Characterization of nuclear fuels by ICP mass-spectrometric techniques

Isotopic analyses of radioactive materials such as irradiated nuclear fuel are of major importance for the optimization of the nuclear fuel cycle and for safeguard aspects. Among the mass-spectrometric techniques available, inductively coupled plasma mass spectrometry (ICP-MS) and thermal ionization mass spectrometry are the most frequently applied methods for nuclear applications. Because of the low detection limits, the ability to analyze the isotopic composition of the elements and the applicability of the techniques for measuring stable as well as radioactive nuclides with similar sensitivity, both mass-spectrometric techniques are an excellent amendment to classical radioactivity counting methods. The paper describes selected applications of multicollector ICP-MS in combination with chromatographic separation techniques and laser ablation for the isotopic analysis of irradiated nuclear fuels. The advantages and limitations of the selected analytical technique for the characterization of such a heterogeneous sample matrix are discussed.     

Concentration of radioactive components in liquid low-level radioactive waste by membrane distillation

The paper addresses some aspects of liquid low-level radioactive waste (LLLW) purification. Since the volume of liquid low-level wastes is usually large and the activity is rather low, the radioactive substances separated from the non-active portion have to be concentrated into the small volume for subsequent conditioning and disposal. The need for the improvement of decontamination and minimisation of the costs have led to new specific methods being under examination and development. The method proposed in the paper is membrane distillation. The experimental work described below supports the statement that membrane distillation can be an attractive alternative for liquid radioactive waste treatment. The advantages of membrane distillation over the other processes commonly used for the processing of LLLW are discussed in the paper.     

Uranium leaching using mixed organic acids produced by Aspergillus niger

Source term information is required for to reconstruct a device used in a dispersed radiological dispersal device. Simulating a radioactive environment to train and exercise sampling and sample characterization methods with suitable sample materials is a continued challenge. The Idaho National Laboratory has developed and permitted a radioactive response training range (RRTR), an 800 acre test range that is approved for open air dispersal of activated KBr, for training first responders in the entry and exit from radioactively contaminated areas, and testing protocols for environmental sampling and field characterization. Members from the Department of Defense, Law Enforcement, and the Department of Energy participated in the first contamination exercise that was conducted at the RRTR in the July 2011. The range was contaminated using a short lived radioactive ⁸²Br isotope (activated KBr). Soil samples contaminated with KBr (dispersed as a solution) and glass particles containing activated potassium bromide that emulated dispersed radioactive materials (such as ceramic-based sealed source materials) were collected to assess environmental sampling and characterization techniques. This presentation summarizes the performance of a radioactive materials surrogate for use as a training aide for nuclear forensics.     

Rapid radiochemical sample preparation for alpha spectrometry using polymer ligand films

Rapid radioanalytical methods are adversely affected by many different sample-matrix interferences, which make analyzing samples a difficult and time consuming process. A new method for preparing radioactive samples for analysis by alpha spectrometry has been demonstrated. In this technique, a selective extractive ligand is immobilized in a polymer film coated on a metal surface. This polymer ligand film is then used to extract plutonium and other radioactive analytes from solution over a short period of time. The prepared substrate is then counted directly by alpha spectroscopy in a small single detector alpha spectrometer. The method has been demonstrated for the analysis of americium and plutonium in liquid samples such as water and urine.     

