Annie B. Kersting

Russia's invasion of Ukraine continues to have a devastating effect on the well-being of Ukrainians and their environment. We evaluated a major environmental hazard caused by the war: the potential for groundwater contamination in proximity to the Zaporizhzhia Nuclear Power Plant (NPP). We quantified groundwater vulnerability with the DRASTIC index, which was originally developed by the United States Environmental Protection Agency and has been used at various locations worldwide to assess relative pollution potential. We found that there are two major gradients of groundwater vulnerability in the region: (1) broadly higher risk to the northeast of the NPP and lower risk to the southeast driven by a regional gradient in water availability and water table depth; and (2) higher risk in proximity to the channels and floodplains of the Dnipro River and tributaries, which host coarser-textured soils and sedimentary deposits. We also found that the DRASTIC vulnerability index can be used to identify and prioritize groundwater well-network monitoring. These and more detailed assessments will be necessary to prioritize monitoring and remediation strategies across Ukraine in the event of a nuclear accident, and more broadly demonstrate the utility of the DRASTIC approach for prognostic contamination risk assessment.

Over 4 million liters of mixed acidic (∼pH 2.5), high ionic strength (∼5 M nitrate) plutonium (Pu) processing waste were released into the 216-Z-9 (Z-9) trench at the Hanford Site, USA, and trace Pu has migrated 37 m below the trench. In this study, we used flowthrough columns to investigate Pu transport in simplified processing waste through uncontaminated Hanford sediments to determine the conditions that led to Pu migration. In low pH aqueous fluids, some Pu breakthrough is observed at pH < 4, and increased Pu transport (14% total Pu breakthrough) is observed at pH < 2. However, Pu migrates in organic processing solvents through low pH sediments virtually uninhibited with approximately 94 and 86% total Pu breakthrough observed at pH 1 and pH 3, respectively. This study demonstrates that Pu migration can occur both with and without organic solvents at pH < 4, but significantly more Pu can be transported when partitioned into organic processing solvents. Our data suggest that under acidic conditions (pH < 4) in the vadose zone beneath the Z-9 trench, Pu present in organic processing solvents moved relatively unhindered and may explain the historical downward migration of Pu tens of meters below the Z-9 trench.

Minor actinides are major contributors to the long-term radiotoxicity of nuclear fuels and other radioactive wastes. In this context, understanding their interactions with natural chelators and minerals is key to evaluating their transport behavior in the environment. The lanmodulin family of metalloproteins is produced by ubiquitous bacteria and Methylorubrum extorquens lanmodulin (LanM) was recently identified as one of nature's most selective chelators for trivalent f-elements. Herein, we investigated the behavior of neptunium, americium, and curium in the presence of LanM, carbonate ions, and common minerals (calcite, montmorillonite, quartz, and kaolinite). We show that LanM's aqueous complexes with Am(III) and Cm(III) remain stable in carbonate-bicarbonate solutions. Furthermore, the sorption of Am(III) to these minerals is strongly impacted by LanM, while Np(V) sorption is not. With calcite, even a submicromolar concentration of LanM leads to a significant reduction in the Am(III) distribution coefficient (K_d, from >10⁴ to ∼10² mL/g at pH 8.5), rendering it even more mobile than Np(V). Thus, LanM-type chelators can potentially increase the mobility of trivalent actinides and lanthanide fission products under environmentally relevant conditions. Monitoring biological chelators, including metalloproteins, and their biogenerators should therefore be considered during the evaluation of radioactive waste repository sites and the risk assessment of contaminated sites.

The U.S. Department of Energy's Office of Scientific and Technical Information

Anthropogenic radionuclides, including long-lived heavy actinides such as americium and curium, represent the primary long-term challenge for management of nuclear waste. The potential release of these wastes into the environment necessitates understanding their interactions with biogeochemical compounds present in nature. Here, we characterize the interactions between the heavy actinides, Am³⁺ and Cm³⁺, and the natural lanthanide-binding protein, lanmodulin (LanM). LanM is produced abundantly by methylotrophic bacteria, including Methylorubrum extorquens, that are widespread in the environment. We determine the first stability constant for an Am³⁺-protein complex (Am₃LanM) and confirm the results with Cm₃LanM, indicating a ∼5-fold higher affinity than that for lanthanides with most similar ionic radius, Nd³⁺ and Sm³⁺, and making LanM the strongest known heavy actinide-binding protein. The protein’s high selectivity over ²⁴³Am’s daughter nuclide ²³⁹Np enables lab-scale actinide-actinide separations as well as provides insight into potential protein-driven mobilization for these actinides in the environment. The luminescence properties of the Cm³⁺-LanM complex, and NMR studies of Gd³⁺-LanM, reveal that lanmodulin-bound f-elements possess two coordinated solvent molecules across a range of metal ionic radii. Finally, we show under a wide range of environmentally relevant conditions that lanmodulin effectively outcompetes desferrioxamine B, a hydroxamate siderophore previously proposed to be important in trivalent actinide mobility. These results suggest that natural lanthanide-binding proteins such as lanmodulin may play important roles in speciation and mobility of actinides in the environment; it also suggests that protein-based biotechnologies may provide a new frontier in actinide remediation, detection, and separations.