Silicon control of strontium and cesium partitioning in hydroxide-weathered sediments

Cation partitioning and speciation in an aqueous soil suspension may depend on the coupling of reaction time, sorbate amount and mineral weathering reactions. These factors were varied in sediment suspension experiments to identify geochemical processes that affect migration of Sr²⁺ and Cs⁺ introduced to the subsurface by caustic high level radioactive waste (HLRW). Three glacio-fluvial and lacustrine sediments from the Hanford Site (WA, USA) were subjected to hyperalkaline (pH > 13), Na-Al-NO₃-OH solution conditions within a gradient field of (i) sorptive concentration (10^-5-10^-3 m) and (ii) reaction time (0-365 d). Strontium uptake (q_Sr) exceeded that of cesium at nearly all reaction times. Sorbent affinity for both Cs⁺ and Sr²⁺ increased with clay plus silt content at early times, but a prolonged slow uptake process was observed over the course of sediment weathering that erased the texture effect for Sr²⁺; all sediments showed similar mass normalized uptake after several months of reaction time. Strontium became progressively recalcitrant to desorption after 92 d, with accumulation and aging of neoformed aluminosilicates. Formation of Cs⁺ and Sr²⁺-containing cancrinite and sodalite was observed after 183 d by SEM and synchrotron μ-XRF and μ-XRD. EXAFS data for q_Sr ≈ 40 mmol kg^-1 showed incorporation of Sr²⁺ into both feldspathoid and SrCO₃(s) coordination environments after one year. Adsorption was predominant at early times and low sorbate amount, whereas precipitation, controlled largely by sediment Si release, became increasingly important at longer times and higher sorbate amount. Kinetics of contaminant desorption at pH 8 from one year-weathered sediments showed significant dependence on background cation (Ca²⁺ versus K⁺) composition. Results of this study indicate that co-precipitation and ion exchange in neoformed aluminosilicates may be an important mechanism controlling Sr²⁺ and Cs⁺ mobility in siliceous sediments impacted by hyperalkaline HLRW.