Synthesis and Characterization of Functionalized Chitosan Nanoparticles with Pyrimidine Derivative for Enhancing Ion Sorption and Application for Removal of Contaminants.

Modified chitosan has been widely used for heavy metals removal during the last few decades. In this research, the study was focused on the effect of modified chitosan particles after grafting with heterocyclic constituent for enhancing the sorption of Cr(VI) ions. Chitosan was functionalized by 2-thioxodihydropyrimidine-4,6(1H,5H)-dione, in which the synthesized composite considered as a nanoscale size with average 5-7 nm. This explains the fast kinetics of sorption with large surface area. The prepared sorbent was characterized by Fourier-transform infrared (FTIR), elemental analysis (EA), Brunauer-Emmett-Teller (BET surface area) theory, thermogravimetric analysis (TGA), mass spectroscopy, and scanning electron microscopy (SEM) with energy dispersive X-ray analysis (EDX) analyses. The experimental part of this work involved the application of the synthesized sorbent for the removal of Cr(VI) ions from highly contaminated tannery effluents that are characterized by a high concentration toward chromate ions with other associated toxic elements, i.e., Pb(II) and Cd (II) ions, which underscore the importance of this treatment. Under the selected conditions (K2Cr2O7 salt, Co: 100 mg L-1 and pH: 4), the sorption diagram shows high Cr(VI) sorption and fast uptake kinetics. The sorption was enhanced by functionalization to 5.7 mmol Cr g-1 as well as fast uptake kinetics; 30 min is sufficient for total sorption compared with 1.97 mmol Cr g-1 and 60 min for the non-grafted sorbent. The Langmuir and Sips equations were fitted for the sorption isotherms, while the pseudo-first order rate equation (PFORE) was fitted for the uptake kinetics.

U(VI) and Th(IV) recovery using silica beads functionalized with urea- or thiourea-based polymers - Application to ore leachate.

Urea and thiourea have been successfully deposited at the surface of silica beads (through one-pot reaction with formaldehyde) for designing new sorbents for U(VI) and Th(IV) recovery (UR/SiO2 and TUR/SiO2 composites, respectively). These materials have been characterized by FTIR, titration, elemental analysis, BET, TGA, SEM-EDX for identification of structural and chemical properties, and interpretation of binding mechanisms. Based on deprotonation of reactive groups (amine, carbonyl, or thiocarbonyl) and metal speciation, the optimum pH was ~4. Uptake kinetics was fast (equilibrium within 60-90 min). Although the kinetic profiles are fitted by the pseudo-first order rate equation, the resistance to intraparticle diffusion cannot be neglected. Sorption isotherms were fitted by Langmuir equation (maximum sorption capacities: 1-1.2 mmol g-1). Thermodynamics are also investigated showing differences between the two types of functionalized groups: exothermic for TUR/SiO2 and endothermic for UR/SiO2. Metal desorption is highly effective using 0.3-0.5 M HCl solutions: total desorption occurs within 30-60 min; sorption/desorption properties are remarkably stable for at least 5 cycles. The sorbents have marked preference for U(VI) and Th(IV) over alkali-earth and base metals at pHeq ~4.8. By preliminary precipitation steps, it is possible "cleaning" ore leachates of pegmatite ore, and recovering U(VI) and Th(IV) using functionalized silica beads. After elution and selective recovery by precipitation with oxalate (Th-cake) and alkaline (U-cake), the metals can be valorized.

Phosphorylation of Guar Gum/Magnetite/Chitosan Nanocomposites for Uranium (VI) Sorption and Antibacterial Applications.

The development of new materials is needed to address the environmental challenges of wastewater treatment. The phosphorylation of guar gum combined with its association to chitosan allows preparing an efficient sorbent for the removal of U(VI) from slightly acidic solutions. The incorporation of magnetite nanoparticles enhances solid/liquid. Functional groups are characterized by FTIR spectroscopy while textural properties are qualified by N2 adsorption. The optimum pH is close to 4 (deprotonation of amine and phosphonate groups). Uptake kinetics are fast (60 min of contact), fitted by a pseudo-first order rate equation. Maximum sorption capacities are close to 1.28 and 1.16 mmol U g-1 (non-magnetic and magnetic, respectively), while the sorption isotherms are fitted by Langmuir equation. Uranyl desorption (using 0.2 M HCl solutions) is achieved within 20-30 min; the sorbents can be recycled for at least five cycles (5-6% loss in sorption performance, complete desorption). In multi-component solutions, the sorbents show marked preference for U(VI) and Nd(III) over alkali-earth metals and Si(IV). The zone of exclusion method shows that magnetic sorbent has antibacterial effects against both Gram+ and Gram- bacteria, contrary to non-magnetic material (only Gram+ bacteria). The magnetic composite is highly promising as antimicrobial support and for recovery of valuable metals.

Synthesis of Eco-Friendly Biopolymer, Alginate-Chitosan Composite to Adsorb the Heavy Metals, Cd(II) and Pb(II) from Contaminated Effluents.

Efficient removal of Cd(II) and Pb(II) from contaminated water is considered a fundamental point of view. Synthetic hydrogel biopolymers based on chitosan and alginate (cost-effective and eco-friendly) were successfully designed and characterized by highly efficient removal contaminants. The sorbents are characterized by FTIR, SEM-EDX, TGA, XPS analyses and textural properties which are qualified by N2 adsorption. The sorption properties are firstly investigated by the effect of pH, sorption isotherms, uptake kinetics, and selectivity from multi-metal solution with equi-molar concentration. The sorbent with 1:3 ratios (of chitosan and alginate respectively) is the most effective for metal removal (i.e., 0.81 mmol Cd g-1 and 0.41 mmol Pb g-1). Langmuir and Sip's models fitted better the adsorption isotherms compared to the Freundlich model. Uptake kinetics was well fitted by pseudo-first-order rate equation, while the saturation was achieved within 40 min. The sorbent shows good reproducibility through duplicate the experiments with negligible decreasing efficiency (>2.5%). The sorbent was applied for water treatment on samples collected from the industrial area (i.e., 653 and 203 times over the MCL for Cd(II) and Pb(II) respectively according to WHO). The concentration of Cd and Pb was drastically decreased in the effluents as pH increased with removal efficiency up to 99% for both elements at pH 5.8 and SD equivalent 1 g L-1 for 5 h.