Plutonium oxidation states in the Waste Isolation Pilot Plant repository

• Published in: Applied geochemistry 2020-05, Vol.116, p.104561, Article 104561
• Main Authors: Schramke, J.A., Santillan, E.F.U., Peake, R.T.
• Format: Article
• Language: English
• Subjects: Oxidation states; Plutonium; Redox; Solubility; Speciation; Transuranic; Waste disposal
• ISSN: 0883-2927; 1872-9134
• DOI: 10.1016/j.apgeochem.2020.104561

The Waste Isolation Pilot Plant (WIPP), a deep geologic repository located 660 m underground in bedded salt, is designed to isolate U.S. defense-related transuranic waste from the accessible environment. Plutonium isotopes are the most important radionuclides in WIPP waste. Plutonium solubility in WIPP brines (ionic strengths from 5.3 to 7.4) is strongly dependent on its oxidation state, with much lower solubilities associated with Pu(III) and Pu(IV) than with the higher Pu(V) and Pu(VI) oxidation states. The large quantity of metallic iron in WIPP waste and waste containers is expected to undergo anoxic corrosion, producing strongly reducing conditions and high hydrogen gas pressures after repository closure and brine intrusion. Because reducing conditions will prevail in the WIPP repository, the most important long-term oxidation states will be Pu(III) and Pu(IV). We performed a literature review to evaluate the effects of WIPP chemical and physical processes on dissolved (not colloidal) plutonium oxidation states that included reactions with reducing agents such as iron solids and aqueous species and radiolysis of solids and aqueous species. The results of this review indicate that equilibrium between Pu(III) solids and aqueous species will control dissolved plutonium concentrations in WIPP brines. We also performed geochemical modeling calculations using the ThermoChimie database to support this assessment of plutonium oxidation states in the long-term WIPP repository. Control of plutonium solubilities by Pu(III) solid instead of Pu(IV) solid may lead to higher predicted plutonium concentrations in brines potentially released to the ground surface by an inadvertent drilling intrusion into the long-term WIPP repository. The results of this study demonstrate that Pu(III) solid solubilities provide a reasonable upper bound for dissolved plutonium concentrations in WIPP brines. •Anoxic Fe metal corrosion will make the long-term WIPP environment highly reducing.•Anoxic Fe metal corrosion will stabilize Pu(III) aqueous and solid species in WIPP.•Pu(III) solid will control aqueous Pu solubilities under long-term WIPP conditions.•SIT modeling provides a qualitative assessment of Pu redox in reducing conditions.•Accurate modeling of actinides in brines requires additional Pitzer data.