gli Fan

Biosorption of uranium by chemically modified Rhodotorula glutinis

The present paper reports the biosorption of uranium onto chemically modified yeast cells, Rhodotorula glutinis, in order to study the role played by various functional groups in the cell wall. Esterification of the carboxyl groups and methylation of the amino groups present in the cells were carried out by methanol and formaldehyde treatment, respectively. The uranium sorption capacity increased 31% for the methanol-treated biomass and 11% for the formaldehyde-treated biomass at an initial uranium concentration of 140 mg/L. The enhancement of uranium sorption capacity was investigated by Fourier transform infrared (FTIR) spectroscopy analysis, with amino and carboxyl groups were determined to be the important functional groups involved in uranium binding. The biosorption isotherms of uranium onto the raw and chemically modified biomass were also investigated with varying uranium concentrations. Langmuir and Freundlich models were well able to explain the sorption equilibrium data with satisfactory correlation coefficients higher than 0.9.

Synthesis and detection of a seaborgium carbonyl complex

A carbonyl compound that tips the scales Life is short for the heaviest elements. They emerge from high-energy nuclear collisions with scant time for detection before they break up into lighter atoms. Even et al. report that even a few seconds is long enough for carbon to bond to the 106th element, seaborgium (see the Perspective by Loveland). The authors used a custom apparatus to direct the freshly made atoms out of the hot collision environment and through a stream of carbon monoxide and helium. They compared the detected products with theoretical modeling results and conclude that hexacarbonyl Sg(CO)6 was the most likely structural formula. Science, this issue p. 1491; see also p. 1451 A special apparatus enables synthesis of a compound with carbon bonds to a short-lived element produced via nuclear reaction. [Also see Perspective by Loveland] Experimental investigations of transactinoide elements provide benchmark results for chemical theory and probe the predictive power of trends in the periodic table. So far, in gas-phase chemical reactions, simple inorganic compounds with the transactinoide in its highest oxidation state have been synthesized. Single-atom production rates, short half-lives, and harsh experimental conditions limited the number of experimentally accessible compounds. We applied a gas-phase carbonylation technique previously tested on short-lived molybdenum (Mo) and tungsten (W) isotopes to the preparation of a carbonyl complex of seaborgium, the 106th element. The volatile seaborgium complex showed the same volatility and reactivity with a silicon dioxide surface as those of the hexacarbonyl complexes of the lighter homologs Mo and W. Comparison of the product’s adsorption enthalpy with theoretical predictions and data for the lighter congeners supported a Sg(CO)6 formulation.

Biosorption of uranium by magnetically modified Rhodotorula glutinis.

Adsorption of uranium from aqueous solution onto the magnetically modified yeast cell, Rhodotorula glutinis, was investigated in a batch system. Factors influencing sorption such as initial solution pH, biomass dosage, contact time, temperature, initial uranium concentration and other common cations were analyzed. Sorption isotherm, kinetic and thermodynamic studies of uranium on magnetically modified R. glutinis were also carried out. The temperature dependent equilibrium data agreed well with the Langmuir model. Kinetic data obtained at different temperatures were simulated using pseudo-first-order and pseudo-second-order kinetic models, the pseudo-second-order kinetic model was found to describe the data better with correlation coefficients near 1.0. The thermodynamic parameters, ΔH°, ΔS° and ΔG° were calculated from the sorption data gained at different temperatures. These thermodynamic parameters showed that the sorption process was endothermic and spontaneous. All results indicated that magnetically modified R. glutinis can be a potential sorbent for uranium wastewater treatment.

Equilibrium, kinetic and thermodynamic studies of uranium biosorption by calcium alginate beads.

