Diffuse Reflectance Spectroscopy and Principal Component Analysis to Retrospectively Determine Production History of Plutonium Dioxide

Eliel Villa-Aleman; Jonathan H. Christian; Jason R. Darvin; Bryan J. Foley; Don D. Dick; Brent Fallin; Kimberly A.S. Fessler

doi:10.1177/00037028221145724

Diffuse Reflectance Spectroscopy and Principal Component Analysis to Retrospectively Determine Production History of Plutonium Dioxide

Eliel Villa-Aleman, Jonathan H. Christian, Jason R. Darvin, Bryan J. Foley, Don D. Dick, Brent Fallin, Kimberly A.S. Fessler

Materials & Chemistry Group

Research output: Contribution to journal › Article › peer-review

6 Scopus citations

Abstract

Diffuse reflectance spectroscopy measurements in the shortwave infrared (930–1600 nm) spectral region were acquired for Pu₂(C₂O₄)₃•9H₂O and its thermal decomposition product, PuO₂. We analyzed a total of eight PuO₂ samples that were produced at different calcination temperatures (300, 350, 450, 525, 600, 675, 750, and 900 °C). Our goal was to identify spectroscopic fingerprints that could be used to gain retrospective information regarding the production parameters of these important nuclear compounds. The diffuse reflectance spectrum of Pu₂(C₂O₄)₃•9H₂O features several broad bands that currently preclude detailed analysis. However, all PuO₂ samples produced relatively sharp spectral features that got sharper and more intense for samples that were produced at higher calcination temperatures. The electronic band observed at 1433 nm in the diffuse reflectance spectra of PuO₂ was found to be a sensitive indicator of crystallinity; a result that is corroborated by ancillary Raman spectroscopy measurements. Principal component analysis of diffuse reflectance spectra was able to clearly rank and categorize PuO₂ samples based on the calcination temperature that was employed during their production. Thus, we show herein that important retrospective information pertaining to the process history of PuO₂ can be gained through the relatively simplistic combination of diffuse reflectance spectroscopy and principal component analysis. This discovery presents a new method for determining the provenance and process history of PuO₂ and should have an impact in the fields of nuclear forensics and nuclear nonproliferation.

Original language	English
Pages (from-to)	449-456
Number of pages	8
Journal	Applied Spectroscopy
Volume	77
Issue number	5
DOIs	https://doi.org/10.1177/00037028221145724
State	Published - May 2023

Funding

This work was produced by Battelle Savannah River Alliance, LLC under Contract no. 89303321CEM000080 and/or a predecessor contract with the U.S. Department of Energy. Publisher acknowledges the U.S. Government license to provide public access under the DOE Public Access Plan (http://energy.gov/downloads/doe-public-access-plan ). We also would like to acknowledge Mr. Michael Maxwell and Mr. Ross Smith for engineering and assembly of double-walled cells used in this research. The author(s) disclosed receipt of the following financial support for the research, authorship, and/or publication of this article: This work was funded by the SRNL Laboratory Directed Research & Development under the project LDRD-2022-00186 and the Office of Defense Nuclear Nonproliferation Research and Development within the U.S. Department of Energy’s National Nuclear Security Administration under project SR19-Spec-Signatures NDD3Bb and OR19-ML-Fuel Cycle Material-PD1Ab. The author(s) disclosed receipt of the following financial support for the research, authorship, and/or publication of this article: This work was funded by the SRNL Laboratory Directed Research & Development under the project LDRD-2022-00186 and the Office of Defense Nuclear Nonproliferation Research and Development within the U.S. Department of Energy’s National Nuclear Security Administration under project SR19-Spec-Signatures NDD3Bb and OR19-ML-Fuel Cycle Material-PD1Ab.

Keywords

calcination
nonproliferation
nuclear forensics
PCA
plutonium dioxide
Plutonium oxalate
principal component analysis

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10.1177/00037028221145724

Cite this

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title = "Diffuse Reflectance Spectroscopy and Principal Component Analysis to Retrospectively Determine Production History of Plutonium Dioxide",

abstract = "Diffuse reflectance spectroscopy measurements in the shortwave infrared (930–1600 nm) spectral region were acquired for Pu2(C2O4)3•9H2O and its thermal decomposition product, PuO2. We analyzed a total of eight PuO2 samples that were produced at different calcination temperatures (300, 350, 450, 525, 600, 675, 750, and 900 °C). Our goal was to identify spectroscopic fingerprints that could be used to gain retrospective information regarding the production parameters of these important nuclear compounds. The diffuse reflectance spectrum of Pu2(C2O4)3•9H2O features several broad bands that currently preclude detailed analysis. However, all PuO2 samples produced relatively sharp spectral features that got sharper and more intense for samples that were produced at higher calcination temperatures. The electronic band observed at 1433 nm in the diffuse reflectance spectra of PuO2 was found to be a sensitive indicator of crystallinity; a result that is corroborated by ancillary Raman spectroscopy measurements. Principal component analysis of diffuse reflectance spectra was able to clearly rank and categorize PuO2 samples based on the calcination temperature that was employed during their production. Thus, we show herein that important retrospective information pertaining to the process history of PuO2 can be gained through the relatively simplistic combination of diffuse reflectance spectroscopy and principal component analysis. This discovery presents a new method for determining the provenance and process history of PuO2 and should have an impact in the fields of nuclear forensics and nuclear nonproliferation.",

