The application of nuclear techniques to high temperature oxidation studies

The¹⁸O(p, α)¹⁵N reaction has been used to determine the¹⁸O distribution in the oxides of a number of alloys which have been oxidised sequentially in natural gas and¹⁸O-labelled gas. A significant feature of all the cases investigated is the penetration of¹⁸O into the oxide formed previously in the natural gas. This penetration may occur in various ways and would be difficult to study by other techniques. The evidence presented here shows that there are subtle differences in oxidation behaviour and confirms that penetration of oxygen is a feature in the oxidation of alloys in which the predominant mechanism is transport of cations. This may have implications in explanations given to account for oxidation kinetics and adhesion and buckling of scales.     

Modified on-line monitoring of total gaseous mercury in flue gases using Semtech® Hg 2000 analyzer

The Semtech Hg 2000 analyzer continuously monitors the Hg⁰ content in flue gas. An on-line measurement method of total gaseous mercury in flue gas developed in our laboratory is described, which uses the absorption cell of the Semtech Hg Analyzer connected to a converter that is located in a furnace heated up to 650?°C. The converter can be heated up to 800?°C by both the furnace and an extra heating of a Ni-Cr alloy heating wire. Both the absorption cell and the converter are made of quartz. All gaseous Hg²⁺ species in flue gas are thermally reduced to Hg⁰ by the converter and detected by the Semtech Hg 2000 analyzer. The thermal reduction efficiencies of different conversion materials, which were filled in the converter, such as quartz chips, granular MgO, Ni and CoO powder, were tested using different flue gas conditions. Studies have shown that HCl is the major factor to inhibit the thermal reduction of Hg²⁺ to Hg⁰, and in the converter and the absorption cell Hg⁰ will react readily with HCl to form HgCl₂. Both MgO and Ni could be used in the converter to absorb HCl in the flue gas, but Ni has better absorption efficiency. By using an original Semtech and a modified one, both Hg⁰ and total gaseous Hg contents in flue gas could be monitored simultaneously and continuously.     

Theoretical study on concentration polarization in gas separation membrane processes

A mathematical model was established successfully to analyze the gas separation concentration polarization which becomes an important problem due to the rapid development of membranes, especially the increase of permeation rate. The influences of membrane performance and operation parameters on concentration polarization were studied in terms of permeation fluxes of the more and the less permeable gases and separation factor. Sample calculations were presented for the two typical gas separation applications, hydrogen recovery and air separation, with shell side feed in hollow fiber module. The permeation rate was found to be a dominating factor in affecting concentration polarization, while the influences of separation factor to be significant initially and to level off gradually. Increasing feed gas velocity leads to a decrease in the concentration polarization. Operation pressures' effect is limited and the composition of feed gas shows no effect. The range in which concentration polarization is significant has been identified by studying the combined effects of the permeation rate, separation factor and feed gas velocity. Concentration polarization is important for process analysis and design when the permeation rate of the more permeable gas is larger than 1×10⁻⁴ cm³ (STP) cm⁻² s⁻¹ cmHg⁻¹ (100 GPU).     

Adsorption of <Superscript>85</Superscript>Kr radioactive inert gas into hardening mixtures

Changes in volumetric activity of ⁸⁵Kr radioactive inert gas take place in the atmosphere: it has increased by around 50% during the past 15 years. The main source of such gas is the operation of nuclear power plants and spent nuclear fuel reprocessing plants. ⁸⁵Kr as an inert gas spreads throughout the entire atmosphere and its ionizing radiation may result in changes of atmospheric electric phenomena. Therefore it is necessary to control ⁸⁵Kr emission into the atmosphere. However, there is no effective method for this as inert gases, under normal conditions, can hardly be adsorbed in different adsorbents and stored in special containers for a long period of time. This paper tries to show the possibility of keeping ⁸⁵Kr longer within the adsorbent by changing its aggregate state: gas is adsorbed into liquid adsorbent and desorption takes place from solid adsorbent. For this purpose, an epoxy resin is used which, after adding a special hardener at room temperature, turns into a solid material with density of around 1.2 × 10³ kg m⁻³. As a result of sample blending with substances which contribute to better solubility of ⁸⁵Kr, diffusion coefficient of this gas (i.e. desorption speed) changes within the adsorbent in the solid state.     

