Modern state of underground storage of liquid radioactive waste

Underground storage of liquid radioactive waste (LRW) has been successfully carried out in Russia over the past 40 years. Stages of development of the technology, its realization and chemical transformations of LRW components are considered and discussed, as well as the modern approach to underground storage. Control of the state of waste products and migration radionuclides and toxic compounds remains the key issue of providing safety of LRW storage. Radiation thermal and biochemical transformations of components of waste form new chemical compounds and, first of all, gases. The formation of gases is one of the important factors determining the safety of underground LRW storage.     

Biosorption of some ions on different bacterial species from aqueous and radioactive waste solutions

The uptake of metal ions, cerium, Ce(III); cobalt, Co(II); thorium, Th(IV); and uranium U(VI) by Bacillus pumilus-LRW1, Bacillus cereus-LRW2 and Micrococcus lylae-LRW3 from aqueous solution was examined as a function of metal ion concentration, pH, temperature, and the presence of some foreign ions. The bacterial species exhibited high affinity to accumulate metal ions from their solutions at pH 4–5.0±0.5. The amount of each ion (in mg) accumulated by one gram dry weight of each bacteria was calculated. The uptake by the Bacillus cereus-LRW2 from aqueous solutions and simulated radioactive wastes were also investigated. Electron microscopic investigations showed that the ions were accumulated around the cell wall.     

Removal of cobalt from liquid radioactive waste by in situ electrochemical synthesis of ferrite

This study combined electrochemical synthesis with traditional ferrite method to remove Co²⁺ from simulated liquid radioactive waste (LRW). The experiment investigated the effects of various reaction conditions including current density, reaction time for electrosynthesis, reaction temperature, initial pH value and boric acid concentration as well as the type of power supply by measuring the concentration of Co²⁺ in the effluent, explored the reaction mechanism by measuring particles using XRD. The results showed that it was feasible to remove Co²⁺ from simulated LRW by electrochemical synthesis of ferrite. The best removal efficiency of 99.99% (the concentration of Co²⁺ in the effluent was 0.447 μg/L) was achieved under the optimal reaction conditions, the sediment was mainly composed of the mixture of CoFe₂O₄ and Fe₃O₄.     

Radioactive contamination of groundwater at the Andreeva Bay Shore Technical Base,Northwest Russia

The Andreeva Bay Shore Technical Base is one of the largest, most contaminated nuclear legacy sites in Northwest Russia. Radioactive contamination at the site stems from servicing and maintenance activites for Russian Northern Fleet nuclear submarine. Studies of groundwater contamination have been conducted using measurements taken at different boreholes around the site. Results indicate that groundwater contamination has occurred in some areas of the Andreeva Bay facility. These areas are primarily located near Building 5 where accidental releases occurred in 1982 during storage of spent nuclear fuel (SNF) and near the liquid and solid radioactive waste (LRW and SRW) storage facilities which have been infiltrated by precipitation waters.     

An alternative view on the kinetics of optical stimulated luminescence decay

In this work, it was made similitude between radioactive decay and luminescence decay. An alternative approach related with the radioactive decay law of successive disintegrations from a composite radioactive material to describe the optical stimulated luminescence (OSL) decay curve was introduced. The modified radioactive decay law was applied to find the individual components of the different synthetic and experimental OSL decay curves. The suggested relation was named as “Active-OSL Approximation”. This work offers an alternative view on the kinetics of OSL decay.     

Determination of rare earth elements and heavy metals in river water by preconcentration on chelex 100 and neutron activation

The neutron activation determination of rare earth elements and heavy metals in river water has been studied with Chelex 100 resin as a preconcentration agent. The resin is applied directly as a support for irradiation and for radiochemical separation. The radioactive rare earth elements are recovered selectively and quantitatively from the irradiated resin by elution with hot 1 M sodium carbonate solution; radioactive heavy metals are recovered with 2 M nitric acid. Activities from each eluate are counted with a Ge(Li) detector connected to a multichannel analyzer; La, Sm, Eu, Dy, Mn, Cu and Zn can be determined. The recoveries were almost quantitative and the measurement of chemical yield was unnecessary.     

