Identification and Quantification of Multiphase U(VI) Speciation on Gibbsite with pH using TRLFS and PARAFAC of Excitation Emission Matrices

Laura Lopez Odriozola; Samuel Shaw; Liam Abrahamsen-Mills; Charlotte Waters; Louise Natrajan

doi:10.1021/acs.est.4c06133

Identification and Quantification of Multiphase U(VI) Speciation on Gibbsite with pH using TRLFS and PARAFAC of Excitation Emission Matrices

Laura Lopez Odriozola, Samuel Shaw, Liam Abrahamsen-Mills, Charlotte Waters, Louise Natrajan

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

Abstract

The significant abundance of uranium in radioactive waste inventories worldwide necessitates a thorough understanding of its behavior. In this work, the speciation of uranyl(VI), (UO ₂ ²⁺) in a gibbsite system under ambient conditions has been determined as a function of pH by deconvolution and analysis of luminescence spectroscopic data. Uniquely, a combined experimental and statistical approach utilizing time-resolved luminescence spectroscopy and parallel factor analysis (PARAFAC) of excitation emission matrices has been successfully utilized to identify four separate luminescent U(VI) species in the uranyl-gibbsite system for the first time. The speciation of all luminescent U(VI) species in an environmentally relevant system over a pH range of 6-11 is discerned through the analysis of emission fingerprints at low temperature (20 K). Comparison of the deconvoluted luminescence spectra with mineral standards and geochemical models of the system allows the assignment of the luminescent chemical species as metaschoepite, Na-compreignacite, surface adsorbed ≡AlO ₂-UO ₂(OH) and ≡AlO ₂-UO ₂(CO ₃) ₂ ^4- complexes, with assignments supported by fitting of extended X-ray absorption fine structure data. The combined spectroscopic techniques in this study show that assignment and quantification of uranyl(VI) species in a sorption system over a large pH range can be accurately achieved using PARAFAC to deconvolute a three way emission spectroscopic data set.

Original language	English
Pages (from-to)	17916-17925
Number of pages	10
Journal	Environmental Science & Technology
Volume	58
Issue number	40
Early online date	24 Sept 2024
DOIs	https://doi.org/10.1021/acs.est.4c06133
Publication status	Published - 8 Oct 2024

Keywords

PARAFAC
TRLFS
speciation
uranium
Uranium/chemistry
Factor Analysis, Statistical
Luminescent Measurements
Hydrogen-Ion Concentration

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10.1021/acs.est.4c06133Licence: CC BY

Molecular Environmental Science - Research Group
Garwood, R. (PI), Shaw, S. (PI), Lloyd, J. (PI), Morris, K. (PI), Polya, D. (PI), Van Dongen, B. (PI), Boult, S. (PI), Coker, V. (PI), Richards, L. (PI), Nixon, S. (PI), Lowe, A. (PI), Robinson, C. (PI), Taylor, K. (PI), Pittman, J. (PI), Neill, T. (PI), Heath, S. (PI) & Livens, F. (PI)
Project: Research

Cite this

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title = "Identification and Quantification of Multiphase U(VI) Speciation on Gibbsite with pH using TRLFS and PARAFAC of Excitation Emission Matrices",

abstract = "The significant abundance of uranium in radioactive waste inventories worldwide necessitates a thorough understanding of its behavior. In this work, the speciation of uranyl(VI), (UO 2 2+) in a gibbsite system under ambient conditions has been determined as a function of pH by deconvolution and analysis of luminescence spectroscopic data. Uniquely, a combined experimental and statistical approach utilizing time-resolved luminescence spectroscopy and parallel factor analysis (PARAFAC) of excitation emission matrices has been successfully utilized to identify four separate luminescent U(VI) species in the uranyl-gibbsite system for the first time. The speciation of all luminescent U(VI) species in an environmentally relevant system over a pH range of 6-11 is discerned through the analysis of emission fingerprints at low temperature (20 K). Comparison of the deconvoluted luminescence spectra with mineral standards and geochemical models of the system allows the assignment of the luminescent chemical species as metaschoepite, Na-compreignacite, surface adsorbed ≡AlO 2-UO 2(OH) and ≡AlO 2-UO 2(CO 3) 2 4- complexes, with assignments supported by fitting of extended X-ray absorption fine structure data. The combined spectroscopic techniques in this study show that assignment and quantification of uranyl(VI) species in a sorption system over a large pH range can be accurately achieved using PARAFAC to deconvolute a three way emission spectroscopic data set.",

