Kinetic Modeling and Mechanisms of Manganese Removal from Alkaline Mine Water Using a Pilot Scale Column Reactor

Manganese (Mn) is a major element in various aqueous and soil environments that is sometimes highly concentrated in mine water and other mineral processing wastewater. In this study, we investigated Mn removal from alkaline mine water (pH > 9) with an Mn-coated silica sand packed into a pilot-scale column reactor and examined the specific reaction mechanism using X-ray absorption near-edge structure (XANES) analysis and geochemical kinetic modeling. The kinetic effect of dissolved Mn(II) removal by birnessite (δ-Mn(IV)O2) at pH 6 and 8 was evaluated at different Mn(II)/Mn(IV) molar ratios of 0.1–10. Our results confirmed the positive effect of the presence of δ-MnO2 on the short-term removal (60 min) of dissolved Mn. XANES analysis results revealed that δ-MnO2 was more abundant than Mn(III)OOH in the reactor, which may have accumulated during a long-term reaction (4 months) after the reactor was turned on. A gradual decrease in dissolved Mn(II) concentration with depth was observed in the reactor, and comparison with the kinetic modeling result confirmed that δ-MnO2 interaction was the dominant Mn removal mechanism. Our results show that δ-MnO2 contents could play a significant role in controlling Mn removability from mine water in the reactor.

Application of the Remote Interaction Effect and Molecular Imprinting in Sorption of Target Ions of Rare Earth Metals

The goal of the present work is a comparative study of the effectiveness of the application of intergel systems and molecularly imprinted polymers for the selective sorption and separation of neodymium and scandium ions. The following physico-chemical methods of analysis were used in this study: colorimetry and atomic-emission spectroscopy. The functional polymers of polyacrylic acid (hPAA) and poly-4-vinylpyridine (hP4VP) in the intergel system undergo significant changes in the initial sorption properties. The remote interaction of the polymers in the intergel system hPAA–hP4VP provides mutual activation of these macromolecules, with subsequent transfer into a highly ionized state. The maximum sorption of neodymium and scandium ions is observed at molar ratios of 83%hPAA:17%hP4VP and 50%hPAA:50%hP4VP. Molecularly imprinted polymers MIP(Nd) and MIP(Sc) show good results in the sorption of Nd and Sc ions. Based on both these types of these macromolecular structures, principally new sorption methods have been developed. The method based on the application of the intergel system is cheaper and easier in application, but there is some accompanying sorption (about 10%) of another metal from the model solution during selective sorption and separation. Another method, based on the application of molecularly imprinted polymers, is more expensive and the sorption properties are higher, with the simultaneous sorption of the accompanying metal from the model solution.

Structural Characterization and Physical Properties of Double Perovskite La2FeReO6+δ Powders

The structural, optical, dielectric, and magnetic properties of double perovskite La2FeReO6+δ (LFRO) powders synthesized by solid-state reaction method under CO reduced atmosphere are reported on in this paper. Reitveld refinements on the XRD data revealed that the LFRO powders crystallized in an orthogonal structure (Pbnm space group) with column-like morphology. The molar ratios of La, Fe, and Re elements were close to 2:1:1. XPS spectra verified the mixed chemical states of Fe and Re ions, and two oxygen species in the LFRO powders. The LFRO ceramics exhibited a relaxor-like dielectric behavior, and the associated activation energy was 0.05 eV. Possible origins of the dielectric relaxation behavior are discussed based on the hopping of electrons among the hetero-valence ions at B-site, oxygen ion hopping through the vacant oxygen sites, and the jumping of electrons trapped in the shallower level created by oxygen vacancy. The LFRO powders display room temperature ferromagnetism with Curie temperature of 746 K. A Griffiths-like phase was observed in the LFRO powders with a Griffiths temperature of 758 K. The direct optical band gap of the LFRO powders was 2.30 eV, deduced from their absorption spectra, as confirmed by their green photoluminescence spectra with a strong peak around 556 nm.