Application of Br-82 as a radioactive tracer isotope to study bromide ion-isotopic exchange reaction in strongly basic anion exchange resin Duolite A-161

In the present investigation Br-82 radioactive isotope was used as a tracer to study the kinetics of exchange reaction taking place between the ion exchange resin and the external bromide ion solution. In an attempt to study the reversible bromide ion-isotopic exchange reaction kinetics, it was expected that whether the initial step was the exchange of radioactive bromide ions from the solution on to the ion exchange resin (forward reaction), or from the ion exchange resin in to the solution (reverse reaction), the two ion-isotopic exchange reactions should occur simultaneously, which was further confirmed from the values of specific reaction rate 0.122 and 0.123 min⁻¹ respectively obtained under identical experimental conditions. The radioactive tracer technique employed in the present investigation will be useful for characterization of various industrial grade ion exchange resins.     

Mathematical study to improve the sensitivity in the neutron activation analysis of fluorspar

A mathematical method to design a neutron activation procedure for analyzing a sample of fluorspar from a concentration plant has been created. The neutron activation is used to bombard a sample with neutrons and record the spectrum radioactive produced. The fluorspar grade is directly proportional to the fluorine content of the sample, and this in turn is directly proportional to the amount of 16N, the radioactive product produced in the bombardment. The ratio between both concentrations has been shown but the aim is to determine the activation parameters that increase the sensitivity of the method. This work discusses the mathematical models used and whose use is expected to increase the sensitivity of the reading.     

Preparation of radioactive enantiomers of amino acids using labelled racemates only

It is shown from experiments on leucine, that is possible to obtain pure enantiomer tracers of amino acids by using radioactive racemates only. The resolution takes place in a single crystallization step after mixing the active racemate with the inactive enantiomer, due to an absolute stereoselection.     

Structural information from the interference effect of electron-capture X-rays

We observed the interference effect of electron-capture X-rays emitted by the nuclear transformations in radioisotopes. This interference is between the direct monochromatic emission from the radioactive atoms and the emission totally reflected by the substrate surface. Nanometer-level structural information about the radioactive atoms can be obtained by analyzing the measured interference fringes because the period of these fringes depends on the position of the radioactive atoms relative to the substrate surface. In this work, we used the functional protein molecules (myosin subfragment 1 (S1)) which were radioiodinated with no carrier added¹²⁵I to observe the conformational changes in aqueous solutions.     

Waste cigarette filters: activated carbon as a novel sorbent for uranium removal

Uranium is important in the nuclear fuel cycle as both as an energy source and as radioactive waste. Herein, activated carbon (AC) prepared from waste cigarette filters by convenient carbonization and functionalization was chosen as the raw materials for radionuclides adsorption. Batch adsorption experiments showed that AC presented comparable UO₂²⁺ adsorption capacity (106 mg g^?1) and very outstanding selectivity. The adsorption process accorded with Langmuir model and the pseudo-second-order kinetics model well. This work combines the waste cigarette filters with the radioactive nuclear treatment materials, which may provide a new strategy for the future treatment of waste cigarette butts.

     

Tracer study of a chemical separation procedure for the determination of impurities in selenium by means of thermal neutron activation analysis

A chemical separation procedure has been developed for the determination of about 50 trace elements in high-purity selenium. The method consists of two distillation steps, followed by a precipitation step. In the first distillation step the halogens, osmium, and part of the ruthenium are volatilised in the second the selenium is distilled together with antimony, tin, arsenic, mercury and germanium. Selenium is precipitated from the second distillate by reduction to the element. The whole procedure has been tested by means of radioactive tracers. Interferences from the selenium matrix with respect to the arsenic and bromine determinations are discussed.     