Passive method for the determination of the equilibrium factor between 222Rn gas and its short period progeny

This work describes a method which was developed to determine the concentration of ²²²Rn gas and the equilibrium factor F between the concentration of the gas and its progeny by means of a single device that uses two Makrofol passive track detectors. The device is completely passive and time integrated. Conditions make it very appropriate to be used in any atmospheres in which human activity takes place, such as houses, schools, works and underground mines. A series of measurements of ²²²Rn gas concentration and equilibrium factor F were made in different cities of the Argentine Republic and the corresponding levels of doses were estimated.     

Gas separation in nanoporous membranes formed by etching ion irradiated polymer foils

Polymer membranes with pores with radii in the range of several 10–100 nm were formed by irradiating polyimide foil with highly energetic heavy ions and etching the latent ion tracks with hypochlorite. The aerial density of the pores could be chosen up to an upper limit of 10⁸ pores cm^?2, at which too many pores start to overlap. The straight cylindrical pores were tested for their gas permeation and gas separation performance. With a gas mixture of CO and CO₂ as model system, gas chromatographic measurements showed that CO penetrates faster through the membrane than CO₂, leading to gas separation. This is possible because the mean free path of the molecules is in the order of the pore radius, which is in the transition flow region close to molecular flow conditions.     

Method for the determination of the solubility of gases in liquids

A rapid and experimentally simple method for the determination of the solubilities of oxygen or hydrogen in liquids is presented The method employs a membrane-enclosed amperometric detector of the well known Clark type to measure the partial pressure of the gas when distributed at equilibrium between the liquid and a gas space for a series of internal volumes of the system. The amounts of all substances and the temperature are maintained constant throughout the series although the internal pressure changes as a result of the volume changes. The glass apparatus is water jacketed for temperature control, has inlet and outlet ports for gas, and the amperometric sensor is mounted in a gas-tight sliding fitting for effecting the volume changes. The liquid content is vigorously stirred by a magnetic bar during measurements. Equations for the interpretation of results at different internal volumes take into account the conservation of the solvent and of the gas, the dependence of the volume of the liquid on the concentration of dissolved gas and Henry's law describing the distribution of the gas between gas and liquid phases at equilibrium. The solution of these equations yields an equation for the dependence of the measured partial pressure on volume, which includes the Henry's law constant H as a parameter. Conditions can usually be arranged to give a straight line dependence of volume on the reciprocal of partial pressure. The method has been applied to several common liquids, and has been shown to produce results which agree with literature solubilities to within about ±5%. Examples which have been studied include oxygen in water (H=4.039 × 10⁶ kPa at 20°C), in acetone (1.25 × 10⁵ kPa at 20°C), in ethanol (1.758 × 10⁵ kPa at 20°C) and in toluene (1.05 × 10⁵ kPa at 20°C) as well as hydrogen in water (6.89 × 10⁶ kPa at 20°C).     

Production of fission 131I

Summary A method of iodine separation from other radionuclides generated by ²³⁵U fission has been developed in order to explore the possibilities to obtain ¹³¹I as by-product of the ⁹⁹Mo routine production in the Ezeiza Atomic Centre. The experiments were designed to remove this element to gas phase, and the recoveries were investigated both with and without carrier addition. High volatilization percentages were achieved in the presence of iodine carrier. Some other alternatives to increase the iodine displacement to the gaseous phase, namely vacuum distillation, addition of hydrogen peroxide and use of a carrier gas, were also studied. The method developed, which employs a carrier gas stream, without carrier addition, allows the recovery of about 97% of the ¹³¹I, with high specific activity, in a simple and clean way.     

Reactor production of anhydrous18F ion

The direct production of anhydrous¹³F ion has been achieved through the incorporation of a new approach to hot atom reactions for reactor generated radiopharmaceuticals. Capitalizing on the traditional Li₂CO₃ method for hydrated¹⁸F production, a unique target design and geometry utilizing neutron generated energetic tritions emerging from the surface of a thin LiF embedded stainless steel matrix react with gaseous O₂ to produce¹⁸F as a free recoiling anhydrous species. Approximately 10–15 MBq of reactive anhydrous¹⁸F ion absorbed onto a metallic foil has been produced by this method. Verification of the production of¹⁸F was substantiated through decay measurements using Ge(Li) spectroscopic analysis, and by the synthesis of¹⁸F-fluoromethane gas. Cyclotron gas target chemistry which has been instrumental in the preparation of¹⁸F-2FDG and other metabolic tracers may be reproduced using this technique by the addition of 1% F₂ scavenger gas to a recirculating reactor gas handling system.     

