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Title: A Piecewise Local Partial Least Squares (PLS) Method for the Quantitative Analysis of Plutonium Nitrate Solutions

Abstract

Here, we have developed a piecewise local (PL) partial least squares (PLS) analysis method for total plutonium measurements by absorption spectroscopy in nitric acid-based nuclear material processing streams. Instead of using a single PLS model that covers all expected solution conditions, the method selects one of several local models based on an assessment of solution absorbance, acidity, and Pu oxidation state distribution. The local models match the global model for accuracy against the calibration set, but were observed in several instances to be more robust to variations associated with measurements in the process. The improvements are attributed to the relative parsimony of the local models. Not all of the sources of spectral variation are uniformly present at each part of the calibration range. Thus, the global model is locally overfitting and susceptible to increased variance when presented with new samples. A second set of models quantifies the relative concentrations of Pu(III), (IV), and (VI). Standards containing a mixture of these species were not at equilibrium due to a disproportionation reaction. Therefore, a separate principal component analysis is used to estimate of the concentrations of the individual oxidation states in these standards in the absence of independent confirmatory analysis. The PLmore » analysis approach is generalizable to other systems where the analysis of chemically complicated systems can be aided by rational division of the overall range of solution conditions into simpler sub-regions.« less

Authors:
ORCiD logo [1];  [1];  [1]
  1. Savannah River National Lab., Aiken, SC (United States)
Publication Date:
Research Org.:
Savannah River Site (SRS), Aiken, SC (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1439429
Report Number(s):
SRNL-STI-2016-00697
Journal ID: ISSN 0003-7028; TRN: US1900610
Grant/Contract Number:  
AC09-08SR22470
Resource Type:
Accepted Manuscript
Journal Name:
Applied Spectroscopy
Additional Journal Information:
Journal Volume: 71; Journal Issue: 12; Journal ID: ISSN 0003-7028
Publisher:
Society for Applied Spectroscopy
Country of Publication:
United States
Language:
English
Subject:
47 OTHER INSTRUMENTATION; Partial least squares; PLS; process analysis; plutonium; absorbance; classification

Citation Formats

Lascola, Robert, O'Rourke, Patrick E., and Kyser, Edward A. A Piecewise Local Partial Least Squares (PLS) Method for the Quantitative Analysis of Plutonium Nitrate Solutions. United States: N. p., 2017. Web. doi:10.1177/0003702817734000.
Lascola, Robert, O'Rourke, Patrick E., & Kyser, Edward A. A Piecewise Local Partial Least Squares (PLS) Method for the Quantitative Analysis of Plutonium Nitrate Solutions. United States. doi:10.1177/0003702817734000.
Lascola, Robert, O'Rourke, Patrick E., and Kyser, Edward A. Thu . "A Piecewise Local Partial Least Squares (PLS) Method for the Quantitative Analysis of Plutonium Nitrate Solutions". United States. doi:10.1177/0003702817734000. https://www.osti.gov/servlets/purl/1439429.
@article{osti_1439429,
title = {A Piecewise Local Partial Least Squares (PLS) Method for the Quantitative Analysis of Plutonium Nitrate Solutions},
author = {Lascola, Robert and O'Rourke, Patrick E. and Kyser, Edward A.},
abstractNote = {Here, we have developed a piecewise local (PL) partial least squares (PLS) analysis method for total plutonium measurements by absorption spectroscopy in nitric acid-based nuclear material processing streams. Instead of using a single PLS model that covers all expected solution conditions, the method selects one of several local models based on an assessment of solution absorbance, acidity, and Pu oxidation state distribution. The local models match the global model for accuracy against the calibration set, but were observed in several instances to be more robust to variations associated with measurements in the process. The improvements are attributed to the relative parsimony of the local models. Not all of the sources of spectral variation are uniformly present at each part of the calibration range. Thus, the global model is locally overfitting and susceptible to increased variance when presented with new samples. A second set of models quantifies the relative concentrations of Pu(III), (IV), and (VI). Standards containing a mixture of these species were not at equilibrium due to a disproportionation reaction. Therefore, a separate principal component analysis is used to estimate of the concentrations of the individual oxidation states in these standards in the absence of independent confirmatory analysis. The PL analysis approach is generalizable to other systems where the analysis of chemically complicated systems can be aided by rational division of the overall range of solution conditions into simpler sub-regions.},
doi = {10.1177/0003702817734000},
journal = {Applied Spectroscopy},
number = 12,
volume = 71,
place = {United States},
year = {2017},
month = {10}
}

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Works referenced in this record:

Spectroscopic monitoring of spent nuclear fuel reprocessing streams: an evaluation of spent fuel solutions via Raman, visible, and near-infrared spectroscopy
journal, September 2011

  • Bryan, S. A.; Levitskaia, Tatiana G.; Johnsen, A. M.
  • Radiochimica Acta, Vol. 99, Issue 9
  • DOI: 10.1524/ract.2011.1865

Structural and Spectroscopic Characterization of Plutonyl(VI) Nitrate under Acidic Conditions
journal, May 2011

  • Gaunt, Andrew J.; May, Iain; Neu, Mary P.
  • Inorganic Chemistry, Vol. 50, Issue 10
  • DOI: 10.1021/ic200525u

Absorption spectroscopic properties for Pu(III, IV and VI) in nitric and hydrochloric acid media
journal, July 2007

