Adsorption of REEs from Aqueous Solution by EDTA-Chitosan Modified with Zeolite Imidazole Framework (ZIF-8).

Chitosan (CS) modified with ethylenediamine tetraacetic acid (EDTA) was further modified with the zeolite imidazole framework (ZIF-8) by in situ growth method and was employed as adsorbent for the removal of rare-earth elements (REEs). The material (EDTA-CS@ZIF-8) and ZIF-8 and CS were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscope (SEM), and nitrogen adsorption/desorption experiments (N2- Brunauer-Emmet-Teller (BET)). The effects of adsorbent dosage, temperature, the pH of the aqueous solution, contact time on the adsorption of REEs (La(III), Eu(III), and Yb(III)) by EDTA-CS@ZIF-8 were studied. Typical adsorption isotherms (Langmuir, Freundlich, and Dubinin-Radushkevich (D-R)) were determined for the adsorption process, and the maximal adsorption capacity was estimated as 256.4 mg g-1 for La(III), 270.3 mg g-1 for Eu(III), and 294.1 mg g-1 for Yb(III). The adsorption kinetics results were consistent with the pseudo-second-order equation, indicating that the adsorption process was mainly chemical adsorption. The influence of competing ions on REE adsorption was also investigated. After multiple cycles of adsorption/desorption behavior, EDTA-CS@ZIF-8 still maintained high adsorption capacity for REEs. As a result, EDTA-CS@ZIF-8 possessed good adsorption properties such as stability and reusability, which have potential application in wastewater treatment.

Adsorption of Chromium (III) and Chromium (VI) Ions from Aqueous Solution Using Chitosan-Clay Composite Materials.

In this work, biopolymer chitosan and natural clay were used to obtain composite materials. The overall aim of this study was to improve the properties (porosity, thermal stability and density) of pure chitosan beads by the addition of clay and to obtain a chitosan-based composite material for the adsorption of heavy metals from an aqueous solution, using Mongolian resources, and to study the adsorption mechanism. The natural clay was pre-treated with acid and heat to remove the impurities. The chitosan and pre-treated clay were mixed in different ratios (8:1, 8:2 and 8:3) for chemical processing to obtain a composite bead for the adsorption of chromium ions. The adsorption of Cr(III) and Cr(VI) was studied as a function of the solution pH, time, temperature, initial concentration of the chromium solution and mass of the composite bead. It was found that the composite bead obtained from the mixture of chitosan and treated clay with a mass ratio of 8:1 and 8:2 had the highest adsorption capacity (23.5 and 17.31 mg·g-1) for Cr(III) and Cr(VI), respectively, in the optimum conditions. The properties of the composite materials, prepared by mixing chitosan and clay with a ratio of 8:1 and 8:2, were investigated using XRD, SEM-EDS, BET and TG analysis. The adsorption mechanism was discussed based on the XPS analysis results. It was confirmed that the chromium ions were adsorbed in their original form, such as Cr(III) and Cr(VI), without undergoing oxidation or reduction reactions. Furthermore, Cr(III) and Cr(VI) were associated with the hydroxyl and amino groups of the composite beads during adsorption. The kinetic, thermodynamic and isothermal analysis of the adsorption process revealed that the interaction between the chitosan/clay composite bead and Cr(III) and Cr(VI) ions can be considered as a second-order endothermic reaction, as such the adsorption can be assessed using the Langmuir isotherm model. It was concluded that the composite bead could be used as an adsorbent for the removal of chromium ions.

Contribution Factors of the First Kind Calculated for the Marcus Electron-Transfer Rate and Their Applications.