Method for the detection of Tc in seaweed samples coupling the use of Re as a chemical tracer and isotope dilution inductively coupled plasma mass spectrometry

Analysis of the artificial radionuclide ⁹⁹Tc in environmental samples requires a chemical separation due to its low concentration, and therefore the use of a chemical yield tracer is peremptory. From a practical viewpoint, Re can be used for this purpose, due to its chemical similarities with Tc. Thus, the use of a radioactive tracer for Tc recovery calculation can be avoided. However, results from a recent intercomparison exercise showed that using of Re as a chemical yield tracer appears to underestimate the Tc concentration relative to the result obtained with isotopes of Tc. In the present work, the methodology used to design a simple separation method for the measurement of ⁹⁹Tc in environmental samples is described. Tc recovery is estimated throughout the Re recovery calculation by the isotope dilution technique coupled with ICP-MS (ID-ICP-MS) technique. For chemical separation, a chromatographic resin is used. Interfering elements are removed using a resin washing step carefully designed to avoid any element fractionation between Re and Tc; the care taken in this step is of major importance to assure the equivalence of the chemical recoveries for both elements. Agreement is tested using five replicates of five seaweed samples. The average recoveries for ^95mTc and Re were 93±6 and 95±7%, respectively, those are within the uncertainty intervals for each other. The results explained here demonstrate the possibility of applying Re chemical recoveries to calculate the Tc concentrations with the advantage of not introducing systematic errors.     

Quasi-steady-state approximations in air pollution modeling: Comparison of two numerical schemes for oxidant prediction

A numerical method to solve the set of differential equations which describes the chemical development in polluted air is presented. The photochemical lifetimes, continuously monitored for all compounds, determine how the integrations are performed at all times. Components with lifetimes less than 10% of the time step, which is taken as 30 sec, are assumed to be in photochemical equilibrium, while compounds with photochemical lifetimes greater than 100 times the time step are computed according to Euler's method. All other components are calculated from the exponential solution of the continuity equation. The computational accuracy may be improved by iteration on components assumed to be determined by the instant values of other components. The convergence of the iteration is speeded up by ordering the short-lived compounds in a hierarchical sequence. Since computational errors connected with QSSA methods are difficult to assess, comparison with an automatic scheme is necessary. Our method has been compared with Gear's method for a range of model mixtures of hydrocarbons, nitrogen oxides, and air, thought to cover most conceivable situations of atmospheric pollution. The agreement with Gear's method is within a few percent for all components all the time, in most cases even within 1%. No accumulation of deviations occur during long-term integrations (e.g., 48 hr with day and night shiftings), and differences which appear during periods with strong concentration gradients (e.g., after sunrise) vanish when the activity has culminated. The method presented here is considerably more efficient than Gear's method, with respect to both computer time and storage.     

High-performance liquid chromatography with continuous gradient elution in screening for unknown metabolites of butoprozine directly in dog bile

This paper describes the screening for metabolites of butoprozine, a new anti-anginal drug, in dog bile by means of reverse-phase HPLC. Although it does involve a simple clean-up step to remove a substantial amount of endogenous bile compounds, this screening method nevertheless avoids extraction of metabolites and thus allows all metabolites to be introduced into the chromatographic system. A single run of 100 minutes from 100% water to 100% methanol in a linear gradient effects adequate separation of the great majority of metabolites without interference from remaining endogenous compounds. Two methods of differentiating between metabolite peaks and endogenous peaks have been worked out. The first one makes use of ¹⁴C-labeled butoprozine by measuring the amount of radioactivity in the column effluent while simultaneously recording the UV absorbance. The second method compares continuous gradient chromatograms of bile recorded before and after butoprozine administration under very similar conditions. The latter method can be applied to both radioactive and non-radioactive materials.     