Solvent extraction of uranium(VI) with benzyloctadecyldimethylammonium chloride (BODMAC) from highly concentrated chloride solution

The ²²²Rn emanation fraction (EF) released from the technically enhanced naturally occurring radioactive material (TE-NORM) wastes at certain sites of petroleum and gas production was determined. The samples were analyzed by γ-ray spectrometry to determine the activity concentration of the ²²⁶Ra content, of which the ²²²Rn emanation fraction was calculated. The results showed that the ²²²Rn emanation fraction differs in the oil and gas production sites and it is independent of the activity concentration of ²²⁶Ra. This revised version was published online in August 2006 with corrections to the Cover Date.     

Nitrite and Nitrate Production by NO and NO2 Dissolution in Water Utilizing Plasma Jet Resembling Gas Flow Pattern

This study investigated the reactive dissolution of nitric oxide (NO) and nitrogen dioxide (NO₂) mixtures in deionized water. The dissolution study was carried out in a flat surface type gas–liquid reaction chamber utilizing a gas flow-pattern resembling plasma jets which are often used in biomedical applications. The concentration of NO and NO₂ in the gas mixtures was varied in a broad range by oxidizing up to 800 ppm of nitric oxide in Ar carrier gas with variable amount of ozone. The production of nitrite (NO₂^?) and nitrate (NO₃^?) in the water was proportional to treatment time up to 50 min. The concentration of NO₃^? was a power function of gas phase NO₂ while the concentration of NO₂^? increased approximately linearly with gas phase NO₂. The formation of NO₂^? and NO₃^? could be described by reactions between dissolved NO₂ and NO in the water while the production rate was determined by diffusion-limited mass transport of nitrogen oxides to the bulk of the liquid. At higher NO₂ concentrations, the formation of dinitrogen tetraoxide (N₂O₄) increased the formation rate of NO₂^? and NO₃^?. The identified mass transport limitation by diffusion suggests that convection of water created by the gas jet is insufficient and dissolution of nitrogen oxides can be increased by additional mixing. In respect of practical applications, the ratio of NO₂^? /NO₃^? in water could be varied from 0.8 to 5.3 with treatment time and gas phase NO₂ and NO concentrations.

     

Detection of tritium and alpha decaying radionuclides in L/ILW by measurements of helium isotopes

As decay products, helium isotopes can clearly indicate the presence of tritium and alpha decaying isotopes in a closed system. This study presents the helium and neon measurements and their interpretation of long-term headspace gas investigations in L/ILW waste drums from Paks Nuclear Power Plant and closed vaults of the Radioactive Waste Treatment and Disposal Facility, Püspökszilágy, Hungary. Development of special sampling methods and preparation lines as well as isotope-analytical measurements of the headspace gas samples were done in the Hertelendi Laboratory of Environmental Studies in the ATOMKI. In the gas samples helium isotopes as well as neon isotopes have been determined mass spectrometrically. While neon content can be of atmospheric origin only, helium can be produced either by alpha decay (⁴He) or decay of tritium (³He). ³H/⁴He and He/Ne ratios have been used to determine the different origin of the helium isotopes. Helium isotope ratios always represented ³He enrichment in the headspace gases produced by the decay of the tritium in the waste. Using the recent ³He concentration in headspace gas the total amount of ³H restored in L/ILW vaults was estimated. The investigated seven different vaults were closed between 1979 and 1995 when they had been full with L/ILW. The calculated tritium activities based on the He measurements showed good agreement with the documented isotope inventory of the vaults. Typical tritium activity concentrations were between 0.1 and 10 Bq/L gas in the drums and between 10 and 1000 Bq/L gas in the vaults. Additionally, one drum showed a higher He/Ne ratio compared to air, which clearly indicates ⁴He excess, thus the presence an alpha source in the waste.     

