A biogeochemical framework for bioremediation of plutonium(V) in the subsurface environment

Accidental release of plutonium (Pu) from storage facilities in the subsurface environment is a concern for the safety of human beings and the environment. Given the complexity of the subsurface environment and multivalent state of Pu, we developed a quantitative biogeochemical framework for bioremediation of Pu(V)O(2) (+) in the subsurface environment. We implemented the framework in the biogeochemical model CCBATCH by expanding its chemical equilibrium for aqueous complexation of Pu and its biological sub-models for including Pu's toxicity and reduction reactions. The quantified framework reveals that most of the Pu(V) is speciated as free Pu(V)O(2) (+) ((aq)), which is a problem if the concentration of free Pu(V)O(2) (+) is ≥28 μM (the half-maximum toxicity value for bacteria able to reduce Pu(V) to Pu(III)PO(4(am))) or ≥250 μM (the full-toxicity value that takes the bioreduction rate to zero). The framework includes bioreduction of Fe(3+) to Fe(2+), which abiotically reduces Pu(V)O(2) (+) to Pu(IV) and then to Pu(III). Biotic (enzymatic) reduction of Pu(V)O(2) (+) directly to Pu(III) by Shewanella alga (S. alga) is also included in the framework. Modeling results also reveal that for formation of Pu(III)PO(4(am)), the desired immobile product, the concentration of coexisting model strong ligand-nitrilotriacetic acid (NTA)-should be less than or equal to the concentration of total Pu(III).