Laboratory actinide partitioning: Whitlockite/liquid and influence of actinide concentration levels

Abstract

Fission and alpha track radiography techniques have been used to measure partition coefficients (D) at trace (ppm) concentration levels for the actinide elements Th, U, and Pu between synthetic whitlockite and coexisting "haplobasaltic" silicate liquid at 1 bar pressure and 1250°C at oxygen fugacities from 10^(−8.5) and 10^(−0.7) bars. Pu is much more readily incorporated into crystalline phases than is U or Th under reducing conditions (fO_2 = 10^(−8.5)), because Pu is primarily trivalent, whereas U and Th are tetravalent. Definitive valence state assignments cannot be made, but our best estimates of corrected partition coefficients for Pu^(+3), Pu^(+4), Th^(+4), U^(+4), and U^(+6) are, for whitlockite 3.6/<⩽0.6/1.2/0.5/⩽0.002. The effect of changing pressure and liquidus temperature is relatively small, which probably reflects a weak temperature dependence for D (whitlockite) but possibly could be due to cancellation of opposing temperature and pressure effects. Comparison of experiments at trace U levels with those containing percent concentrations of UO_2 indicate that Si is involved in the substitution of U in whitlockite with U + 2Si ⇄ Ca + 2P being the most likely mechanism. D_u is lower. 0.3 vs 0.5. at percent levels compared to 20 ppm. This is best explained by the effect of U on melt structure or by a decrease in the fraction of tetravalent U at high U concentrations.

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