Nouvelle méthode de préparation pour les complexes endoédriques atome de gaz rare–fullerène C60

New route for preparation of endohedral complexes of rare gas atom–C₆₀. Preparation of endohedral complexes of a rare gas atom–fullerene is described, in which a sample of C₆₀ powder, surrounded by a high pressure rare gas, is sublimated and excited by a strong nanosecond pulse laser beam. Experiments were carried out with the following rare gases: pure ⁴He, a mixture of 2 % of ³He in ⁴He, and pure Ar. Macroscopic quantities of these complexes were obtained in estimated concentations up to 20 %.     

Application of Spray-Type Atmospheric Pressure Glow Plasma Reactor: Ashing of Organic Compounds II

When plasma treatment is carried out in the after glow region of an electrical discharge, the decay rate and the density of the active species are very important factors for the treatment efficiency. They are known to depend on the linear gas flow rate (gas velocity) and on the residence time of the treatment gas in the discharge zone, respectively. In our previous study, we found that the spray-type atmospheric pressure glow plasma reactor with O₂/He or O₂/Ar mixture treatment gases had a satisfactory ashing rate of a solid organic compound (OFPR-800; a photoresist). However, the relationships between the gas velocity or the residence time and the ashing rate had not yet been examined. The present study showed clearly that the gas velocity influenced only the transit time, that is the time which the gas mixture took to progress from the slit nozzle to the sample surface, but it did not influence the generation of the active species. On the other hand, the generation rate of active species in the discharge zone was found to be strongly dependent on the residence time. The ashing rate was found to increase with increasing the residence time up to about 30 ms, beyond which it saturated. From optical emission spectroscopy measurements, the maximum ashing rate could be correlated with the emission intensities corresponding to He 3p³P-2s³S (388.8 nm) and O 3d⁵D-3p⁵P (926.5 nm) bands. These results are of practical interest.     

Determination of thoron and radon ratio by liquid scintillation spectrometry

Summary A portable liquid scintillation counter was applied for the analysis of alpha-ray energy spectrum to determine the ratio of ²²⁰Rn/²²²Rn in fumarolic gas in the field. A surface-polished vial was developed, by which a Gaussian distribution could be approximated for the alpha-ray energy spectra and the peak areas of the nuclides could be estimated independently, because of the wide FWHM in the liquid scientillation pulse. A fumarolic gas sample was collected in Mt. Kamiyama (Hakoneyama geothermal field in Japan) having low ²²⁰Rn/²²²Rn ratio of 2.20±0.13.     

Direct analysis of ultra-trace semiconductor gas by inductively coupled plasma mass spectrometry coupled with gas to particle conversion-gas exchange technique

An inductively coupled plasma mass spectrometry (ICPMS) coupled with gas to particle conversion-gas exchange technique was applied to the direct analysis of ultra-trace semiconductor gas in ambient air. The ultra-trace semiconductor gases such as arsine (AsH₃) and phosphine (PH₃) were converted to particles by reaction with ozone (O₃) and ammonia (NH₃) gases within a gas to particle conversion device (GPD). The converted particles were directly introduced and measured by ICPMS through a gas exchange device (GED), which could penetrate the particles as well as exchange to Ar from either non-reacted gases such as an air or remaining gases of O₃ and NH₃. The particle size distribution of converted particles was measured by scanning mobility particle sizer (SMPS) and the results supported the elucidation of particle agglomeration between the particle converted from semiconductor gas and the particle of ammonium nitrate (NH₄NO₃) which was produced as major particle in GPD. Stable time-resolved signals from AsH₃ and PH₃ in air were obtained by GPD-GED-ICPMS with continuous gas introduction; however, the slightly larger fluctuation, which could be due to the ionization fluctuation of particles in ICP, was observed compared to that of metal carbonyl gas in Ar introduced directly into ICPMS. The linear regression lines were obtained and the limits of detection (LODs) of 1.5 pL L⁻¹ and 2.4 nL L⁻¹ for AsH₃ and PH₃, respectively, were estimated. Since these LODs revealed sufficiently lower values than the measurement concentrations required from semiconductor industry such as 0.5 nL L⁻¹ and 30 nL L⁻¹ for AsH₃ and PH₃, respectively, the GPD-GED-ICPMS could be useful for direct and high sensitive analysis of ultra-trace semiconductor gas in air.     

