Thermodynamic determination of condensation behavior for the precursory elements of radioxenon following an...

The measurement of radioactive xenon isotopes (radioxenon) in the atmosphere is a tool used to detect underground nuclear explosions, provided that some radioxenon escaped containment and that fractionation leading to the alteration of the relative proportions of these isotopes, is accounted for. After the explosion, volatilization followed by melting of the surrounding rocks produces a magma where the more refractory radioactive species get dissolved while the more volatile ones contribute to the gas phase that might escape. Indium, tin, antimony, tellurium and iodine are the main fission products involved in the decay chains leading to radioxenon. In this study, condensation as a function of temperature for these precursors of radioxenon were determined using thermodynamic calculations for systems with complex chemical composition corresponding to major environments of known underground nuclear explosions and for a range of pressure values representative of the cavity evolution. Our results illustrate a large difference between the relevant condensation temperatures for the radioxenon precursors and the tabulated boiling temperatures of the pure compounds often used as indicators of their volatility. For some precursory elements such as tin, the often-considered Heaviside function represents an oversimplification of the concept of condensation temperature, as condensation occurs over a temperature range as large as 2000 K. This results from the speciation of the elements in the gas phase mainly driven by the formation of oxides. Condensation also strongly depends on pressure while it moderately depends on the bulk chemical composition of the system. This study shows the importance and complexity of the condensation process following underground nuclear explosions. It also shows how thermodynamic computations allow the prediction of the quantity and the relative proportions of radioactive xenon isotopes in the gas phase in the presence of magma, before their potential emission to the atmosphere. Better detection, discrimination and understanding of underground nuclear explosions should arise by taking into account the fractionation resulting from the condensation of the radionuclides producing radioxenon in nuclear cavities.