Neptunium(V) sorption to goethite at attomolar to micromolar concentrations

Sorption of 10(-18)-10(-5)M neptunium (Np) to goethite was examined using liquid scintillation counting and gamma spectroscopy. A combination approach using (239)Np and long lived (237)Np was employed to span this wide concentration range. (239)Np detection limits were determined to be 2×10(-18)M and 3×10(-17)M for liquid scintillation counting and gamma spectroscopy, respectively. Sorption was found to be linear below 10(-11)M, in contrast to the non-linear behavior observed at higher concentrations both here and in the literature. 2-site and 3-site Langmuir models were used to simulate sorption behavior over the entire 10(-18)-10(-5)M range. The 3-site model fit yielded Type I and II site densities of 3.56 sites/nm(2) (99.6%) and 0.014±0.007 sites/nm(2) (0.4±0.1%), consistent with typical "high affinity" and "low affinity" sites reported in the literature [21]. Modeling results for both models suggest that sorption below ~10(-11)M is controlled by a third (Type III) site with a density on the order of ~7×10(-5)sites/nm(2) (~0.002%). While the nature of this "site" cannot be determined from isotherm data alone, the sorption data at ultra-low Np concentrations indicate that Np(V) sorption to goethite at environmentally relevant concentrations will be (1) linear and (2) higher than previous (high concentration) laboratory experiments suggest.