Comment on “Hydrolysis of neptunium(V) at variable temperatures (10-85 °C)” by L. Rao, T.G. Srinivasan, A.Yu. Garnov, P. Zanonato, P. Di Bernardo, and A. Bismondo

In a recent study [Rao, L., Srinivasan, T.G., Garnov, A.Yu., Zanonato, P., Di Bernardo, P., Bismondo, A., 2004. Hydrolysis of neptunium(V) at variable temperatures (10-85 °C). Geochim. Cosmochim. Acta 68, 4821-4830.] the hydrolysis of Np(V) was investigated at 10-85 °C by absorption spectroscopy, potentiometry, and microcalorimetry along the titration of Np(V) solutions with tetramethylammonium hydroxide up to pH 10. However, there is strong evidence that the precautions to avoid competing reactions with carbonate were not sufficient and that the measured effects are not caused by the formation of Np(V) hydroxide complexes but primarily by the formation of Np(V) carbonate complexes. The reported equilibrium constants, enthalpies, entropies, and heat capacities for the complexes NpO2OH(aq) and NpO2(OH)2- are severely in error and must not be used for the geochemical modeling of neptunium. If the hydrolysis constants reported by Rao et al. [Rao, L., Srinivasan, T.G., Garnov, A.Yu., Zanonato, P., Di Bernardo, P., Bismondo, A., 2004. Hydrolysis of neptunium(V) at variable temperatures (10-85 °C). Geochim. Cosmochim. Acta 68, 4821-4830] are used to calculate neptunium solubilities in alkaline solutions relevant for nuclear waste repositories, the Np(V) concentrations are overestimated by orders of magnitude.