); and the chelating agent ethylenediaminetetraacetic acid desorbed Nd(III) preferably over other metals, indicating the potential for further selective recovery processes. The characterization analyses indicated that the loaded vermiculite preserved the original structure, composition, functional groups, and thermal stability. Also, X-ray photoelectron spectroscopy corroborated the cation exchange mechanism between interlayer magnesium in the REM sorption. Thus, the experimental findings and a cost analysis compared to the literature demonstrated the cost-effectiveness and potential of vermiculite for the valorization of NdFeB magnet leachates.

Bentonite-Chitosan composites or beads for lead (Pb) adsorption: Design, preparation, and characterisation

This study investigated the efficiency of mixing bentonite with chitosan via different preparation methods, subsequently the different forms were investigated for their ability to remove Pb(II) ions from solution. The different forms of bentonite-chitosan (Bt-Ch), composites and beads, were prepared via solution blending and precipitation methods, respectively and in the weight ratios of 90%/10%, 70%/30% and 50%/50%. The beads were further subdivided, identified as “beads-A" and “beads-B", and were formed by adding either bentonite suspension or bentonite powder, respectively, to solubilised chitosan solution. The composites and beads were characterised by X-ray fluorescence (XRF), thermogravimetric analysis (TGA), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and pH at zero point charge. XRF analysis showed a cation exchange mechanism occurred when chitosan was initially mixed with the bentonite. TGA results confirmed that beads contained more chitosan compared to their corresponding weight ratio equivalent composites. XRD results showed that chitosan was intercalated within the interlayer space of the bentonite for Bt-Ch composites and Bt-Ch beads-A and that the interlayer spacings increased with increasing chitosan loading. Though similar amounts of chitosan were present in both Bt-Ch beads-A and beads-B, there were fewer reflection shifts for beads B suggesting less intercalation of chitosan when the bentonite was added as a powder. FTIR spectra from the Bt-Ch composites and beads confirmed the presence of both chitosan and bentonite, and the NH bands of chitosan shifted to lower frequencies demonstrating their involvement in the bonding mechanism of chitosan with bentonite. The experimental adsorption data correlated well with both non-linear Langmuir and Freundlich isotherm models, and in which both chemisorption and physisorption processes played crucial roles. The Langmuir-maximum adsorption capacities of Pb(II) ions for all the analysed Bt-Ch composites and beads was found to range from 42.48 ± 4.22 to 94.60 ± 5.63 mg/g. The amount of chitosan present in the adsorbent and its distribution within or outside the interlayer space of the bentonite was shown to have pronounced effects on the Pb(II) uptake by the different Bt-Ch composites/beads, and although the chitosan greatly enhanced the adsorption of Pb(II) a cation exchange mechanism with the clay was still a dominant process. The adsorption of Pb(II) was also significantly affected by the presence of other multi-competing ions. Moreover, the developed Bt-Ch composites/beads exhibited good potential for re-use after five cycles of regeneration, thus, indicating their potential as cost-effective adsorbents for removal of Pb(II) ions from both drinking and wastewater.

Simultaneous speciation analysis of Hg and Se in fish by high-performance liquid chromatography and inductively coupled plasma-mass spectrometry following microwave-assisted enzymatic hydrolysis.

This study reports the development and validation of a new analytical method for simultaneous speciation analysis of Se and Hg in fish muscle. For this purpose, four Se species (selenite/Se(IV), selenate/Se(VI), selenomethionine/SeMet, and selenocysteine/SeCys) and two Hg species (inorganic mercury/iHg and methylmercury/MeHg) were extracted simultaneously by microwave-assisted enzymatic hydrolysis and then separated by HPLC in less than 15min by using a column with both anion and cation exchange mechanisms and a mobile phase consisting of a mixture of methanol 5% (v/v), 45mM HNO3, 0.015% 2-mercaptoethanol, and 1.5mM sodium 3-mercapto-1-propanesulfonate. The separated species of Hg and Se were detected online by inductively coupled plasma-mass spectrometry (ICP-MS). The speciation analysis method was validated by means of the accuracy profile approach by carrying out three series of measurements in duplicate on three different days over a time-span of 3weeks. The limits of quantification (LOQ) are in the range of 0.010-0.013mg/kg wet weight (ww) for all selenium species, except for Se(IV) (0.15mg/kg ww), while the coefficient of variation in terms of intermediate reproducibility (CVR) was < 7%. The LOQ for MeHg was 0.006mg/kg ww, while the CVR was 3%. The method was successfully applied to the analysis of muscle samples from four different fish species: rainbow trout, tuna, swordfish, and dogfish.