Computer generation of chemical structures from known fragments

The interactive generation of chemical structures from given fragments is described and discussed. It is implemented as a part of our expert system CARBON, based on C-13 NMR spectra. As it is designed, this program can also be a useful tool in the structure elucidation process when information on parts of the structure is obtained by other means (IR, mass and other spectrometries, chemical analysis, other relevant information). The topological characteristics of candidate fragments are first chosen interactively and then the elements are connected in all topologically possible ways. In the following step, the topological building blocks are substituted by chemical structural fragments resulting in a set of all chemical structures consistent with the input information.     

Ruthenium-catalyzed reactions of 1-cyclopropyl-2-propyn-1-ols with anilines and water via allenylidene intermediates: selective preparation of tri- and tetrasubstituted conjugated enynes

Ruthenium-catalyzed efficient preparation of the conjugated enynes can be carried out in the reactions of 1-cyclopropyl-2-propyn-1-ols with nitrogen- and oxygen-centered nucleophiles such as anilines and water in the presence of a catalytic amount of sulfur-bridged diruthenium complexes. The use of such complexes as catalysts realizes the completely stereoselective preparation of tri- and tetrasubstituted conjugated enynes, where ruthenium-allenylidene complexes work as key intermediates. The direct attack of nucleophiles on a cyclopropane ring connected to an allenylidene ligand is a key step to obtain the enynes stereoselectively.     

Solid-phase synthesis of a branched hexasaccharide using a highly efficient synthetic strategy.

The solid-phase synthesis of branched lacto-N-neohexaose derivative 1 occurring in human milk is described. The new building block of lactose 3 bearing the orthogonal temporary hydroxy protecting groups 9-fluorenylmethyloxycarbonyl (Fmoc) and levulinoyl (Lev) has been prepared. Its use, together with that of lactosamine donor 4, glucosamine donor 5, and O-galactosyl trichloroacetimidate 6, has enabled the preparation of hexasaccharide 22 following two different approaches in excellent overall yield (43%, 90% per step over eight steps). An additional key feature of this work is the successful use of newly prepared ester-type linker 2, having a benzylic spacer connected to the anomeric oxygen. This linker presents the advantage of producing a benzylic anomeric moiety after cleavage from the polymer support, which could be easily removed to obtain the unprotected oligosaccharide 1.     

Research on underground water pollution caused by geological fault through radioactive stratum

The earthquakes cause appearance of new geological fault and dislocation of rock stratum; the original permeable rock breaks, then the fault can conduct water under the effect of pressure; the stratum with radionuclide is dislocated and connected to the water-conducting fault under the effect of the fault. Under the effect of water the stratum with seepage and the one with radionuclide link up. It causes radioactive pollution on underground water, based on which this paper does a research and makes an analysis of the radioactive pollutant concentration that diffuses along the top and bottom section and centre line of the fault following the seepage. It turns out that in the rock stratum with seepage suffering rupture, the radioactive pollutant effects an elliptical spherical diffusion. In the turning point of the fault, the elliptical sphere makes a turn following the seepage.     

Actinorhodin Biosynthesis Terminates with an Unprecedented Biaryl Coupling Reaction

A plethora of dimeric natural products exist with diverse chemical structures and biological activities. A major strategy for dimerization is aryl coupling catalyzed by cytochrome P450 or laccase. Actinorhodin (ACT) from Streptomyces coelicolor A3(2) has a dimeric pyranonaphthoquinone structure connected by a C−C bond. In this study, we identified an NmrA-family dimerizing enzyme, ActVA-ORF4, and a cofactor-independent oxidase, ActVA-ORF3, both involved in the last step of ACT biosynthesis. ActVA-ORF4 is a unique NAD(P)H-dependent enzyme that catalyzes the intermolecular C−C bond formation using 8-hydroxydihydrokalafungin (DHK-OH) as the sole substrate. On the other hand, ActVA-ORF3 was found to be a quinone-forming enzyme that produces the coupling substrate, DHK-OH and the final product, ACT. Consequently, the functional assignment of all essential enzymes in the biosynthesis of ACT, one of the best-known model natural products, has been completed.