In this study, we applied the concept of the "contribution factor of the first kind (CFFK)" to the original electron-transfer (ET) rate theory proposed by Marcus. Mathematical derivations provided simple and convenient formulas for estimating the relative contributions of ten physical and chemical parameters involved in the Marcus ET rate formula: (1) the maximum strength of the electronic coupling energy between two molecules, (2) the exponential decay rate of the electronic coupling energy versus the distance between both molecules, (3) the distance between both molecules, (4) the equilibrium distance between both molecules, (5) the Gibbs free energy, (6) reorganization free energy in the prefactor of the Marcus ET rate equation, (7) reorganization free energy in the denominator of the exponential term, (8) reorganization free energy in the argument of the exponential term, (9) Boltzmann constant times absolute temperature in the prefactor of the rate equation, and (10) Boltzmann constant times absolute temperature in the denominator of the exponential term. We applied our theories to (i) ET reactions at bacterial photosynthesis reaction centers, PSI and PSII, and soluble ferredoxins (Fd); (ii) intraprotein ET reactions for designed azurin mutants; and (iii) ET reactions in flavodoxin (Fld). The formulas and calculations suggest that the theory behind the CFFK is useful for quantitatively identifying major and minor physical and chemical factors and corresponding trade-offs, all of which affect the magnitude of the Marcus ET rate.

Enhanced uranium separation by charge enabling γ-MnO2 with oxygen vacancies.

Numerous efforts have been devoted to understanding the electron transfer process of uranium (UO22+) on adsorbent materials, whereas the potential oxygen vacancies (OVs) in metal oxides have long been overlooked. Once these interactions are taken into account, the emerging molecular orbital effects undoubtedly affect the adsorption process. Here, we synthesized CC/γ-MnO2 by growing MnO2 on carbon cloth (CC), followed by the creation of oxygen vacancies (OVs) through electrochemical methods to form CC/γ-MnO2-OVs. The CC/γ-MnO2-OVs shows significantly enhanced selectivity and durability for UO22+, with the maximum adsorption capacity increasing from 456.8 to 1648.1 mg/g (by a factor of 3.6). Theoretical calculations suggest that the generation of OVs leads to an increase in charge transfer and a decrease in adsorption energy between UO22+ and CC/γ-MnO2, due to the interaction between Mn 3d orbital in CC/γ-MnO2 and O 2p orbital in UO22+. The OVs in CC/γ-MnO2 provide a spatial structure for anchoring the OU=O moiety of UO22+, while the surface van der Waals forces and the formation of chemical bonds between Mn-U contribute to charge interactions. This synergistic effect allows CC/γ-MnO2-OVs to exhibit favorable selectivity, a large adsorption capacity, and rapid adsorption kinetics towards uranyl ions. This work achieves enhanced UO22+ separation by introducing OVs in CC/γ-MnO2 through a facile electrochemical strategy, highlighting the great potential for nuclear waste processing.

Behavior and distribution of heavy metals including rare Earth elements, thorium, and uranium in sludge from industry water treatment plant and recovery method of metals by biosurfactants application.

In order to investigate the behavior, distribution, and characteristics of heavy metals including rare earth elements (REEs), thorium (Th), and uranium (U) in sludge, the total and fractional concentrations of these elements in sludge collected from an industry water treatment plant were determined and compared with those in natural soil. In addition, the removal/recovery process of heavy metals (Pb, Cr, and Ni) from the polluted sludge was studied with biosurfactant (saponin and sophorolipid) elution by batch and column experiments to evaluate the efficiency of biosurfactant for the removal of heavy metals. Consequently, the following matters have been largely clarified. (1) Heavy metallic elements in sludge have generally larger concentrations and exist as more unstable fraction than those in natural soil. (2) Nonionic saponin including carboxyl group is more efficient than sophorolipid for the removal of heavy metals in polluted sludge. Saponin has selectivity for the mobilization of heavy metals and mainly reacts with heavy metals in F3 (the fraction bound to carbonates) and F5 (the fraction bound to Fe-Mn oxides). (3) The recovery efficiency of heavy metals (Pb, Ni, and Cr) reached about 90-100% using a precipitation method with alkaline solution.

Adsorption of an Anionic Surfactant (Sodium Dodecyl Sulfate) from an Aqueous Solution by Modified Cellulose with Quaternary Ammonium.

