Environmental Speciation of Actinides

TLDR

Light actinides such as Th, Pa, U, Np, Pu, Am, and Cm, though scarce in the crust and seawater, are significant environmental contaminants from mining, nuclear energy, and legacy waste, and their solubility, transport, bioavailability, and toxicity depend on speciation. This review examines the abundance, production, and environmental sources of naturally occurring and some man‑made light actinides. The authors review aqueous speciation of U, Np, and Pu across pH and Eh ranges, their interactions with inorganic and organic ligands, minerals, colloids, gels, natural organic matter, and microbes, and discuss speciation and remediation histories at major DOE sites. Surface interactions can either inhibit or enhance the dispersal of light actinides, and in some cases alter their oxidation states, thereby influencing the behavior of redox‑sensitive actinides such as U, Np, and Pu.

Abstract

Although minor in abundance in Earth's crust (U, 2–4 ppm; Th, 10–15 ppm) and in seawater (U, 0.003 ppm; Th, 0.0007 ppm), light actinides (Th, Pa, U, Np, Pu, Am, and Cm) are important environmental contaminants associated with anthropogenic activities such as the mining and milling of uranium ores, generation of nuclear energy, and storage of legacy waste resulting from the manufacturing and testing of nuclear weapons. In this review, we discuss the abundance, production, and environmental sources of naturally occurring and some man-made light actinides. As is the case with other environmental contaminants, the solubility, transport properties, bioavailability, and toxicity of actinides are dependent on their speciation (composition, oxidation state, molecular-level structure, and nature of the phase in which the contaminant element or molecule occurs). We review the aqueous speciation of U, Np, and Pu as a function of pH and Eh, their interaction with common inorganic and organic ligands in natural waters, and some of the common U-containing minerals. We also discuss the interaction of U, Np, Pu, and Am solution complexes with common Earth materials, including minerals, colloids, gels, natural organic matter (NOM), and microbial organisms, based on simplified model system studies. These surface interactions can inhibit (e.g., sorption to mineral surfaces, formation of insoluble biominerals) or enhance (e.g., colloid-facilitated transport) the dispersal of light actinides in the biosphere and in some cases (e.g., interaction with dissimilatory metal-reducing bacteria, NOM, or Mn- and Fe-containing minerals) can modify the oxidation states and, consequently, the behavior of redox-sensitive light actinides (U, Np, and Pu). Finally, we review the speciation of U and Pu, their chemical transformations, and cleanup histories at several U.S. Department of Energy field sites that have been used to mill U ores, produce fissile materials for reactors and weapons, and store high-level nuclear waste from both civilian and defense operations, including Hanford, WA; Rifle, CO; Oak Ridge, TN; Fernald, OH; Fry Canyon, UT; and Rocky Flats, CO.