EPR Study of the Mn-Doped Magnesium Titanate Ceramics

Manganese-doped magnesium titanate ceramic samples obtained by a solid-state reaction via sintering in the air from a mixture of MgO and TiO2 powders of different molar ratios were analyzed by electron paramagnetic resonance (EPR) technique. The EPR signals of Mn2+ ions (S = 5/2, І = 5/2) in crystal phases of MgO, Mg2TiO4, and MgTiO3 were detected. We have obtained the following spin Hamiltonian parameters for Mn2+ ions: g = 2.0015, A ~ 81 ∗ 10-4 cm-1 (in MgO phase); g = 2.0029, A ~ 73.8 ∗ 10-4 cm-1, b2 0 = 35 ∗ 10-4 cm-1 (in Mg2TiO4 phase); g = 2.004, A ~ 79 ∗ 10-4 cm-1, b2 0 = 165 ∗ 10-4 cm-1 (in MgTiO3 phase). Despite the presence of Mn4+ centers in both Mg2TiO4:Mn and MgTiO3:Mn ceramics confirmed by previous optical studies, no EPR signals related to Mn4+ ions (S = 3/2, І = 5/2) were found. The Mn2+ EPR signals are proposed as structural probes in manganese-doped magnesium titanate ceramics.

Effect of Aluminum Incorporation on the Reaction Process and Reaction Products of Hydrated Magnesium Silicate

In this study, we investigated the impact of aluminium ion (Al3+) incorporation on the microstructure and the phase transformation of the magnesium silicate hydrate system. The magnesium silicate hydrate system with aluminium was prepared by mixing magnesium oxide and silica fume with different aluminium ion contents (the Al/Si molar ratios of 0.01, 0.02, 0.05, 0.1, 0.2) at room temperature. The high degree of polymerization of the magnesium silicate hydrate phases resulted in the limited incorporation of aluminium in the structure of magnesium silicate hydrate. The silicon-oxygen tetrahedra sites of magnesium silicate hydrate layers, however, were unable to substitute for silicon sites through inverted silicon-oxygen linkages. The increase in aluminium ion content raised the degree of polymerization of the magnesium silicate hydrate phases from 0.84 to 0.92. A solid solution was formed from residual aluminum-amorphous phases such as hydroxyl-aluminum and magnesium silicate hydrate phases. X-ray diffraction (XRD), field emission scanning electron microscope (F-SEM), and 29Si and 27Al MAS NMR data showed that the addition of Al3+ promotes the hydration process of MgO and has an obvious effect on the appearance of M-S-H gel. The gel with low aluminum content is fluffy, while the gel with high aluminum content has irregular flakes. The amount of Al3+ that enters the M-S-H gel increased with the increase of Al3+ content, but there was a threshold: the highest Al/Si molar ratio of M-S-H gel can be maintained at about 0.006.

Surface Chemistry Study of the Interactions of Sesame Oil with Meibomian Films

A possible approach for the treatment of meibomian gland disease (MGD) can be the supplementation of meibomian gland secretion (MGS) with nonpolar lipids (NPL) rich plant oils. Sesame oil (SO), approximately equal in monounsaturated fat (oleic acid, 40% of total) and polyunsaturated fat (linoleic acid, 42% of total), has shown multiple health benefits due to its anti-inflammatory and antioxidant effects. Thus, the interactions between SO and MGS in surface layers deserve further study. Therefore, pseudobinary films were formed with controlled MGS/SO molar ratios (0%, 10%, 30%, 50%, and 100% SO) at the air/water surface of the Langmuir trough over phosphate buffered saline (pH 7.4) subphase. Surface pressure (π)-area (A) isotherms and Brewster angle microscopy observations showed nonideal interactions where SO aggregates with MGS and complements the NPL stratum of the meibomian layers. The analysis of stress relaxation transients with Kohlrausch–Williams–Watts equation revealed that the supplementation of fixed amount of MGS with excess lipids via SO altered the dilatational elasticity of the films as reflected by the increase of the exponent β. Thus, SO with its unique combination of high oxidative stability and abundance of long polyunsaturated acyl chains might be a useful supplement to MGS layers.

