A Literature Survey to Identify Potentially Volatile Iodine-Bearing Species Present in Off-Gas Streams
Four radionuclides have been identified as being sufficiently volatile in the reprocessing of nuclear fuel that their gaseous release needs to be controlled to meet regulatory requirements (Jubin et al. 2011, 2012). These radionuclides are 3H, 14C, 85Kr, and 129I. Of these, 129I has the longest half-life and potentially high biological impact. Accordingly, control of the release of 129I is most critical with respect to the regulations for the release of radioactive material in stack emissions. It is estimated that current EPA regulations (EPA 2010) would require any reprocessing plant in the United States to limit 129I release to less than 0.05 Ci/MTIHM for a typical fuel burnup of 55 gigawatt days per metric tonne (GWd/t) (Jubin 2011). The study of inorganic iodide in off-gas systems has been almost exclusively limited to I2 and the focus of organic iodide studies has been CH3I. In this document, we provide the results of an examination of publically available literature that is relevant to the presence and sources of both inorganic and organic iodine-bearing species in reprocessing plants. We especially focus on those that have the potential to be poorly sequestered with traditional capture methodologies. Based on the results of the literature survey and some limited thermodynamic modeling, the inorganic iodine species hypoiodous acid (HOI) and iodine monochloride (ICl) were identified as potentially low-sorbing iodine species that could present in off-gas systems. Organic species of interest included both short chain alkyl iodides such as methyl iodide (CH3I) and longer alkyl iodides up to iodododecane (C10H21I). It was found that fuel dissolution may provide conditions conducive to HOI formation and has been shown to result in volatile long-chain alkyl iodides, though these may not volatilize until later in the reprocessing sequence. Solvent extraction processes were found to be significant sources of various organic iodine-bearing species; formation of these was facilitated by the presence of radiolytic decomposition products resulting from radiolysis of tri-n-butyl phosphate and dodecane. Primarily inorganic iodine compounds were expected from waste management processes, including chlorinated species such as ICl. Critical knowledge gaps that must still be addressed include confirmation of the existence and quantification of low-sorbing species in the off-gas of reprocessing facilities. The contributions from penetrating forms of iodine to the plant DF are largely unknown and highly dependent on the magnitude of their presence. These species are likely to be more difficult to remove and it is likely that their sequestration could be improved through the use of different sorbents, through design modifications of the off-gas capture system, or through chemical conversion prior to iodine abatement that would produce more easily captured forms.