title: Surface complexation model for strontium sorption to amorphous silica and goethite.
abstract: Strontium sorption to amorphous silica and goethite was measured as a function of pH and dissolved strontium and carbonate concentrations at 25 degrees C. Strontium sorption gradually increases from 0 to 100% from pH 6 to 10 for both phases and requires multiple outer-sphere surface complexes to fit the data. All data are modeled using the triple layer model and the site-occupancy standard state; unless stated otherwise all strontium complexes are mononuclear. Strontium sorption to amorphous silica in the presence and absence of dissolved carbonate can be fit with tetradentate Sr2+ and SrOH+ complexes on the beta-plane and a monodentate Sr2+complex on the diffuse plane to account for strontium sorption at low ionic strength. Strontium sorption to goethite in the absence of dissolved carbonate can be fit with monodentate and tetradentate SrOH+ complexes and a tetradentate binuclear Sr2+ species on the beta-plane. The binuclear complex is needed to account for enhanced sorption at hgh strontium surface loadings. In the presence of dissolved carbonate additional monodentate Sr2+ and SrOH+ carbonate surface complexes on the beta-plane are needed to fit strontium sorption to goethite. Modeling strontium sorption as outer-sphere complexes is consistent with quantitative analysis of extended X-ray absorption fine structure (EXAFS) on selected sorption samples that show a single first shell of oxygen atoms around strontium indicating hydrated surface complexes at the amorphous silica and goethite surfaces. Strontium surface complexation equilibrium constants determined in this study combined with other alkaline earth surface complexation constants are used to recalibrate a predictive model based on Born solvation and crystal-chemistry theory. The model is accurate to about 0.7 log K units. More studies are needed to determine the dependence of alkaline earth sorption on ionic strength and dissolved carbonate and sulfate concentrations for the development of a robust surface complexation database to estimate alkaline earth sorption in the environment.
authors.affiliation: Chemistry, Materials, Earth, and Life Sciences Directorate, Lawrence Livermore National Laboratory, Livermore, California, USA. carroll6@llnl.gov
authors.forename: Susan A
authors.initials: SA
authors.lastname: Carroll
authors.forename: Sarah K
authors.initials: SK
authors.lastname: Roberts
authors.forename: Louise J
authors.initials: LJ
authors.lastname: Criscenti
authors.forename: Peggy A
authors.initials: PA
authors.lastname: O'Day