A scheme was developed for the determination of oxidation states of plutonium in environmental samples. The method involves a combination of solvent extractions and coprecipitation. It was tested on solutions with both high-level and trace-level concentrations. The scheme was used to determine Pu oxidation states in solutions from solubility experiments in groundwater from a potential nuclear waste disposal site. At steady-state conditions, Pu was found to be soluble predominantly as Pu(V) and Pu(VI).