In this study, a method of removing an anionic surfactant sodium dodecyl sulfate (SDS) from an aqueous solution by cellulose modified with quaternary ammonium cation was discussed. Cellulose, as the adsorbent, was obtained from medical cotton balls, and the quaternary ammonium cation (synthesized from dodecyl dimethyl tertiary amine and epichlorohydrin) was grafted onto the sixth hydroxyl group of D-glucose in the cellulose by the Williamson reaction under alkaline conditions. The modified cellulose was characterized by Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS); and the zeta potential of the material was also measured after confirmation of the synthesis of quaternary ammonium salts by nuclear magnetic resonance (NMR). From these analyses, a peak of the quaternary ammonium group was observed at 1637 cm-1; and it was found that the surface of the material exhibited a positive charge in pH 2-7. The optimal conditions for SDS adsorption by modified cellulose were pH of 7, contact time of 3 h, and temperature of 60 °C in this study. Typical adsorption isotherms (Langmuir and Freundlich) were determined for the adsorption process, and the maximal adsorption capacity was estimated as 32.5 mg g-1. The results of adsorption kinetics were more consistent with the pseudo-second-order equation, indicating that the adsorption process was mainly controlled by chemical adsorption. Furthermore, thermodynamic analysis indicated that the adsorption process of SDS on the modified cellulose was endothermic and spontaneous and that an increasing temperature was conducive to adsorption.

Preparation and Characterization of Low-Cost Ceramic Membrane Coated with Chitosan: Application to the Ultrafine Filtration of Cr(VI).

In this work, low-cost ceramic membranes (CMs) were prepared from ultrafine starting powders such as kaolin, clay, and starch by a dry compaction method. The ceramic membranes were sintered at different temperatures and times and were characterized by XRD, XRF, TG-DTA, SEM-EDS, N2-BET, water absorption, compressive strength, and pure water flux. The optimal membrane, sintered at 1000 °C for 3 h, possessed water absorption of 27.27%, a compressive strength of 31.05 MPa, and pure water flux of 20.74 L/h m2. Furthermore, chitosan crosslinked with glutaraldehyde was coated on the surface of the ceramic membrane by the dip coating method, and the pore size of the chitosan-coated ceramic membrane (CCCM) was 16.24 nm. Eventually, the separation performance of this membrane was assessed for the removal of chromium(VI) from aqueous solution. The ultrafine filtration of Cr(VI) was studied in the pH range of 2-7. The maximum removal of Cr(VI) was observed to be 71.25% with a pH of 3. The prepared CCCM showed good membrane properties such as mechanical stability and ultrafine structure, which have important applications for the treatment of wastewater including such heavy metals.

Biosorption of Lanthanides from Aqueous Solutions Using Pretreated Buccinum tenuissimum Shell Biomass.

Biosorption experiment from aqueous solutions containing known amount of rare earth elements (REEs) using pre-treated Buccinum tenuissimum shell was explored to evaluate the efficiency of shell biomass as sorbent for REEs. In this work, four kinds of sieved shell samples: (a) "Ground original sample", (b) "Heat-treatment (480°C, 6 hours) sample", (c) "Heat-treatment (950°C, 6 hours) sample" and (d) "Heat-treatment (950°C, 6 hours) and water added sample" were used. Furthermore, to confirm the characteristics of the shell biomass, the crystal structure, the surface morphology, and the specific surface area of these shell samples were determined. Consequently, the following matters have been mainly clarified. (1) The crystal structure of the shell biomass was transformed from aragonite (CaCO(3)) into calcite (CaCO(3)) phase by heat-treatment (480°C, 6 hours); then mainly transformed into calcium oxide (CaO) by heat-treatment (950°C, 6 hours), and calcium hydroxide (Ca(OH)(2)) by heat-treatment (950°C, 6 hours) and adding water. (2) The shell biomass showed excellent sorption capacity for lanthanides. (3) Adsorption isotherms using the shell biomass can be described by Langmuir and Freundlich isotherms satisfactorily for lanthanides except "heat-treatment (950°C, 6 hours) sample". (4) Shell biomass (usually treated as waste material) can be an efficient sorbent for lanthanides in future.

Experimental and Theoretical Studies on the Adsorption Mechanisms of Uranium (VI) Ions on Chitosan.