keywords = "calcination, nonproliferation, nuclear forensics, PCA, plutonium dioxide, Plutonium oxalate, principal component analysis",

author = "Eliel Villa-Aleman and Christian, {Jonathan H.} and Darvin, {Jason R.} and Foley, {Bryan J.} and Dick, {Don D.} and Brent Fallin and Fessler, {Kimberly A.S.}",

note = "Publisher Copyright: {\textcopyright} The Author(s) 2023.",

year = "2023",

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doi = "10.1177/00037028221145724",

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T1 - Diffuse Reflectance Spectroscopy and Principal Component Analysis to Retrospectively Determine Production History of Plutonium Dioxide

AU - Villa-Aleman, Eliel

AU - Christian, Jonathan H.

AU - Darvin, Jason R.

AU - Foley, Bryan J.

AU - Dick, Don D.

AU - Fallin, Brent

AU - Fessler, Kimberly A.S.

N1 - Publisher Copyright: © The Author(s) 2023.

PY - 2023/5

Y1 - 2023/5

N2 - Diffuse reflectance spectroscopy measurements in the shortwave infrared (930–1600 nm) spectral region were acquired for Pu2(C2O4)3•9H2O and its thermal decomposition product, PuO2. We analyzed a total of eight PuO2 samples that were produced at different calcination temperatures (300, 350, 450, 525, 600, 675, 750, and 900 °C). Our goal was to identify spectroscopic fingerprints that could be used to gain retrospective information regarding the production parameters of these important nuclear compounds. The diffuse reflectance spectrum of Pu2(C2O4)3•9H2O features several broad bands that currently preclude detailed analysis. However, all PuO2 samples produced relatively sharp spectral features that got sharper and more intense for samples that were produced at higher calcination temperatures. The electronic band observed at 1433 nm in the diffuse reflectance spectra of PuO2 was found to be a sensitive indicator of crystallinity; a result that is corroborated by ancillary Raman spectroscopy measurements. Principal component analysis of diffuse reflectance spectra was able to clearly rank and categorize PuO2 samples based on the calcination temperature that was employed during their production. Thus, we show herein that important retrospective information pertaining to the process history of PuO2 can be gained through the relatively simplistic combination of diffuse reflectance spectroscopy and principal component analysis. This discovery presents a new method for determining the provenance and process history of PuO2 and should have an impact in the fields of nuclear forensics and nuclear nonproliferation.

AB - Diffuse reflectance spectroscopy measurements in the shortwave infrared (930–1600 nm) spectral region were acquired for Pu2(C2O4)3•9H2O and its thermal decomposition product, PuO2. We analyzed a total of eight PuO2 samples that were produced at different calcination temperatures (300, 350, 450, 525, 600, 675, 750, and 900 °C). Our goal was to identify spectroscopic fingerprints that could be used to gain retrospective information regarding the production parameters of these important nuclear compounds. The diffuse reflectance spectrum of Pu2(C2O4)3•9H2O features several broad bands that currently preclude detailed analysis. However, all PuO2 samples produced relatively sharp spectral features that got sharper and more intense for samples that were produced at higher calcination temperatures. The electronic band observed at 1433 nm in the diffuse reflectance spectra of PuO2 was found to be a sensitive indicator of crystallinity; a result that is corroborated by ancillary Raman spectroscopy measurements. Principal component analysis of diffuse reflectance spectra was able to clearly rank and categorize PuO2 samples based on the calcination temperature that was employed during their production. Thus, we show herein that important retrospective information pertaining to the process history of PuO2 can be gained through the relatively simplistic combination of diffuse reflectance spectroscopy and principal component analysis. This discovery presents a new method for determining the provenance and process history of PuO2 and should have an impact in the fields of nuclear forensics and nuclear nonproliferation.

KW - calcination

KW - nonproliferation

KW - nuclear forensics

KW - PCA

KW - plutonium dioxide

KW - Plutonium oxalate

KW - principal component analysis

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JO - Applied Spectroscopy

JF - Applied Spectroscopy

IS - 5

ER -

Diffuse Reflectance Spectroscopy and Principal Component Analysis to Retrospectively Determine Production History of Plutonium Dioxide

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