Latest achievements in the analytical chemistry of actinides

New methods for separation and determination of actinides, widely used in analysis of actinides in technological and environmental samples are reviewed. Special attention is paid to obtaining and stabilizing transplutonium elements. (TPE) in extreme oxidation states. Their use in analytical practice resulted in expanding possibilities of methods for separation and determination of TPE. Solvent extraction, sorption and extraction chromatography are the basic methods for separation of TPE. Solvent extraction, sorption and extraction chromatography are the basic methods for separation of TPE. Methods of separation in gas phase and some other methods such as precipitation and coprecipitation are applied, however, to a lesser degree. Trends of development of these methods including those of various types of membrane extraction that succeeded in separation of TPE in both trivalent and other valence states have been shown. Attention is paid mainly to consideration of modern methods for determination of actinides, special distinction of such methods being low limits of determination, high precision and selectivity. Alpha- and beta-spectrometric methods with semiconductor detectors are the most advanced among various methods based on registration of nuclear radiation. Tremendous success has been achieved in development of emission-spectrometric methods for determination of trace amounts of actinides and various impure elements occurring in samples of actinides. Sensitive mass-spectrometric methods are widely used for determination of both isotope composition and content of elements in various samples including those which are highly radioactive. More simple and precise titrimetric methods based on using oxidizing-reducing or complexing agents are developed successfully. A large number of coulometric methods for determination of americium and berkelium, characterizing high precision and selectivity as well as luminescence methods have been developed.     

Monitoring of large scale contamination of the environment: The learning of Chernobyl

The Chernobyl fallout offered the possibility to test new monitoring methods and better understand the behaviour of radionuclides in natural and semi-natural environments. The research started after the Chernobyl accident confirmed previous knowledge, yet producing new information on the radioecology of forested ecosystems. Biological indicators were used with success to establish a relationship between ground deposition and radioactive transfer to wildlife and to evaluate the biological effects of ionizing radiations at low doses.     

Methods and techniques for the selective extraction and recovery of oxoanions

An important goal in environmental chemistry is the extraction of metals that are toxic or radioactive from soils and waters. For many such metals, the problem is solved by designing compounds with coordination sites that are specific for that particular metal. For cases such as oxoanions, however, where the inorganic center is already fully coordinated by oxygens, different strategies need to be used. Chromate, phosphate, selenate, pertechnetate, and aluminate are such anions. These species are problematic contaminants in soils and waters because they are either toxic, environmentally undesirable, or radioactive. Furthermore, under both acidic and basic conditions, the coordination positions of these oxoanions are occupied by oxygens. Chromium(VI) as either chromate or dichromate presents a particular problem because it is a strong oxidizing agent. In this review the different methods of extracting this group of pseudotetrahedral oxoanions are discussed, along with the individual advantages and limitations of each strategy.     

Chemiluminescent tags in immunoassays

Although radioimmunoassay procedures have a number of advantages they do pose problems, especially with regard to the disposal of radioactive waste. Alternative methods, such as chemiluminescence, enzyme, fluorescence, or spin immunoassays, have been tested with the aim of replacing radioactive labels without loss of sensitivity, precision and accuracy.     

Preparation and thermal stability of Al2O3-clay and Fe2O3-clay nanocomposites, with potential application as remediation of radioactive effluents

In the last years metal/clays, aluminosilicates with properties and characteristics of microporous materials, have received more attention, due to the possibility of their use as matrix for nanoparticles encapsulation and stabilization processes. Some types of clays were comparatively evaluated for treating the simulated radioactive wastewater. The raw clay from Valea Chioarului Romania and its pillared forms with Al, Fe, pillars for decontamination of waste-waters with medium and low radioactivity were used. Characterization of the obtained materials was carried out using techniques such as X-ray diffraction, Fourier transform infrared spectroscopy, BET analyses and thermogravimetric analysis (DTG-TG), respectively. Also, the thermal stability of nanocomposites was highly superior to native clay due to the presence of the well-dispersed clay nanolayer, which has a barrier property in a composite system. Clay nanocomposite sample materials were obtained with good thermal stability after calcination. Clay nanocomposites samples were evaluated for remediation of radioactive effluents by treating the radioactive wastes streams. The ion-exchange characteristics and the abilities to uptake radioisotopes of indigene clay from Valea Chioarului area-Romania were examined. The results showed that the precursor used in sample preparation influenced the structural and textural properties of nanocomposites and also capability of prepared modified clay samples by pillaring to be potential candidates for use in connection with environmental protection, remediation of radioactive effluents, respectively.     

