Transient Radiation-Induced Berkelium(III) and Californium(III) Redox Chemistry in Aqueous Solution

Horne, Gregory P.; Rotermund, Brian M.; Grimes, Travis S.; Sperling, Joseph M.; Meeker, David S.; Zalupski, Peter R.; Beck, Nicholas; Huffman, Zachary K.; Martinez, Daniela Gomez; Beshay, Andrew; Peterman, Dean R.; Layne, Bobby H.; Johnson, Jason; Cook, Andrew R.; Albrecht-Schönzart, Thomas E.; Mezyk, Stephen P.

doi:10.1021/acs.inorgchem.2c01106

Title: Transient Radiation-Induced Berkelium(III) and Californium(III) Redox Chemistry in Aqueous Solution

Journal Article · Fri Jul 01 00:00:00 EDT 2022 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.2c01106· OSTI ID:1874890

^[1]; Rotermund, Brian M. ^[2];

^[1];

^[2]; Meeker, David S. ^[3];

^[1]; Beck, Nicholas ^[2]; Huffman, Zachary K. ^[2]; Martinez, Daniela Gomez ^[2]; Beshay, Andrew ^[4];

^[1]; Layne, Bobby H. ^[5]; Johnson, Jason ^[2];

^[5];

^[2]; Mezyk, Stephen P. ^[4]

Idaho National Lab. (INL), Idaho Falls, ID (United States)
Florida State University, Tallahassee, FL (United States)
Idaho National Lab. (INL), Idaho Falls, ID (United States); Florida State University, Tallahassee, FL (United States)
California State University (CalState), Long Beach, CA (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)

We report despite the significant impact of radiation-induced redox reactions on the accessibility and lifetimes of actinide oxidation states, fundamental knowledge of aqueous actinide metal ion radiation chemistry is limited, especially for the late actinides. A quantitative understanding of these intrinsic radiation-induced processes is essential for investigating the fundamental properties of these actinides. We present here a picosecond electron pulse reaction kinetics study into the radiation-induced redox chemistry of trivalent berkelium (Bk(III)) and californium (Cf(III)) ions in acidic aqueous solutions at ambient temperature. New, and first of a kind, second-order rate coefficients are reported for the transient radical-induced reduction of Bk(III) and Cf(III) by the hydrated electron (e_aq^-) and hydrogen atom (H^•), demonstrating significant reactivity (up to 10¹¹M^-1s^-1) indicative of a preference of these metals to adopt divalent states. Additionally, we reportthe first-ever second-order rate coefficients for the transient radical-induced oxidation of these elements by reaction with hydroxyl (^•OH) and nitrate (NO₃^•) radicals, which also exhibited fast reactivity (ca. 10⁸ M^-1s^-1). Transient Cf(II), Cf(IV), and Bk(IV) absorption spectra are also reported. Overall, the presented data highlight the existence of rich, complex, intrinsic late actinide radiation-induced redox chemistry that has the potential to influence the findings of other areas of actinide science.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States); Idaho National Laboratory (INL), Idaho Falls, ID (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE Laboratory Directed Research and Development (LDRD) Program; Nuclear Energy Universities; USDOE Office of Nuclear Energy (NE)

Grant/Contract Number:: SC0012704; AC07-05ID14517; SC0021372; NE0008406; FC02-04ER15533

OSTI ID:: 1874890

Alternate ID(s):: OSTI ID: 1899171

Report Number(s):: BNL-223090-2022-JAAM; INL/JOU-22-66647-Rev000

Journal Information:: Inorganic Chemistry, Vol. 61, Issue 28; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
Berkelium
Californium
Radiation Chemistry
Electron Pulse Radiolysis
Reaction Kinetics

Title: Transient Radiation-Induced Berkelium(III) and Californium(III) Redox Chemistry in Aqueous Solution

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