The aqueous chemistry of polonium (Po) in environmental and anthropogenic processes

The longest-lived naturally occurring isotope of polonium is polonium-210, one of the daughters of uranium-238 (138 days half-life). As a daughter radionuclide of radon-222, polonium-210 can become enriched in pore fluids in U-bearing rocks, leading to contents in excess of 100 Bq.g^-1 in some products from the mineral, coal, oil and gas industries (e.g., anode slimes in copper refinement; sludge from the oil and gas industry). Since 2006, IAEA recommendation limits require polonium and other radionuclides from the U- and Th-series decay to be regulated for products and wastes that contain >1 Bq.g^-1, which results in the classification of large amounts of industrial products and waste as radioactive. To develop effective methods for polonium removal and/or control, it is necessary to acquire an understanding of its aqueous chemistry. Based on a review of available experimental data, we developed a self-consistent thermochemical model for polonium in inorganic aqueous solutions. Polonium exists mainly in two oxidation states in aqueous solutions: Po(IV) and Po(II). The importance of Po(II) is unique, as Te(II) or Se(II) complexes do not appear to play a significant role in aqueous solution at room temperature. The model is used to discuss polonium speciation in some environmental and process waters.