AbstractThe gamma radiolytic degradation behavior of n‐dodecane (n‐DD) was investigated under conditions both with and without the presence of nitric acid. The physicochemical property alterations due to radiolysis were quantified and compared against an unirradiated system. Compositional changes in n‐DD post radiolysis was measured, and the degraded n‐DD was characterized using Fourier‐transform infrared (FT‐IR) spectroscopy, gas chromatography (GC), and gas chromatography–mass spectrometry (GC–MS) analysis. The presence of nitric acid was observed to accelerate the radiolytic degradation of n‐DD. The extent of diluent degradation caused by gamma irradiation was assessed through the retention behavior of uranium [U(VI)], plutonium [Pu(IV)], and zirconium [Zr(IV)] in 1.1 M tri‐n‐butyl phosphate (TBP) in irradiated diluent. Furthermore, the effectiveness of hydrazine carbonate (HC) as a solvent wash reagent for the removal of diluent degradation products was evaluated.