Calcium alginate beads are potential biosorbent for radionuclides removal as they contain carboxyl groups. However, until now limited information is available concerning the uptake behavior of uranium by this polymer gel, especially when sorption equilibrium, kinetics and thermodynamics are concerned. In present work, batch experiments were carried out to study the equilibrium, kinetics and thermodynamics of uranium sorption by calcium alginate beads. The effects of initial solution pH, sorbent amount, initial uranium concentration and temperature on uranium sorption were also investigated. The determined optimal conditions were: initial solution pH of 3.0, added sorbent amount of 40 mg, and uranium sorption capacity increased with increasing initial uranium concentration and temperature. Equilibrium data obtained under different temperatures were fitted better with Langmuir model than Freundlich model, uranium sorption was dominated by a monolayer way. The kinetic data can be well depicted by the pseudo-second-order kinetic model. The activation energy derived from Arrhenius equation was 30.0 kJ/mol and the sorption process had a chemical nature. Thermodynamic constants such as ΔH(0), ΔS(0) and ΔG(0) were also evaluated, results of thermodynamic study showed that the sorption process was endothermic and spontaneous.

On-line gas chromatographic studies of Rf, Zr, and Hf bromides

The Heavy Element Volatility Instrument (HEVI), an on-line isothermal gas chromatography system, has been used to separate the volatile bromide compounds of the group 4 elements Zr and Hf and the transactinide Rf according to their volatilities, and to provide data on the gas phase chemical properties of very short-lived isotopes in amounts as low as a few atoms. For these studies Rf was produced via the Cm(O, 5n) reaction.Hf was produced via the reactionEu(F, xn), andZr was produced via the Cu(Si, 3p3n) reaction. The half-life forRf was measured to be 7567 seconds. A Monte Carlo code was used to deduce the enthalpy of adsorption ( ∆Ha) from the observed volatility and parameters of the chromatography system. The resulting adsorption enthalpies for the Zr, Hf, and Rf tetrabromides are: 210865 kJ · mol , 211365 kJ · mol 21 and 28767 kJ · mol, respectively. Volatilities of the group 4 bromides support the conclusion from previous results for the group 4 chlorides that Rf deviates from the trend expected by simple extrapolation of the properties of its lighter homologs in the periodic table. The group 4 bromides are also observed to be less volatile than their respective chlorides, as predicted by relativistic calculations.

Extraction Behavior of Mo(VI) and W(VI) as Homologs of Sg with α‐Benzoinoxime

Solvent extraction of molybdenum and tungsten as homologues of Sg with α‐benzoinoxime from HCl solutions has been investigated. The extraction equilibration was achieved at 20s for Mo and W. Molybdenum was almost quantitatively extracted from 0.001 to 4 M HCl solutions, and the extraction yields decreased at higher and lower acid concentrations due to the formation of anionic oxychloride complex and anionic species MO4 2−, respectively. The extraction yield of W was lower than that of Mo during the whole range of acid concentration. The composition of the extracted species was determined by using the slope method in present experiment. The elemental analysis, IR and 1H NMR spectra of the extracted species suggest that the extracted complex contain one MoO2 2+ or WO2 2+ groups bonded with two α‐benzoinoxime molecules.

Gas-phase chemistry of Mo, Ru, W, and Os metal carbonyl complexes

Abstract Metal carbonyl complexes were used for studying the gas-phase chemical behavior of Mo, Ru, W and Os isotopes with an on-line low temperature isothermal gas chromatography apparatus. Short-lived Mo and Ru isotopes were produced by a 252Cf spontaneous fission source. Short-lived nuclides of W and Os were produced using the heavy ion reactions 19F +159Tb and 165Ho, respectively. Short-lived products were thermalized in a recoil chamber filled with a gas mixture of helium and carbon monoxide. The carbonyls formed were then transported through capillaries to an isothermal chromatography column for study of the adsorption behavior as a function of temperature. On-line isothermal chromatography (IC) experiments on Teflon (PTFE) and quartz surfaces showed that short-lived isotopes of the listed elements can form carbonyl complexes which are very volatile and interact most likely in physical sorption processes. Deduced adsorption enthalpies of Mo and Ru carbonyls were − 38 ± 2 kJ/mol and − 36 ± 2 kJ/mol, respectively. These values are in good agreement with literature data, partly obtained with different chromatographic techniques. A validation of the applied Monte Carlo model to deduce adsorption enthalpies with Mo isotopes of different half-lives proved the validity of the underlying adsorption model. The investigations using a gas-jet system coupled to a heavy ion accelerator without any preseparator clearly showed the limitations of the approach. The He and CO gas mixture, which was directly added into the chamber, will result in decomposition of CO gas and produce some aerosol particles. After the experiment of 173W and 179Os in the heavy ion experiments, the Teflon column was covered by a yellowish deposit; the adsorption enthalpy of W and Os carbonyls could therefore not be properly deduced using Monte Carlo simulations.

