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Title: Plutonium Redox Transformation in the Presence of Iron, Organic Matter, and Hydroxyl Radicals: Kinetics and Mechanistic Insights

Journal Article · · Environmental Science and Technology

Plutonium (Pu) redox and complexation processes in the presence of natural organic matter and associated iron can impact the fate and transport of Pu in the environment. In this work, we studied the fate of Pu(IV) in the presence of humic acid (HA) and Fe(II) upon reaction with H2O2 that may be generated by photochemical and other reactions. A portion of Pu(IV) was oxidized to Pu(V/VI), which is primarily ascribed to the generation of reactive intermediates from the oxidation of Fe(II) and Fe(II)–HA complexes by H2O2. The kinetics of Pu(IV) oxidation is pH-dependent and can be described by a model that incorporates Pu redox kinetics with published HA-modified Fenton reaction kinetics. At pH 3.5, the presence of HA slowed Pu(IV) oxidation, while at pH 6, HA accelerated Pu(IV) oxidation in the first several hours followed by a reverse process where the oxidized Pu(V/VI) was reduced back to Pu(IV). Analysis of Pu-associated particle size suggests that Pu oxidation state is a major driver in its complexation with HA and formation of colloids and heteroaggregates. Our results revealed the H2O2-driven oxidation of Pu(IV)–HA–Fe(II) colloids with implications to the transient mobilization of Pu(V/VI) in organic-rich redox transition zones.

Research Organization:
Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Biological and Environmental Research (BER)
Grant/Contract Number:
AC52-07NA27344
OSTI ID:
1777328
Report Number(s):
LLNL-JRNL-808740; 1014280
Journal Information:
Environmental Science and Technology, Vol. 55, Issue 3; ISSN 0013-936X
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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