  • Lee, M. H.; Park, Y. J.; Kim, W. H.
  • Journal of Radioanalytical and Nuclear Chemistry, Vol. 273, Issue 2
  • DOI: 10.1007/s10967-007-6848-1

Complexation of Lanthanides with Nitrate at Variable Temperatures: Thermodynamics and Coordination Modes
journal, February 2009

  • Rao, Linfeng; Tian, Guoxin
  • Inorganic Chemistry, Vol. 48, Issue 3
  • DOI: 10.1021/ic801604f

An Introduction to Multivariate Calibration and Analysis
journal, September 1987

  • Beebe, Kenneth R.; Kowalski, Bruce R.
  • Analytical Chemistry, Vol. 59, Issue 17
  • DOI: 10.1021/ac00144a725

Detection and quantification of Pu(III, IV, V, and VI) using a 1.0-meter liquid core waveguide
journal, January 2005


Enhanced batch process monitoring using just-in-time-learning based kernel partial least squares
journal, April 2013


IUPAC-Consistent Approach to the Limit of Detection in Partial Least-Squares Calibration
journal, July 2014

  • Allegrini, Franco; Olivieri, Alejandro C.
  • Analytical Chemistry, Vol. 86, Issue 15
  • DOI: 10.1021/ac501786u

The absorption spectra of plutonium ions in perchloric acid solutions
journal, March 1961


A thermodynamic model of plutonium (IV) nitrate solutions
journal, March 2012

  • Kubic, William L.; Jackson, J. Christopher
  • Journal of Radioanalytical and Nuclear Chemistry, Vol. 293, Issue 2
  • DOI: 10.1007/s10967-012-1703-4

The local paradigm for modeling and control: from neuro-fuzzy to lazy learning
journal, July 2001


The influence of data preprocessing on the robustness and parsimony of multivariate calibration models
journal, April 1994


Estimating the number of factors to include in a high-dimensional multivariate bilinear model
journal, January 2000

  • Sug Park, Eun; Henry, Ronald C.; Spiegelman, Clifford H.
  • Communications in Statistics - Simulation and Computation, Vol. 29, Issue 3
  • DOI: 10.1080/03610910008813637

Characterization of the nitrate complexes of Pu(IV) using absorption spectroscopy, 15N NMR, and EXAFS
journal, October 1994


Constructing NARMAX models using ARMAX models
journal, November 1993


Nonlinear process monitoring using JITL-PCA
journal, March 2005


Analytical Chemistry of Plutonium
journal, December 1957


Batch process monitoring based on just-in-time learning and multiple-subspace principal component analysis
journal, October 2014


Capability of detection of an analytical method evaluating false positive and false negative (ISO 11843) with partial least squares
journal, November 2003

  • Ortiz, M. C.; Sarabia, L. A.; Herrero, A.
  • Chemometrics and Intelligent Laboratory Systems, Vol. 69, Issue 1-2
  • DOI: 10.1016/S0169-7439(03)00110-2

Spectrophotometric method for precision determination of elements of the nuclear fuel cycle
journal, September 2012


Spectrophotometric method for the analysis of plutonium and nitric acid using partial least-squares regression
journal, August 1989

  • Carey, W. Patrick.; Wangen, Lawrence E.; Dyke, James T.
  • Analytical Chemistry, Vol. 61, Issue 15
  • DOI: 10.1021/ac00190a016

The spectrum-based learner: A new local approach for modeling soil vis–NIR spectra of complex datasets
journal, March 2013


Restoring important process information from complex optical spectra with MCR-ALS: Case study of actinide reduction in spent nuclear fuel reprocessing
journal, August 2015


Comparing a new algorithm with the classic methods for estimating the number of factors
journal, June 1999

  • Henry, Ronald C.; Park, Eun Sug; Spiegelman, Clifford H.
  • Chemometrics and Intelligent Laboratory Systems, Vol. 48, Issue 1
  • DOI: 10.1016/S0169-7439(99)00015-5

Dosage spectrophotometrique du plutonium apres oxydation par le rium(IV)
journal, March 1981


The parsimony principle applied to multivariate calibration
journal, May 1993


Locally Weighted Regression: An Approach to Regression Analysis by Local Fitting
journal, September 1988


Speciation Model Selection by Monte Carlo Analysis of Optical Absorption Spectra: Plutonium(IV) Nitrate Complexes
journal, June 2000

  • Berg, John M.; Veirs, D. Kirk; Vaughn, Randolph B.
  • Applied Spectroscopy, Vol. 54, Issue 6
  • DOI: 10.1366/0003702001950436

Disproportionation of Pu(IV): A reassessment of kinetic and equilibrium properties
journal, May 2007


Combination of optical spectroscopy and chemometric techniques—a possible way for on-line monitoring of spent nuclear fuel (SNF) reprocessing
journal, March 2012

  • Kirsanov, D.; Babain, V.; Agafonova-Moroz, M.
  • Radiochimica Acta, Vol. 100, Issue 3
  • DOI: 10.1524/ract.2012.1901

Smoothing and Differentiation of Data by Simplified Least Squares Procedures.
journal, July 1964

  • Savitzky, Abraham.; Golay, M. J. E.
  • Analytical Chemistry, Vol. 36, Issue 8
  • DOI: 10.1021/ac60214a047