Enthalpy of Uranium Adsorption onto Hematite
Shanna L. Estes, Brian A. Powell
Abstract
The influence of temperature on the adsorption of metal ions at the solid–water interface is often overlooked, despite the important role that adsorption plays in metal-ion fate and transport in the natural environment where temperatures vary widely. Herein, we examine the temperature-dependent adsorption of uranium, a widespread radioactive contaminant, onto the ubiquitous iron oxide, hematite. The multitemperature batch adsorption data and surface complexation models indicate that the adsorption of uranium, as the hexavalent uranyl (UO22+) ion, increases significantly with increasing temperature, with an adsorption enthalpy (ΔHads) of +71 kJ mol–1. We suggest that this endothermic, entropically driven adsorption behavior is linked to reorganization of the uranyl-ion hydration and interfacial water structures upon UVI adsorption at the hematite surface. Overall, this work provides fundamental insight into the thermodynamics driving metal-ion adsorption reactions and provides the specific enthalpy value necessary for improved predictive geochemical modeling of UVI adsorption in the environment.