The isotopic composition and atomic weight of molybdenum

The isotopic composition of molybdenum in a shelf reagent standard (MoO₃, 99.99%), 13 molybdenites, and three iron meteorites has been determined with a thermal ionization mass spectrometer. No especially-evident variations of molybdenum isotopes among these samples have been found. The mass fractionation of molybdenum occurring in isotopes during the measurements is discussed and our preferred natural abundances of molybdenum isotopes are:⁹²Mo, 14.7287 ± 0.0010;⁹⁴Mo, 9.2118 ± 0.0006;⁹⁵Mo, 15.8935 ± 0.0011;⁹⁶Mo, 16.6731 ± 0.0011;⁹⁷Mo, 9.5692 ± 0.0007;⁹⁸Mo, 24.2289 ± 0.0017;¹⁰⁰Mo, 9.6950 ± 0.0007. Thus, the atomic weight of molybdenum is 95.9415 ± 0.0001 (the value currently accepted by IUPAC [IUPAC Inorganic Chemistry Division, Pure Appl. Chem., 63 (1991) 991] is 95.94 ± 0.01). The uncertainties correspond to the 95% confidence limit calculated from all the terrestrial and meteoritic samples.     

Spontaneous fission yields for 238U in molybdenum measured in Archaean zircons

The relative cumulative fission yields of ^95,97,98,100Mo produced by spontaneous fission of ²³⁸U contained in Archaean zircons, were measured by sensitive thermal ionization mass spectrometry (TIMS). The relative yields for ^95,97,98,100Mo are 0.58 : 1.08 : 1.04 : 1.0, respectively. Combined with mass spectrometrically-determined ^{99,101,102,104}Ru fission yields,¹ the mass distribution from 95￡A￡104 can be delineated. Assuming an “absolute” fission yield of 6.1±0.4% for the cumulative fission yield at mass 97, it is possible to express the Mo and Ru relative spontaneous fission yields for ²³⁸U as “absolute” values. There is no evidence for a significant isotope anomaly at mass 98. This revised version was published online in July 2006 with corrections to the Cover Date.     

Computerized on-line measurement the yield of short-lived bromine and iodine isotopes from thermal neutron fission of235U

The short-lived bromine and iodine isotopes from thermal neutron fission of²³⁵U have been separated from fission products by one step solvent extraction combined with an ion exchange fast chemistry system. The measured gamma spectra have been acquisited by an automatic computer on-line system. The results include experimental independent fission yields of⁸⁶Br,^134mI,^134gI,^136mI, and^136gI, the cumulative yields of⁸⁷Br,⁸⁸Br,¹³⁷I,¹³⁸I. The isomeric yield ratio of¹³⁴I and¹³⁶I has been determined and the iodine isotopic distribution curve has been constructed and analyzed.     

Separation of iodine produced from fission with a porous metal silver column in99Mo production

In Argentina, at the Ezeiza Atomic Center,¹³¹I is produced by wet distillation of natural tellurium dioxide irradiated with thermal neutrons in a pool-type reactor. In order to recover the¹³¹I present in the production process of fission⁹⁹Mo obtained by irradiation of UAL_x/Al targets (with 90% enriched uranium) a separation method was developed. Iodine isotopes can be separated from a sodium hydroxide solution containing fission products using a column filled with alternate beds of glass microspheres and porous metal silver. Tests with tracers were performed in radiochemical laboratory. Following this results, a series of tests with higher activities (3 TBq of⁹⁹Mo and 0.7 TBq of¹³¹I) were carried out in hot cells. Molybdenum passes through the silver column, while¹³¹I retention was 92–97% in tracer test and 90% in optimised hot cell tests. This result depends on several facts that are discussed. An initial separation of iodine isotopes diminishes radiation damage on ion-exchange resin used in the subsequent molybdenum purification, improving its retention and elution yield.     