Field alpha-spectroscopy of radon (<Superscript>222</Superscript>Rn) and actinon (<Superscript>219</Superscript>Rn) progeny in soil gas: Locating a radon source

Summary The activities of²¹⁸Po,²¹⁴Po and²¹¹Bi were determined in samples obtained of soil/gas. Sampling work was taken in Jáchymov (Czech Republic) at the outcrop of the Geister-vein,by electrostatic precipitation from filtered soil gas on stainless steel disks.The samples were measured in a field laboratory using a semi-conductor alpha-spectrometer.The activities of²¹⁸Po,²¹⁴Po and²¹¹Bi were calculated.Samples taken from active dump material (near-by radon source) exhibited a high²¹¹Bi/²¹⁴Po ratio, while those of the vein outcrop (a relatively deeper source) had a low ratio.A mathematical model was employed to determine the radon age calculated from the actinon/radon input ratio.This varied in a range of 5.6 to -7.7 seconds.Negative age values are probably caused by the preference for actinon, which rapidly comes into equilibrium with the source of this gas.     

Spectral Signatures of Protonated Noble Gas Clusters of Ne,Ar, Kr,and Xe: From Monomers to Trimers

The structures and spectral features of protonated noble gas clusters are examined using a first principles approach. Protonated noble gas monomers (NgH⁺) and dimers (NgH⁺Ng) have a linear structure, while the protonated noble gas trimers (Ng₃H⁺) can have a T-shaped or linear structure. Successive binding energies for these complexes are calculated at the CCSD(T)/CBS level of theory. Anharmonic simulations for the dimers and trimers unveil interesting spectral features. The symmetric NgH⁺Ng are charactized by a set of progression bands, which involves one quantum of the asymmetric Ng-H⁺ stretch with multiple quanta of the symmetric Ng-H⁺ stretch. Such a spectral signature is very robust and is predicted to be observed in both T-shaped and linear isomers of Ng₃H⁺. Meanwhile, for selected asymmetric NgH⁺Ng’, a Fermi resonance interaction involving the first overtone of the proton bend with the proton stretch is predicted to occur in ArH⁺Kr and XeH⁺Kr.     

Coordinative saturation of cationic niobium– and rhodium–argon complexes

Mass spectra of Nb⁺ and Rh⁺ complexes with argon ligands exhibit `magic' peaks Nb⁺Ar₄ and Rh⁺Ar₆, similar to observations for V⁺Ar₄ and Co⁺Ar₆, indicating coordinative saturation. A consistent explanation is obtained by assuming that the rare gas ligands seek out electron density minima in the valence shell of the ion, which permit a closer approach to the metal core and a stronger charge-induced dipole bond. Ab initio density functional calculations, which predict stable square planar complexes for the d⁴ ions and octahedral for the d⁸ species, support this interpretation and show that rare gas complexes of d⁴ metal ions fit perfectly well into the coordination chemical framework based on the Jahn–Teller effect.     

Comparison of no gas and He/H2 cell modes used for reduction of isobaric interferences in selenium speciation by ion chromatography with inductively coupled plasma mass spectrometry

Inductively coupled plasma mass spectrometry (ICP-MS) used for the detection of most common selenium isotopes ⁷⁸Se (23.8%, abundance) and ⁸⁰Se (49.6%, abundance) is interfered in the presence of ³⁸Ar⁴⁰Ar⁺ and ⁴⁰Ar⁴⁰Ar⁺ in argon (Ar) gas. To address this issue, ICP-MS with an octopole reaction system (ORS) was explored for the detection of selenite and selenate, which was separated by anion-exchange chromatography. Results indicate that it was possible to detect ⁷⁸Se using no collusion gas, while to detect ⁸⁰Se a H₂ as the collusion/reaction gas was recommended since the background and noise were significantly reduced using H₂ as the gas. The selenium speciation interested was separated on a new column (G3154/101A, Agilent technologies) within 5 min using a mobile phase containing 10 mM NH₄H₂PO₄ and 20 mM NH₄NO₃ at pH 6.5. Linear plots were obtained in a concentration range of 1–200 μg/L with detection limits less than of 0.4 μg/L for ⁸⁰Se (IV) and 0.6 μg/L for ⁸⁰Se (VI) using H₂ as the reaction gas. Finally, the proposed method was used in the determination of selenium in water and soil.