Microbial processes can affect the environmental behavior of redox sensitive radionuclides, and understanding these reactions is essential for the safe management of radioactive wastes. Neptunium, an alpha-emitting transuranic element, is of particular importance because of its long half-life, high radiotoxicity, and relatively high solubility as Np(V)O(2)(+) under oxic conditions. Here, we describe experiments to explore the biogeochemistry of Np where Np(V) was added to oxic sediment microcosms with indigenous microorganisms and anaerobically incubated. Enhanced Np removal to sediments occurred during microbially mediated metal reduction, and X-ray absorption spectroscopy showed this was due to reduction to poorly soluble Np(IV) on solids. In subsequent reoxidation experiments, sediment-associated Np(IV) was somewhat resistant to oxidative remobilization. These results demonstrate the influence of microbial processes on Np solubility and highlight the critical importance of radionuclide biogeochemistry in nuclear legacy management.
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Dalton Trans
November 2024
Institute of Nuclear and New Energy Technology, Tsinghua University, 100084, Beijing, China.
High-level liquid waste (HLLW) generated through nuclear reactions and spent fuel reprocessing contains the critical transuranic element neptunium (Np). Thus, the efficient recovery of Np from HLLW the TRPO (trialkylphosphine oxide) process is not only beneficial for radioactive contamination remediation but also boosts the recycling of precious nuclear resources. However, this process including Np(V)-Np(IV) conversion is highly dependent on the components coexisting in HLLW, and its underlying mechanism is still not clear, restricting the recovery of Np in multiple scenarios.
View Article and Find Full Text PDFChem Sci
August 2024
Los Alamos National Laboratory (LANL) P. O. Box 1663, Los Alamos New Mexico 87545 USA
Recent advances enabled the discovery of heterometallic molecules for many metals: main group, d-block, lanthanides, and some actinides (U, Th). These complexes have at least two different metals joined by bridging ligands or by direct metal-metal bonding interactions. They are attractive because they can enable chemical cooperativity between metals from different parts of the periodic table.
View Article and Find Full Text PDFJ Environ Radioact
September 2024
Institute of Radiological Science, National Institutes for Quantum Science and Technology (QST), 491 Anagawa, Inage, Chiba, 263-8555, Japan.
For the quality control in determining transuranic nuclides in fallout samples, this work first reported the Np activity concentration in a reference fallout material and further calculated the activity ratios of Np/Pu and Np/Am, and the atom ratio of Np/Pu in it. The reference fallout material prepared by the Meteorological Research Institute was collected at 14 stations throughout Japan in 1963-1979. The Np and Pu isotopes (Pu and Pu) were separated and purified using AG MP-1M anion-exchange resin, quantified using Pu as an isotope dilution tracer, and determined by the SF-ICP-MS.
View Article and Find Full Text PDFJ Environ Radioact
September 2024
Australian Nuclear Science and Technology Organisation, Lucas Heights, NSW, 2234, Australia.
Three nuclear weapons tests were conducted in the 1950s at the Montebello Islands, Western Australia. The detonations were of different yields and configurations (two tower tests, one ship test), and led to substantial radionuclide contamination within the surrounding terrestrial and marine ecosystems. The region possesses great ecological and recreational significance, particularly within the marine environment.
View Article and Find Full Text PDFNat Chem
September 2024
School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, GA, USA.
Neptunium is an actinide element sourced from anthropogenic production, and, unlike naturally abundant uranium, its coordination chemistry is not well developed in all accessible oxidation states. High-valent neptunium generally requires stabilization from at least one metal-ligand multiple bond, and departing from this structural motif poses a considerable challenge. Here we report a tetrahedral molecular neptunium(V) complex ([Np(NPC)][B(ArF)], 1-Np) (NPC = [NPBu(pyrr)]; Bu = C(CH); pyrr = pyrrolidinyl (N(CH)); B(ArF) = tetrakis(2,3,4,5,6-pentafluourophenyl)borate).
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