Mass Spectrometric Determination of Zirconium from a Resin Bead

Abstract

A sensitive, isotope dilution technique has been developed for the analysis of sub-microgram amounts of zirconium. The analysis is based on the increased thermal ion emission for Zr adsorbed on a single anion resin bead. Zr is isolated from a solution containing the sample and a highly enriched ⁹⁴Zr (96%) spike. The determination is made possible by using a high-sensitivity pulse-counting 2-stage 30-cm radius mass spectrometer. The detection limit depends upon the amount of the isotope spike added and the desired precision. Fifty nanograms of zirconium (sample plus spike) produce sufficient ion signals for reliable isotopic analysis so that fission Zr can be measured with blank correction to a precision of 3%. By this method for fission Zr in spent reactor fuel particles, contamination from normal Zr and Mo can be corrected out by making isotopic measurements before and after spiking and scanning masses 90 and 95 during analysis. Since neither masses 90 nor 95 are stable fission products, their presence is due to sample contamination and can be used for correction based on their normal isotopic distributions. Zone-refined tantalum ribbon, essentially free of normal Zr and Mo was selected as the ionizing filament. This method can be adapted to a wide variety of samples.     

Improved processes of molybdenum-99 production

Two improved processes of⁹⁹Mo production have been developed on laboratory scale. The first one allows to purify Mo of natural isotopic composition from tungsten impurities from 64 to <10 ppm by using preferential adsorption of tungsten on hydrated tin(IV) oxide (SnO₂ nH₂O) before irradiation in a nuclear reactor. The second process deals with the separation of pure fission product⁹⁹Mo from²³⁵U irradiated in a reactor. Two versions of separation process for production of fission⁹⁹Mo have been developed. Both versions start with the dissolution of²³⁵U oxide target in nitric acid and are based on sequential use of alumina and anion exchange resin AG® 1-X8 columns. The yield of⁹⁹Mo in both versions is 80–89%.     

Fine structure of mass and charge distribution in low energy fission

Studies of finer details in mass and charge distribution fission leads to a better understanding of the fission process. Experimental determination of independent and cumulative yields using radiochemical techniques as well as mass spectrometers and fission product recoil separators form the basis of such studies. It has been established that closed shells as well as an even number of nucleons influence both mass and charge distributions. The magnitudes of these effects may be estimated from existing experimental yield data and various fission models. Using our measurements of several fission yields and those existing in the literature we have calculated even-odd proton and neutron effects for various low energy fissioning systems. Where enough data existed, direct calculations were made, whereas for other cases the Z_p-model of WAHL has been used. It is found that the even-odd proton effect is well established and pronounced in thermal neutron fission of²³⁵U and²³³U. Lesser effects were found for reactor neutron induced fission of²³²Th, thermal neutron fission of²³⁹Pu and spontaneous fission of²⁴⁵Cm and²⁴⁹Cf. No effect seems to exist in the thermal neutron fission of²⁴¹Pu and the spontaneous fission of²⁵²Cf. The even-odd neutron effect is found to be much lower than the corresponding proton effect in²³⁵U and²³³U fissions and is nonexistent in the rest of the fissioning systems.     

Cumulative yields of short-lived ruthenium isotopes in the thermal neutron induced fission of233U,235U and239Pu

Cumulative yields of short-lived ruthenium isotopes in the thermal neutron induced fission of²³⁵U,²³⁵U and²³⁹Pu have been determined using a fast radiochemical separation technique followed by gamma spectrometry. The cumulative yields of¹⁰⁷Ru and¹⁰³Ru in²³³U (n_th, f) and¹⁰⁷Ru and¹⁰⁹Ru in²³⁹Pu (n_th, f) are determined for the first time. The measured cumulative yields are converted to chain yields assuming normal charge distribution systematics for comparison with the literature data on chain yields.     

Entwicklung von Methoden zur Abbrandbestimmung von Kernbrennstoffen in Schnellen Reaktoren

The burn up determination of fast reactor fuel is more difficult than for thermal reactors, because a greater number of isotopes fissions. The burn up measurement by fission products needed the determination of fission yields in a fast flux of isotopes contributing considerably to fission. To ease the analysis the sample conditioning was eliminated if applicable. The measurement techniques and the evaluation was automatised. A isotope correlation to check the analysis is mentioned.      

Determination of molybdenum in plant reference material by thermal-ionization isotope-dilution mass spectrometry

Summary An analytical method is described for the determination of the concentration and the isotopic composition of molybdenum in plant samples using thermal ionization mass spectrometry. After microwave acid digestion and liquid-liquid extractive separation with Amberlite LA-2, the molybdenum isotopes are measured as MoO ₃ ^– -ions in a quadrupole mass spectrometer. In all cases, the relative standard deviation of the measurements of both natural and spike molybdenum was better than 3% for all ratios measured. The concentration of molybdenum found in three different plant reference materials agreed well with the certified values.     

