Desorption kinetics of radiocesium from subsurface sediments at Hanford Site, USA

Authors

Chongxuan Liu, Pacific Northwest National LaboratoryFollow
John M. Zachara, Pacific Northwest National LaboratoryFollow
Steven Smith, Pacific Northwest National LaboratoryFollow
James Mckinley, Pacific Northwest National LaboratoryFollow
Calvin Ainsworth, Pacific Northwest National Laboratory

Date of this Version

2003

Citation

Geochimica et Cosmochimica Acta, Vol. 67, No. 16, pp. 2893–2912, 2003

Abstract

The desorption of ¹³⁷Cs⁺ was investigated on sediments from the United States Hanford site. Pristine sediments and ones that were contaminated by the accidental release of alkaline ¹³⁷Cs⁺ -containing high level nuclear wastes (HLW, 2 X 10⁶ to 6 X 10⁷ pCi ¹³⁷Cs⁺/g) were studied. The desorption of ¹³⁷Cs⁺ was measured in Na⁺, K⁺, Rb⁺, and NH₄⁺ electrolytes of variable concentration and pH, and in presence of a strong Cs⁺-specific sorbent (self-assembled monolayer on a mesoporous support, SAMMS). ¹³⁷Cs⁺ desorption from the HLW-contaminated Hanford sediments exhibited two distinct phases: an initial instantaneous release followed by a slow kinetic process. The extent of ¹³⁷Cs⁺ desorption increased with increasing electrolyte concentration and followed a trend of Rb⁺ ≥ K⁺ > Na⁺ at circumneutral pH. This trend followed the respective selectivities of these cations for the sediment. The extent and rate of ¹³⁷Cs⁺ desorption was influenced by surface armoring, intraparticle diffusion, and the collapse of edge-interlayer sites in solutions containing K⁺, Rb⁺, or NH⁴⁺. Scanning electron microscopic analysis revealed HLW-induced precipitation of secondary aluminosilicates on the edges and basal planes of micaceous minerals that were primary Cs⁺ sorbents. The removal of these precipitates by acidified ammonium oxalate extraction significantly increased the long-term desorption rate and extent. X-ray microprobe analyses of Cs⁺-sorbed micas showed that the ¹³⁷Cs⁺ distributed not only on mica edges, but also within internal channels parallel to the basal plane, implying intraparticle diffusive migration of ¹³⁷Cs⁺. Controlled desorption experiments using Cs-spiked pristine sediment indicated that the ¹³⁷Cs⁺ diffusion rate was fast in Na⁺-electrolyte, but much slower in the presence of K⁺ or Rb⁺, suggesting an effect of edge-interlayer collapse. An intraparticle diffusion model coupled with a two-site cation exchange model was used to interpret the experimental results. Model simulations suggested that about 40% of total sorbed ¹³⁷Cs⁺ was exchangeable, including equilibrium and kinetic desorbable pools. At pH 3, this ratio increased to 60–80%. The remainder of the sorbed ¹³⁷Cs⁺ was fixed or desorbed at much slower rate than our experiments could detect.