Abstract
Tributylphosphate (TBP) dimers, formed during radiolysis of the nuclear fuel reprocessing solvent, were studied using tandem mass spectrometry (MS/MS), stable isotopic labelling (2H) and synthetic model compounds. The structures of isomeric dimers and their lower homologues were established, using GC/MS as well as electron impact and chemical ionisation GC/tandem mass spectrometry, with an extensive use of ion chromatograms of characteristic fragment ions from collision-induced decomposition in both non-deuterated and selectively deuterated series. An explanation of isomer ratios and of the restricted number of lower homologues as well as a radiolytic mechanism are advanced. The TBP-dimer fraction represented less than ∼0.03% of the total mixture obtained from radiolysis of solvent.
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