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

Overview

Journal Environ Sci Technol

Publisher American Chemical Society

Specialty Environmental Health

Date 2024 Sep 24

PMID 39315992

Authors

Laura Lopez-Odriozola

Samuel Shaw

Liam Abrahamsen-Mills

Charlotte Waters

Louise S Natrajan

Affiliations

Soon will be listed here.

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) 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-UO(OH) and ≡AlO-UO(CO) 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.

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