Fission yield measurements by inductively coupled plasma mass-spectrometry

Correct prediction of the fission products inventory in irradiated nuclear fuels is essential for accurate estimation of fuel burnup, establishing proper requirements for spent fuel transportation and storage, materials accountability and nuclear forensics. Such prediction is impossible without accurate knowledge of neutron induced fission yields. The uncertainty of the fission yields reported in the ENDF/B-VII.0 library is not uniform across all of the data and much of the improvement is desired for certain fissioning isotopes and fission products. We discuss our measurements of cumulative fission yields in nuclear fuels irradiated in thermal and fast reactor spectra using Inductively Coupled Plasma Mass Spectrometry.     

Using Monte Carlo transport to accurately predict isotope production and activation analysis rates at the University of Missouri research reactor

A detailed Monte Carlo N-Particle Transport Code (MCNP5) model of the University of Missouri research reactor (MURR) has been developed. The ability of the model to accurately predict isotope production rates was verified by comparing measured and calculated neutron-capture reaction rates for numerous isotopes. In addition to thermal (1/v) monitors, the benchmarking included a number of isotopes whose (n, γ) reaction rates are very sensitive to the epithermal portion of the neutron spectrum. Using the most recent neutron libraries (ENDF/B-VII.0), the model was able to accurately predict the measured reaction rates in all cases. The model was then combined with ORIGEN 2.2, via MONTEBURNS 2.0, to calculate production of ⁹⁹Mo from fission of low-enriched uranium foils. The model was used to investigate both annular and plate LEU foil targets in a variety of arrangements in a graphite irradiation wedge to optimize the production of ⁹⁹Mo.     

The pre-Fermi natural reactor: A note on the periodic mode of operation

The isotopic compositions of xenon released from the Oklo reactor at temperatures below 1000°C are such that the abundances of¹³¹Xe,¹³²Xe and¹³⁴Xe relative to¹³⁶Xe are markedly enhanced when compared to the relative fission yields from the thermal neutron-induced fission of²³⁵U. These anomalies can be attributed to the fact that¹³¹Xe,¹³²Xe and¹³⁴Xe have fairly long-lived precursors: 8.04-day¹³¹I, 78.2-hour¹³²Te and 42-minute¹³⁴Te, respectively. It is possible to determine the duration of the time when the reactor was turned off from the ratios of excess¹³²Xe to excess¹³⁴Xe in these anomalous xenon fractions released from the Oklo reactor. Calculations based on the available xenon isotope data that the time period during which the reactor was turned off was approximately 2 to 3 hours.     

Radioxenon production through neutron irradiation of stable xenon gas

The Spectral Deconvolution Analysis Tool (SDAT) software was developed to improve counting statistics and detection limits for nuclear explosion radionuclide measurements. SDAT utilizes spectral deconvolution spectroscopy techniques and can analyze both β–γ coincidence spectra for radioxenon isotopes and high-resolution HPGe spectra from aerosol monitors. The deconvolution algorithm of the SDAT requires a library of β–γ coincidence spectra of individual radioxenon isotopes to determine isotopic ratios in a sample. In order to get experimentally produced spectra of the individual isotopes, we have irradiated enriched samples of ¹³⁰Xe, ¹³²Xe, and ¹³⁴Xe gas with a neutron beam from the TRIGA reactor at The University of Texas. The samples were counted in an Automated Radioxenon Sampler/Analyzer (ARSA) style β–γ coincidence detector. The spectra produced show that this method of radioxenon production yields samples with very high purity of the individual isotopes for ^131mXe and ¹³⁵Xe and a sample with a substantial ^133mXe to ¹³³Xe ratio.     

Evaluation of proton induced reactions on 100Mo: New cross sections for production of 99 mTc and 99Mo

The use of the ⁹⁹Mo^99mTc generator in nuclear medicine is well established world wide. The production of the ⁹⁹Mo (T_1/2 = 66 h) parent as a fission product of ²³⁵U is largely based on the use of reactor technology. From the early 1990's accelerator based production methods to provide either direct produced ^99mTc or the parent ⁹⁹Mo, were studied and suggested as potential alternatives to the reactor based production of ⁹⁹Mo. A possible pathway for the charged particle production of ^99mTc and ⁹⁹Mo is irradiation of molybdenum metal with protons via the reaction ¹⁰⁰Mo(p,2n)^99mTc and ¹⁰⁰Mo(p,pn)⁹⁹Mo, respectively. The earlier published excitation functions show large differences in their maximum that result in large differences in the calculated yields. We therefore decided to study the excitation function for these proton-induced reactions. In this work the newly measured excitation functions as well as an evaluation of earlier measured data and a discussion of the observed disagreements are presented.     