An experiment on the adsorption of uranium (VI) by chitosan was conducted to investigate the efficiency of chitosan as an adsorbent for U(VI). The adsorption potential of U(VI) by chitosan was investigated with ICP-MS by varying the experimental conditions such as the pH in order to obtain the optimum conditions. Adsorption dependence on the pH was confirmed, and the highest uptake of U(VI) was observed at pH 5. In addition, to scrutinize the experimental results, quantum chemistry calculations were performed. The results, taking into account the experimental conditions, show that the adsorption efficiency increases as the total charge of the adsorbent and adsorbate species decreases if both of them are positively charged. It was also found that a slight change in the adsorption geometric configuration controls the adsorption efficiency.

Experimental and Theoretical Studies on the Adsorption and Desorption Mechanisms of Chromate Ions on Cross-Linked Chitosan.

In this work, chitosan bead materials were modified by cross-linking with epichlorohydrin (EP) and glutaraldehyde (GA) for the removal of heavy metals in wastewater. Using these cross-linked chitosan materials, the dependence of adsorption of chromate anions on pH was investigated experimentally and theoretically. The experimental results show that the adsorption process of the chromate (Cr) ions greatly depends on the pH of the solution, with the chitosan modified by cross-linking being an efficient adsorbent for chromate. On the other hand, quantum chemistry calculations were conducted to find out the factor determining the pH dependence of the adsorption efficiency of chromate ions on the dimer chitosan molecule, and show results similar to those found in the experiment. Both the experimental and numerical results show that the total charge numbers of the adsorbent and the adsorbate species and their relative molecular geometries are crucial in determining the adsorption efficiency.

Stable Isotope Analysis of Hydrogen and Oxygen in a Traditional Japanese Alcoholic Beverage, Sake, from Niigata Prefecture in Japan and Other Countries.

Stable hydrogen and oxygen isotopic compositions (δD and δ18O values, respectively) were analyzed for "sake," a traditional Japanese alcohol beverage, to assess these values for the identification of its geographic origin. We collected sake (Junmai-shu; made of only rice, water, and koji) and its source water (i.e., brewing water) from breweries in Niigata Prefecture, Japan, and measured the isotopic compositions of water in these samples. The δD and δ18O values for the sake are well correlated with their respective values for the corresponding brewing water (δD; r = 0.92, δ18O; r = 0.80). Furthermore, based on the δD-δ18O cross plot, sake brewed in Niigata Prefecture is distinguishable from that brewed in countries other than Japan. These results imply that this dual isotope (δD and δ18O) analysis is potentially useful in identifying the geographic origin of sake.

Intravascular ultrasound-guided percutaneous coronary intervention for total occlusion of the proximal left anterior descending artery caused by spontaneous coronary dissection in a young woman.

A 35-year-old woman was admitted to our hospital because of a sudden cardiac arrest caused by an acute anterior myocardial infarction. Emergency coronary angiography showed total occlusion of the proximal left anterior descending artery (LAD). We performed an intravascular ultrasound (IVUS) to detect the LAD orifice and successfully inserted the guidewire to the occluded LAD. An IVUS revealed coronary dissection and no atheromatous plaque from the orifice to the mid-portion of the LAD and the guidewire was in the true lumen. Two bare metal stents were implanted in the proximal and mid portion of the LAD. After stenting to the LAD, coronary dissection retrogradely extended to the left circumflex artery (LCx). Therefore, we performed additional stent implantation from the left main trunk (LMT) to the proximal LCx and the just proximal LAD. An IVUS guided percutaneous coronary intervention (PCI) enabled complete revascularization to spontaneous coronary artery dissection.

Biosorption of uranium and rare Earth elements using biomass of algae.

In order to investigate the behavior of rare earth elements (REEs) and uranium (U) in marine organism, the concentrations of REEs and U in some brown algae samples taken on the coast of Niigata Prefecture were determined. In addition, laboratory model experiment to uptake these elements using living and dried algae (Undaria pinnatifida and Sargassum hemiphyllum) was also carried out to survey the uptake and bioaccumulation mechanism of REEs and U in algae. Consequently, the following matters have been mainly clarified. (1) The order of the concentration of REEs for each organ in Sargassum hemiphyllum is "main branch" > "leaf" > "vesicle," however for U, the order is "leaf" > "vesicle" > "main branch." (2) The concentration of REEs in Sargassum hemiphyllum may be strongly affected by suspended solid in seawater. (3) The uptake and/or accumulate mechanism of REEs in brown algae may be different from that of U.