Selective extraction of naturally occurring radioactive Ra2+

Organic extractants play a significant role in the selective removal of radioactive cations from waste streams. Although, literature on the selective removal of man-made radioactive material such as Americium (Am) is widespread, the selective removal of naturally occurring radioactive material such as Ra2+ is only mentioned sporadically. This tutorial review deals with the selective extraction of the highly radiotoxic Ra2+. Special attention is paid to different types of organic extractants used.     

实时荧光等位基因特异性扩增法快速检测K-ras癌基因点突变

将荧光定量PCR技术与等位基因特异性扩增(Allele specific amplification, ASA)方法相结合, 发展了一种可以快速检测基因点突变的实时荧光等位基因特异性扩增(Real-time ASA)方法. 将该法用于检测K-ras癌基因第12位密码子发生的点突变, 分别采用针对其不同点突变方式(GAT, GTT, CGT)设计的突变型引物对待测样品进行ASA, 只有突变型样品能被顺利扩增出双链DNA产物, 该产物才能与双链DNA染料SYBR Green Ⅰ结合, 发出荧光信号从而被检测到. 用该法检测31例结肠癌组织中的K-ras癌基因点突变, 其中有15例样品检出为突变型. Real-time ASA法可检测到样品中含量为1/1000的突变型基因, 具有灵敏、快速、简便、安全、高通量和低成本等优点, 可望用于大量临床样本的点突变筛查.     

Remote system for the mass production of short-lived radioisotopes in a cyclotron. Development of the system and radioisotope production

A system was developed for producing short-lived radioactive substances (11CO, 11CO2, 13NN, 13NH3, 18F-, 62Zn2+, 123I-, etc.) on a scale enough for clinical use, which could also be used for analyzing them rapidly and for investigating their production methods, with less received dose by workers. The system enabled us to produce remotely several tens mCi of of short-lived radioactive susbtances readily usable for clinical diagnosis, continuosly for radioactive gases, 11CO, 11CO2 and 13NN, or repeatedly at short intervals for radioactive aqueous solutions of 13NH3, 18F-, etc. Employing this system, the average received dose per month was reduced considerably.     

Simultaneous determination of radioactive and stable isotopes of cobalt in environmental samples by the isotopic exchange method

The isotopic exchange method is studied for the simultaneous determination of radioactive and stable isotopes of cobalt in environmental samples. Radioactive cobalt is isotopically exchanged with Co-CyDTA in HC1 solution of the sample. The solvent extraction method is used for the separation of Co2+ and Co-CyDTA species from each other. The amounts of radioactive and stable cobalt isotopes are calculated with activities of Co and Co-CyDTA at the exchange equilibrium. The methods for eliminating interfering ions are discussed. The results are in good concordance with those obtained by the conventional analytical methods.     

Determination of long-lived radionuclides in radioactive wastes from the IEA-R1 nuclear research reactor

Ion-exchange resins and activated charcoal beds are employed for purification of the cooling water that is pumped through the core of pool type nuclear research reactors. Once expended, these media are replaced and become radioactive wastes that contain low concentrations of long-lived fission and activation products, uranium isotopes and transuranium elements. Determination of the radioactive inventory is of paramount importance in the management of such radioactive wastes, which, besides high-energy photon emitters that can be identified and quantified directly by gamma-ray spectrometry, also contain pure alpha, pure beta and low-energy photon emitters whose quantitative determination require radiochemical separation. These later are collectively known as difficult to measure (DTM) radionuclides. A characterization program embracing the DTM radionuclides is currently in progress for spent ion-exchange resins and activated charcoal beds that were definitively withdrawn from the water cleanup system of the IEA-R1 nuclear research reactor. Radiochemical methods used in the characterization program include separations with specific anionic resins, chromatographic extractions and co-precipitation, which enabled the measurement of the activity concentrations of ⁹⁰Sr, ²³⁴U, ²³⁵U, ²³⁸U, ²³⁸Pu, ^239+240Pu, ²⁴¹Pu, ²⁴¹Am and ²⁴⁴Cm. An enhanced retention of uranium and transuranium elements was observed in the activated charcoal compared to the ion-exchange resins as a result of the tendency of actinides to undergo hydrolysis in aqueous solutions.     

