Recovery of high specific activity molybdenum-99 from accelerator-induced fission on low-enriched uranium for technetium-99m generators.

A new process was developed to recover high specific activity (no carrier added) 99Mo from electron-accelerator irradiated U3O8 or uranyl sulfate targets. The process leverages a novel solvent extraction scheme to recover Mo using di(2-ethylhexyl) phosphoric acid following uranium and transuranics removal with tri-n-butyl phosphate. An anion-exchange concentration column step provides a final purification, generating pure 99Mo intended for making 99Mo/99mTc generators. The process was demonstrated with irradiated uranium targets resulting in more than 95% 99Mo recovery and without presence of fission products or actinides in the product.

Speciation of Molybdenum(VI) in Chloride Media at Elevated Mo Concentrations.

Speciation of Mo(VI) in chloride media (0.5-11 M HCl) at elevated Mo concentrations (0.1-300 mM Mo) was investigated using UV spectroscopy. In addition to five major monomeric species, H2MoO4, H3MoO4 +, H3MoO4Cl, MoO2Cl2, and MoO2Cl3 -, chemometric analysis of UV spectra suggests the presence of three cationic dinuclear species that predominate in solutions of 1-4.5 M HCl at >20 mM Mo concentrations. Thermodynamic values and molar absorptivity spectra were calculated from UV spectrophotometric data using refined numerical methods. The stability constants determined for three Mo dimers are log ß = 3.53 ± 0.05 (H2Mo2O5 2+), log ß = 3.60 ± 0.04 (H3Mo2O5 3+), and log ß = 2.91 ± 0.03 (H3Mo2O6Cl2+).

Fission-Produced 99Mo Without a Nuclear Reactor.

99Mo, the parent of the widely used medical isotope 99mTc, is currently produced by irradiation of enriched uranium in nuclear reactors. The supply of this isotope is encumbered by the aging of these reactors and concerns about international transportation and nuclear proliferation. Methods: We report results for the production of 99Mo from the accelerator-driven subcritical fission of an aqueous solution containing low enriched uranium. The predominately fast neutrons generated by impinging high-energy electrons onto a tantalum convertor are moderated to thermal energies to increase fission processes. The separation, recovery, and purification of 99Mo were demonstrated using a recycled uranyl sulfate solution. Conclusion: The 99Mo yield and purity were found to be unaffected by reuse of the previously irradiated and processed uranyl sulfate solution. Results from a 51.8-GBq 99Mo production run are presented.

Spatio-temporal modelling as a way to reconstruct patterns of past human activities.

This paper examines the possibilities of creating quantified models of past human activities in both time and space. The study area lies in the southeastern Czech Republic and western Slovakia. The spatio-temporal model of behavioural categories was calculated with the help of Monte Carlo simulations and statistical testing. One of the main advantages of our approach is that it admits the probabilistic nature of input data, quantifies them and provides probabilistic results comparable with other proxies. It also presents a less biased way of how archaeological data from regions and periods with low numbers of 14C datings can be incorporated into models of past population dynamics.

Population and forest dynamics during the Central European Eneolithic (4500-2000 BC).

The population boom-and-bust during the European Neolithic (7000-2000 BC) has been the subject of lively discussion for the past decade. Most of the research on this topic was carried out with help of summed radiocarbon probability distributions. We aim to reconstruct population dynamics within the catchment of a medium sized lake on the basis of information on the presence of all known past human activities. We calculated a human activity model based on Monte Carlo simulations. The model showed the lowest level of human activity between 4000 and 3000 BC. For a better understanding of long-term socio-environmental dynamics, we also used the results of a pollen-based quantitative vegetation model, as well as a local macrophysical climate model. The beginning of the decline of archaeologically visible human activities corresponds with climatic changes and an increase in secondary forest taxa probably indicating more extensive land-use. In addition, important social and technological innovations, such as the introduction of the ard, wheel, animal traction and metallurgy, as well as changes in social hierarchy characterizing the same period.

The origin of grasslands in the temperate forest zone of east-central Europe: long-term legacy of climate and human impact.

The post-glacial fate of central European grasslands has stimulated palaeoecological debates for a century. Some argued for the continuous survival of open land, while others claimed that closed forest had developed during the Middle Holocene. The reasons behind stability or changes in the proportion of open land are also unclear. We aim to reconstruct regional vegetation openness and test the effects of climate and human impact on vegetation change throughout the Holocene. We present a newly dated pollen record from north-western fringes of the Pannonian Plain, east-central Europe, and reconstruct Holocene regional vegetation development by the REVEALS model for 27 pollen-equivalent taxa. Estimated vegetation is correlated in the same area with a human activity model based on all available archaeological information and a macrophysical climate model. The palaeovegetation record indicates the continuous presence of open land throughout the Holocene. Grasslands and open woodlands were probably maintained by local arid climatic conditions during the early Holocene delaying the spread of deciduous (oak) forests. Significantly detectable human-made landscape transformation started only after 2000 BC. Our analyses suggest that Neolithic people spread into a landscape that was already open. Humans probably contributed to the spread of oak, and influenced the dynamics of hazel and hornbeam.

Redox reactions of Pu(IV) and Pu(III) in the presence of acetohydroxamic acid in HNO(3) solutions.

The reduction of Pu(IV) in the presence of acetohydroxamic acid (HAHA) was monitored by vis-NIR spectroscopy. All experiments were performed under low HAHA/Pu(IV) ratios, where only the Pu(IV)-monoacetohydroxamate complex and Pu uncomplexed with HAHA were present in relevant concentrations. Time dependent concentrations of all absorbing species were resolved using molar extinction coefficients for Pu(IV), Pu(III), and the Pu(AHA)(3+) complex by deconvolution of spectra. From fitting of the experimental data by rate equations integrated by a numeric method three reactions were proposed to describe a mechanism responsible for the reduction and oxidation of plutonium in the presence of HAHA and HNO(3). Decomposition of Pu(AHA)(3+) follows a second order reaction mechanism with respect to its own concentration and leads to the formation of Pu(III). At low HAHA concentrations, a two-electron reduction of uncomplexed Pu(IV) with HAHA also occurs. Formed Pu(III) is unstable and slowly reoxidizes back to Pu(IV), which, at the point when all HAHA is decomposed, can be catalyzed by the presence of nitrous acid.

Spectroscopic study of the uranyl-acetohydroxamate adduct with tributyl phosphate.

The ultraviolet-visible (UV-Vis) and Fourier transform infrared (FT-IR) spectroscopic studies carried out for the system UO2(NO3)/AHA/TBP (uranyl-acetohydroxamate-tributyl phosphate) confirmed the presence of the adduct of UO2(NO3)(AHA) 2TBP with 1:1 stoichiometry for UO2:AHA (acetohydroxamic acid). The spectrum of this complex is identical to the infrared spectrum of the organic phase formed in the uranium distribution experiments with 30% TBP/n-dodecane and AHA present in aqueous phase. Disappearance of the hydroxyl stretching band and a shift in the position of the carbonyl band in the infrared spectra revealed that both the hydroxyl and the carbonyl group of acetohydroxamic acid are involved in the chelate ring with uranium. Also, acetic acid, accrued after acidic hydrolysis of acetohydroxamic acid, was identified in the extraction organic phase.