Pu distribution among mixed waste components at the Hanford legacy site, USA and implications to long-term migration

Abstract

Beginning in 1943, process wastes containing approximately 1.85 × 1015 Bq (200 kg) of plutonium (Pu) were released into unlined cribs, trenches, and field tiles at the Hanford Site, Washington, USA. The 216-Z-9 (Z-9) unlined trench received over 4 × 106 L of mixed Pu processing waste from the Plutonium Finishing Plant (PFP) consisting of high ionic strength (∼ 5 M nitrate, ∼ 0.6 M aluminum), acidic (pH ∼ 2.5) solutions, which also contained the organic solvents: tributyl phosphate (TBP), dibutyl butylphosphonate (DBBP), carbon tetrachloride (CCl4), and lard oil. A small fraction of Pu migrated deep into the subsurface vadose zone to depths of 37 m, but the mechanisms controlling Pu migration beneath the trench are unknown. In this study, we determined Pu partitioning behavior in a series of binary and ternary batch experiments containing aqueous, organic, and solid phases representative of the waste constituents and natural sediments of the Z-9 trench in order to develop a conceptual model for the transport of Pu in the subsurface. Our results show that Pu at equilibrium with low pH, high nitrate waste and in the presence of a TBP/organic phase can migrate as a Pu-TBP-nitrate complex in the organic phase as long as the low pH and high nitrate concentrations are maintained. Reducing the nitrate concentrations or increasing the pH will lead to Pu partitioning into the aqueous phase from the organic phase with subsequent sorption to native Hanford sediments. The results of this work suggest that Pu migration in the subsurface is likely driven by weak sorption of aqueous Pu under low pH conditions as well as the formation of Pu-TBP-nitrate complexes in the organic phase. Long-term Pu migration will be limited by the transient nature of the low pH conditions and the dispersion of the nitrate plume.