Aqueous secondary organic aerosol formation from the direct photosensitized oxidation of vanillin in the absence and presence of ammonium nitrate

Vanillin (VL), a phenolic aromatic carbonyl abundant in biomass burning emissions, forms triplet excited states (3VL∗) under simulated sunlight leading to aqueous secondary organic aerosol (aqSOA) formation. Nitrate and ammonium are among the main components of biomass burning aerosols and cloud or fog water. Under atmospherically relevant cloud and fog conditions, solutions composed of either VL only or VL with ammonium nitrate were subjected to simulated sunlight irradiation to compare aqSOA formation via the direct photosensitized oxidation of VL in the absence and presence of ammonium nitrate. The reactions were characterized by examining the VL decay kinetics, product compositions, and light absorbance changes. Both conditions generated oligomers, functionalized monomers, and oxygenated ring-opening products, and ammonium nitrate promoted functionalization and nitration, likely due to its photolysis products (⚫OH, ⚫NO2, and NO2- or HONO). Moreover, a potential imidazole derivative observed in the presence of ammonium nitrate suggested that ammonium participated in the reactions. The majority of the most abundant products from both conditions were potential brown carbon (BrC) chromophores. The effects of oxygen (O2), pH, and reactants concentration and molar ratios on the reactions were also explored. Our findings show that O2 plays an essential role in the reactions, and oligomer formation was enhanced at pH <4. Also, functionalization was dominant at low VL concentrations, whereas oligomerization was favored at high VL concentrations. Furthermore, oligomers and hydroxylated products were detected from the oxidation of guaiacol (a non-carbonyl phenol) via VL photosensitized reactions. Last, potential aqSOA formation pathways via the direct photosensitized oxidation of VL in the absence and presence of ammonium nitrate were proposed. This study indicates that the direct photosensitized oxidation of VL may be an important aqSOA source in areas influenced by biomass burning and underscores the importance of nitrate in the aqueous-phase processing of aromatic carbonyls.

DIACEREIN-LOADED NIOSOMES (DC-NS): A NEW TECHNIQUE TO SUSTAIN THE RELEASE OF DRUG ACTION

Objective: The study's main goal is to develop a suitable niosomes (NS) encapsulated drug for anti-inflammatory effects such as diacerein (DC) and to evaluate the system's vesicle size (VS), entrapment efficiency (EE %), physical stability and in vitro release. Methods: Tween (40 and 60), cholesterol, and stearylamine were used in a 1:1:0.1 molar ratios as non-ionic surfactants. Thin film hydration was used to create the NS. Results: The higher EE% was observed with NS (F11) prepared from tween 60, cholesterol and 2.5 min sonication. These formulations' release patterns were Higuchi diffusion and first order. For the stability study, NS formulations were stored at temperature between 2-8 °C for 60 d retains the most drugs when compared to room and high temperature conditions. Conclusion: The findings of this study have conclusively shown that after NS encapsulation of DC, drug release is prolonged at a constant and controlled rate.

Fabrication of Fe-doped ZnO/Nanocellulose Nanocomposite as an Efficient Photocatalyst for Degradation of Methylene Blue Under Visible Light

In this work, a photocatalytic nanocomposite, Fe-doped ZnO/nanocellulose, was synthesized using an in-situ method and examined for methylene blue (MB) degradation. For this purpose, pure ZnO (PZ) was synthesized by the chemical precipitation method and then subjected to Fe+3 doping with different concentrations of Fe3+ (1, 3, and 5 mol%). The PZ and Fe-doped ZnO (FZ) samples were characterized using several standard analyses. UV-vis DRS analysis was also used to investigate the effect of Fe3+ doping on the bandgap of PZ. The doping of Fe3+ enhanced the photocatalytic activity of ZnO under visible light. The degradation efficiency of FZ samples (> 50%) was enhanced compared to the pristine ZnO (36.91%) during the same period. The catalyst with the highest degradation efficiency (94.21%) was then conjugated with broom corn stalk-derived nanocellulose (NC) at varying NC/ Zn2+ molar ratios (0.1, 0.2, 0.3, and 0.4) and characterized by various analyses. The NC enhanced the hydroxyl group at the surface of the nanocomposite, consequently improved the photocatalytic performance of the synthesized samples. The ability of the optimized photocatalyst for MB degradation was assessed. The effect of operating parameters such as pH, catalyst dosage, and initial MB concentration was investigated and degradation efficiency of 98.84% was achieved at the optimum condition. Besides, photocatalyst regeneration study indicated the great photocatalytic performance of this nanocomposite with no loss in its degradation efficiency. The facile synthesis and fast degradation rate of this nanocomposite make it a promising candidate for real-world wastewater treatment.