Methodology for the U.S. Food and Drug Administration's radionuclides in foods program

The U.S. Food and Drug Administration (FDA) is responsible for the wholesomeness of the nation's food supply. The FDA modified its food monitoring program in January, 1973, to include radioactive isotopes. The methodology used to perform, analyses on these food products are taken from the standerd setting societies such as the AOAC International, American Society for Testing Materials and American Public Health Association Standard Methods. In addition, methods not tested by these societies are taken from the literature or from Department of Energy manuals such as the Health and Safety Laboratory and also from Environmental Protection Agency, Public Health Service, and Food and Agricultural Organization manuals. These include the methods for long-lived radionuclides such as tritium, strontium-90, cesium-137 and plutonium. Also, the short-lived radionuclides such as iodine-131, radiocesium, radiocerium and radioruthenium. In addition, they include the natural occurring radionuclides such as radium and uranium isotopes. The activity concentrations of gamma-emitters such as radiocesium, iodine-131 and radioruthenium are determined by gamma-ray spectrometry. This is done using intrinsic germanium detectors with the appropriate hardware and software. The alpha and “pure” beta-emitters are determined by various radiochemical methods and techniques. The radiochemical methodology and equipment used in analyzing these radionuclides are described and discussed. Also, the methodology and equipment for the gamma-emitters are described in more detail in this paper. In addition, the limits of detection for the methods used will be discussed.     

Determination of macroconstituents and trace elements in naturally occurring radioactive material in oil exploration waste products

Naturally occurring radioactive materials (NORM) contain radionuclides, such as radium, thorium, and uranium. The existence of NORM remains an issue for oil and gas exploration because once the material becomes concentrated through technological activity, it becomes a radioactive contamination hazard or a radioactive waste. Pipes and tanks used to handle large volumes of produced water at some oil-field sites are coated with scale deposits that contain high levels ²²⁶Ra, ²²⁸Ra and ²¹⁰Pb. Experiments were conducted using thermal and epithermal neutron activation analysis and Compton suppression for the determination of macroconstituents and trace elements in the radioactive scale sample.     

Quantitative in vitro kinase reaction as a guide for phosphoprotein analysis by mass spectrometry

A simple calculation using the radioactive decay of (32)P incorporated into a protein during in vitro kinase reactions is described that allows the overall stoichiometry of phosphorylation for the substrate protein or peptide to be calculated. Prior to using techniques such as diagnostic ion scanning to identify the molecular weight of an unknown phosphopeptide in a complex mixture followed by tandem mass spectrometry (MS/MS) to locate the phosphorylated residue within the phosphopeptide, such calculations are predictive of the chances for successful characterization by these methods. An example of estimating the stoichiometry of peptide phosphorylation will be presented along with calculations that predict when adequate phosphopeptide is present in any given spot on the thin-layer chromatography (TLC) plates used for two-dimensional phosphopeptide (2DPP) mapping to allow extraction and complete characterization by MS/MS.     

Single crystal HPGe (80%) versus BGO shielded CLOVER detector for high precision decay rate measurements: a comparative study

In this study, various detector configurations have been investigated in order to explore the optimal condition for decay rate measurements of radioactive samples using gamma spectroscopy technique. A limitation of detecting low energy gamma rays from decaying radioactive nuclei, is the Compton background which can be significantly reduced by rejecting Compton scattered events through active Bismuth germanate (BGO) shielding. On the other hand, for a CLOVER detector without BGO shielding, one can place the radioactive samples very close to the detector for enhancing geometrical efficiency. A single crystal High Purity Germanium (HPGe) detector can also be used for decay rate measurements. In order to measure the decay rate of nuclei decaying via gamma emission with reasonable intensity, optimal close geometry options have been investigated for various HPGe detector configurations.