Uranium sorption from saline lake brine by amidoximated silica

A series of silica sorbents with different content of amidoxime groups were prepared through co-condensation method and applied to extract uranium from saline lake brine. The optimum amidoxime group content was determined and effects of pH on uranium sorption were investigated. Sorption kinetic and isotherms were also investigated. XPS analysis indicated that the adsorption mechanism of uranium was attributed to the interaction between uranyl ion and N in the amidoxime. Amidoximated silica could efficiently absorb the naturally occurring uranium in the saline lake brine samples from Qinghai, China.

Extraction behavior of short-lived isotopes of Mo/W using α-benzoinoxime: A model system for the study of seaborgium

Abstract The liquid-liquid extraction behavior of short-lived molybdenum and tungsten isotopes from HCl and HNO3 as well as HF/HNO3 acid media was studied using the α-benzoinoxime/chloroform system. The goal of the present experiments was to find an extraction system with a high selectivity for the group 6 elements in the periodic table which is suitable for the study the solution chemistry of seaborgium (Z=106). It was found that Mo and W are both effectively extracted using α-benzoinoxime as an extractant and the maximum extraction yield is 100% and 94% for Mo and W, respectively. Ions of MO22+ (M=Mo, W) exist in HCl between the concentration range of 0.1−3 M and can be extracted quantitatively into the organic phase. The decrease of extraction yields at lower or higher acid concentration is due to the formation of anionic species MO42- or MO2Cl3-. The extraction behavior of Mo and W in HNO3 solution is similar to that in HCl solution. In HNO3/HF mixed acid solutions, due to the formation of MO2F3- a decrease of extraction yield at higher HF concentration, similar to the case of HCl is observed. The extraction equilibrium is reached within 10−30 s, which means the extraction kinetics of α-benzoinoxime/chloroform extraction system is fast enough for the study of the isotope 265Sg. The extraction behavior of molybdenum and tungsten shows a distinct difference in the range of 0.05 to 0.2 M HF with 1 M HNO3. This shows that differences in the complexation with fluoride ion exist in Mo and W. This study focuses on the investigation of the tendency of group 6 element for complexation with fluoride ion.

Synthesis and chemical investigation of Sg(CO)

J. Even†1, A. Yakushev 2, Ch.E. D̈ullmann1,2,3, H. Haba4, M. Asai5, T.K. Sato5, H. Brand2, A. Di Nitto3, R. Eichler6,7, F.L. Fan8, W. Hartmann2, M. Huang4, E. J̈ager2, D. Kaji4, J. Kanaya4, Y. Kaneya5, J. Khuyagbaatar 1, B. Kindler2, J.V. Kratz3, J. Krier2, Y. Kudou4, N. Kurz2, B. Lommel 2, S. Miyashita5,9, K. Morimoto4, K. Morita4,10, M. Murakami 4,11, Y. Nagame 5, H. Nitsche12,13, K. Ooe11, Z. Qin8, M. Scḧadel5, J. Steiner 2, T. Sumita4, M. Takeyama 4, K. Tanaka4, A. Toyoshima 5, K. Tsukada5, A. Türler6,7, I. Usoltsev6,7, Y. Wakabayashi 4, Y. Wang8, N. Wiehl 1,3, and S. Yamaki 4,14