The speciation, transformation kinetics and fate of spiked Pu (IV) in highly saline groundwater

Abstract

The mobility of plutonium (Pu) in groundwater is dependent of its speciation distribution and transformation. The speciation and transformation kinetics of Pu(IV) and its colloids in highly saline groundwater have, however, been rarely studied. In the present study, groundwater (Ionic strength 1 M) from Dunhuang region, NW China, was collected for investigating the speciation, transformation kinetics and fate of spiked Pu (IV) with aging time. The results showed that ~99% of the spiked Pu (IV) (over initial concentration c0 range 2.5 × 10−10–7.8 × 10−7 mol·L−1) was easily associated with the natural colloids and transformed into relatively unstable Pu pseudo-colloids in 1 day, which then gradually deposited and/or adsorbed on the container walls with aging. The suspended Pu pseudo-colloids decreased in similar exponential models, with rate equations r(t) = −3.1 × 10−10e– t/4 and −1.3 × 10−8e–/3 for c0 = 1.25 × 10−9 mol·L−1and 4.17 × 10−8 mol·L−1, respectively. The chemical speciation of the suspended colloidal Pu was dominated by “Fe/Mn Oxides” at the early time, while “Carbonates” with slower depositing rate (r(t) = −6.9 × 10−12e– 0.149t) dominated it (~82%) at equilibrium state. Whatever the c0 was, the concentration of dissolved Pu (i.e., the apparent solubility of Pu) kept at 0.7 × 10−11 mol·L−1 over aging. The valence of dissolved Pu was dominated by Pu(IV) at early time, while Pu(V + VI) would become dominant (~95%) at equilibrium state with transformation rate of r(t) = −92.9e– t/16.6 + 96.9. The equilibrium times of Pu deposition (and/or adsorption), speciation transformation of the suspended colloidal Pu, and valence change of the dissolved Pu were 30 d, 80 d and 120 d, respectively. The kinetic process for each Pu species could be well fitted with exponential model. These results suggest that the majority of released Pu(IV) into highly saline groundwater will be easily associated with natural aquatic colloids and then become immobile in short time due to deposition (and/or adsorption) onto the environmental medium, but potential migration risk caused by stable suspended Pu colloids cannot be ignored.