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Title: Transmutation effects on long-term Cs retention in phyllosilicate minerals from first principles

Abstract

The accidental release and incorporation of radiocesium into soil minerals represents a massive environmental, technical and social challenge. Accurately forecasting the evolving distribution and fate of long- and medium-lived isotopes such as 137Cs and 134Cs over decadal time scales is essential. The cesium cation has long been modeled as a strongly and selectively sorbed species into clay mineral interlayers; however, because of the time scales involved by the radioisotopes half-lives, the effects of radioactive decay on Cs retention have been unknown. We report density functional theory (DFT) simulations of transmutation effects of radiocesium on long-term Cs retention in phlogopite. The calculations show that the progressive appearance of daughter product Ba2+ is accompanied by a proportional increase in thermodynamic driving force to preferentially discharge remaining Cs, both radioactive and stable, back into aqueous solution. Based on thermodynamic analysis, the findings indicate that radiocesium transmutation provides a mean to weaken the binding of Cs in phyllosilicate minerals, therefore potentially involving a premature re-release of Cs back into the environment. In the case where radiogenic Ba2+ ions accumulate in the mineral, collateral effects would ultimately be an increase in the overall interlayer binding energy and a lower resorption capacity.

Authors:
 [1];  [2];  [3]; ORCiD logo [1]
  1. BATTELLE (PACIFIC NW LAB)
  2. VISITORS
  3. THE JAPAN ATOMIC POWER CO
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1518602
Report Number(s):
PNNL-SA-131843
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Physical Chemistry Chemical Physics. PCCP
Additional Journal Information:
Journal Volume: 19; Journal Issue: 39
Country of Publication:
United States
Language:
English

Citation Formats

Sassi, Michel JPC, Okumura, Masahiko, Machida, Masahiko, and Rosso, Kevin M. Transmutation effects on long-term Cs retention in phyllosilicate minerals from first principles. United States: N. p., 2017. Web. doi:10.1039/c7cp04496h.
Sassi, Michel JPC, Okumura, Masahiko, Machida, Masahiko, & Rosso, Kevin M. Transmutation effects on long-term Cs retention in phyllosilicate minerals from first principles. United States. doi:10.1039/c7cp04496h.
Sassi, Michel JPC, Okumura, Masahiko, Machida, Masahiko, and Rosso, Kevin M. Sat . "Transmutation effects on long-term Cs retention in phyllosilicate minerals from first principles". United States. doi:10.1039/c7cp04496h.
@article{osti_1518602,
title = {Transmutation effects on long-term Cs retention in phyllosilicate minerals from first principles},
author = {Sassi, Michel JPC and Okumura, Masahiko and Machida, Masahiko and Rosso, Kevin M.},
abstractNote = {The accidental release and incorporation of radiocesium into soil minerals represents a massive environmental, technical and social challenge. Accurately forecasting the evolving distribution and fate of long- and medium-lived isotopes such as 137Cs and 134Cs over decadal time scales is essential. The cesium cation has long been modeled as a strongly and selectively sorbed species into clay mineral interlayers; however, because of the time scales involved by the radioisotopes half-lives, the effects of radioactive decay on Cs retention have been unknown. We report density functional theory (DFT) simulations of transmutation effects of radiocesium on long-term Cs retention in phlogopite. The calculations show that the progressive appearance of daughter product Ba2+ is accompanied by a proportional increase in thermodynamic driving force to preferentially discharge remaining Cs, both radioactive and stable, back into aqueous solution. Based on thermodynamic analysis, the findings indicate that radiocesium transmutation provides a mean to weaken the binding of Cs in phyllosilicate minerals, therefore potentially involving a premature re-release of Cs back into the environment. In the case where radiogenic Ba2+ ions accumulate in the mineral, collateral effects would ultimately be an increase in the overall interlayer binding energy and a lower resorption capacity.},
doi = {10.1039/c7cp04496h},
journal = {Physical Chemistry Chemical Physics. PCCP},
number = 39,
volume = 19,
place = {United States},
year = {2017},
month = {10}
}

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