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Kinetics of neptunium sorption and desorption in the presence of aluminum (hydr)oxide minerals: Evidence for multi-step desorption at low pH.

Author(s) Baumer, T.; Hixon, A.E.
Journal J Environ Radioact
Date Published 2019 Sep

Kinetics analyses of sorption and desorption provide important insight into reaction mechanisms occurring at the mineral-water interface. They are also needed to determine when equilibrium is achieved, identify intermediate chemical species, and inform models describing neptunium mobility. Neptunium sorption to and desorption from four different aluminum (hydr)oxides - bayerite (α-Al(OH)), gibbsite (γ-Al(OH)), corundum (α-AlO), and γ-alumina (γ-AlO) - were investigated as a function of mineral concentration (5 - 170 m L), neptunium concentration (10 - 10 M), and pH (5.5 - 10.5). Neptunium sorption was characterized by a two-step reaction with an initial fast sorption step occurring within minutes followed by a slower equilibrium process, which was attributed to initial sorption of neptunium to a small number of strong sorption sites followed by sorption of neptunium to a larger number of weak sorption sites. The kinetics data were modeled using the linear and non-linear forms of the pseudo-first and pseudo-second order rate equations and the goodness of fit parameters were compared. Non-linear pseudo-second order rate constants described neptunium sorption to aluminum (hydr)oxides most accurately and were used to determine the reaction orders with respect to mineral concentration and [H]. Neptunium desorption experiments demonstrated that the desorption mechanism changed as a function of pH and that the forward and reverse reactions were not equivalent. At pH ≥ 7.5, desorption reached steady-state within an hour and was accurately described by the non-linear pseudo-second order rate equations. A desorption plateau was observed at pH 5.5 that could not be described by either pseudo-first or -second order kinetics, suggesting the possibility of a multi-step desorption reaction. The comparatively slow desorption kinetics observed here suggests that sorbed neptunium could be slowly released back into the aqueous phase and act as a continuous source of contamination to the environment.

DOI 10.1016/j.jenvrad.2019.05.006
Keywords Adsorption; Aluminum Hydroxide; Aluminum Oxide; Hydrogen-Ion Concentration; Kinetics; Minerals; Neptunium
ISSN 1879-1700
Citation Baumer T, Hixon AE. Kinetics of neptunium sorption and desorption in the presence of aluminum (hydr)oxide minerals: Evidence for multi-step desorption at low pH. J Environ Radioact. 2019;205-206:72-78.