Estimation of isotopic composition of plutonium from thermal reactors by neutron coincidence counting through isotopic correlation technique

Correlations have been established between %Eff ²⁴⁰Pu and various plutonium isotopes formed in thermal reactors. Based on these correlations, a method has been developed for the estimation of isotopic composition of plutonium obtained from thermal reactors. The method is simple, fast, non-destructive and finds application for the verification of plutonium isotopic composition in the finished products of known plutonium content. The method could be applied in the nuclear fuel fabrication to verify and confirm the fissile content (²³⁹Pu+²⁴¹Pu) specification. It has also been shown that in principle, similar correlations could be established for Pu obtained from different thermal reactor fuels with reactor specific fitting parameters.     

Experimental measurements of short-lived fission products from uranium,neptunium, plutonium and americium

Fission yields are especially well characterized for long-lived fission products. Modeling techniques incorporate numerous assumptions and can be used to deduce information about the distribution of short-lived fission products. This work is an attempt to gather experimental (model-independent) data on short-lived fission products. Fissile isotopes of uranium, neptunium, plutonium and americium were irradiated under pulse conditions at the Washington State University 1 MW TRIGA reactor to achieve ~10⁸ fissions. The samples were placed on an HPGe (high purity germanium) detector to initiate counting in less than 3 min post irradiation. The data was analyzed to determine which radionuclides could be quantified and compared to the published fission yield data.     

Concentration measurements and isotopic composition of airborne molybdenum collected in an urban environment

Here, we report the first measurements of the molybdenum (Mo) isotopic composition of aerosols collected on Teflon air filters. Mo concentrations and isotopic compositions were measured at selected locations in the city of Calgary, Canada, including a residence, the isotope laboratory at the University of Calgary, the University of Calgary weather station, and the City of Calgary Transit bus garage. Concentrations ranged from 0.07 ng/m³ in the laboratory to 19.0 ng/m³ in the bus garage. The concentrations of Mo in the air samples collected in the bus garage were the highest measured in this study. To date, there are no reported data for the Mo isotopic composition of airborne Mo. In this study, the δ^98/95Mo values measured for the different urban sampling sites and reported relative to SRM 3134, ranged from ?0.18 to +0.94 ‰. The results of this investigation suggest that measurements of Mo concentrations and isotopic compositions have the potential to trace anthropogenic emissions in an urban environment.     

Yield of near-target product interaction of 47 MeV/A12C ions with bismuth targets

Formation cross sections of near-target products from the reaction of 47MeV/A¹²C with²⁰⁹Bi targets have been measured. Their independent yields were obtained from their cumulative and partially cumulative yields according to the experimental data measured in this work and correction for mother-daughter decay. From the yield distribution curves of Pt, Au and Hg isotopes constructed it was found that for their peak positions at mass numbers A=188.1, 190.9 and 195.8, the widths of charge distributions are = 3.08, 2.80 and 3.74, respectively. The formation cross sections for some near-target neutron-rich new isotopes were extrapolated from the isotopic yield distribution curves.     

The determination of molybdenum in geological samples by Neutron Activation Analysis

A metal-silicate extraction technique combined with neutron activation analysis has been developed to determine molybdenum in geological samples. The samples are equilibrated with Femetal powder at high temperatures. Molybdenum is completely extracted into the metal phase because of very reducing conditions in the furnace. The metal spherule is separated from the silicates, irradiated and dissolved in an acid solution. The molybdenum is precipitated as a sulfide and the precipitate is dissolved in aqua regia and counted on a Ge/Li/detector. The radiochemical yield is obtained by irradiation of the solution. The method avoids production of⁹⁹Mo from induced fission of²³⁵U by performing the metal-silicate separation before irradiation. The precipitation step may be necessary to remove the high background from the decay of⁵⁹Fe. Mo concentrations down to 15 ng/g have been obtained using this method.