keywords = "PARAFAC, TRLFS, speciation, uranium, Uranium/chemistry, Factor Analysis, Statistical, Luminescent Measurements, Hydrogen-Ion Concentration",

author = "{Lopez Odriozola}, Laura and Samuel Shaw and Liam Abrahamsen-Mills and Charlotte Waters and Louise Natrajan",

year = "2024",

month = oct,

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doi = "10.1021/acs.est.4c06133",

language = "English",

volume = "58",

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journal = "Environmental Science & Technology",

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AU - Lopez Odriozola, Laura

AU - Shaw, Samuel

AU - Abrahamsen-Mills, Liam

AU - Waters, Charlotte

AU - Natrajan, Louise

PY - 2024/10/8

Y1 - 2024/10/8

N2 - The significant abundance of uranium in radioactive waste inventories worldwide necessitates a thorough understanding of its behavior. In this work, the speciation of uranyl(VI), (UO 2 2+) in a gibbsite system under ambient conditions has been determined as a function of pH by deconvolution and analysis of luminescence spectroscopic data. Uniquely, a combined experimental and statistical approach utilizing time-resolved luminescence spectroscopy and parallel factor analysis (PARAFAC) of excitation emission matrices has been successfully utilized to identify four separate luminescent U(VI) species in the uranyl-gibbsite system for the first time. The speciation of all luminescent U(VI) species in an environmentally relevant system over a pH range of 6-11 is discerned through the analysis of emission fingerprints at low temperature (20 K). Comparison of the deconvoluted luminescence spectra with mineral standards and geochemical models of the system allows the assignment of the luminescent chemical species as metaschoepite, Na-compreignacite, surface adsorbed ≡AlO 2-UO 2(OH) and ≡AlO 2-UO 2(CO 3) 2 4- complexes, with assignments supported by fitting of extended X-ray absorption fine structure data. The combined spectroscopic techniques in this study show that assignment and quantification of uranyl(VI) species in a sorption system over a large pH range can be accurately achieved using PARAFAC to deconvolute a three way emission spectroscopic data set.

AB - The significant abundance of uranium in radioactive waste inventories worldwide necessitates a thorough understanding of its behavior. In this work, the speciation of uranyl(VI), (UO 2 2+) in a gibbsite system under ambient conditions has been determined as a function of pH by deconvolution and analysis of luminescence spectroscopic data. Uniquely, a combined experimental and statistical approach utilizing time-resolved luminescence spectroscopy and parallel factor analysis (PARAFAC) of excitation emission matrices has been successfully utilized to identify four separate luminescent U(VI) species in the uranyl-gibbsite system for the first time. The speciation of all luminescent U(VI) species in an environmentally relevant system over a pH range of 6-11 is discerned through the analysis of emission fingerprints at low temperature (20 K). Comparison of the deconvoluted luminescence spectra with mineral standards and geochemical models of the system allows the assignment of the luminescent chemical species as metaschoepite, Na-compreignacite, surface adsorbed ≡AlO 2-UO 2(OH) and ≡AlO 2-UO 2(CO 3) 2 4- complexes, with assignments supported by fitting of extended X-ray absorption fine structure data. The combined spectroscopic techniques in this study show that assignment and quantification of uranyl(VI) species in a sorption system over a large pH range can be accurately achieved using PARAFAC to deconvolute a three way emission spectroscopic data set.

KW - PARAFAC

KW - TRLFS

KW - speciation

KW - uranium

KW - Uranium/chemistry

KW - Factor Analysis, Statistical

KW - Luminescent Measurements

KW - Hydrogen-Ion Concentration

U2 - 10.1021/acs.est.4c06133

DO - 10.1021/acs.est.4c06133

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SN - 0013-936X

VL - 58

SP - 17916

EP - 17925

JO - Environmental Science & Technology

JF - Environmental Science & Technology

IS - 40

ER -

Identification and Quantification of Multiphase U(VI) Speciation on Gibbsite with pH using TRLFS and PARAFAC of Excitation Emission Matrices

Abstract

Keywords

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Molecular Environmental Science - Research Group

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