Laura Lopez-Odriozola, Samuel Shaw, Liam Abrahamsen-Mills, Charlotte Waters, Louise S Natrajan
{"title":"利用激发发射矩阵的 TRLFS 和 PARAFAC,识别和量化吉布斯特上多相铀(VI)的 pH 值。","authors":"Laura Lopez-Odriozola, Samuel Shaw, Liam Abrahamsen-Mills, Charlotte Waters, Louise S Natrajan","doi":"10.1021/acs.est.4c06133","DOIUrl":null,"url":null,"abstract":"<p><p>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<sub>2</sub><sup>2+</sup>) 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<sub>2</sub>-UO<sub>2</sub>(OH) and ≡AlO<sub>2</sub>-UO<sub>2</sub>(CO<sub>3</sub>)<sub>2</sub><sup>4-</sup> 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.</p>","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":null,"pages":null},"PeriodicalIF":10.8000,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Identification and Quantification of Multiphase U(VI) Speciation on Gibbsite with pH Using TRLFS and PARAFAC of Excitation Emission Matrices.\",\"authors\":\"Laura Lopez-Odriozola, Samuel Shaw, Liam Abrahamsen-Mills, Charlotte Waters, Louise S Natrajan\",\"doi\":\"10.1021/acs.est.4c06133\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>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<sub>2</sub><sup>2+</sup>) 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<sub>2</sub>-UO<sub>2</sub>(OH) and ≡AlO<sub>2</sub>-UO<sub>2</sub>(CO<sub>3</sub>)<sub>2</sub><sup>4-</sup> 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.</p>\",\"PeriodicalId\":36,\"journal\":{\"name\":\"环境科学与技术\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":10.8000,\"publicationDate\":\"2024-09-24\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"环境科学与技术\",\"FirstCategoryId\":\"1\",\"ListUrlMain\":\"https://doi.org/10.1021/acs.est.4c06133\",\"RegionNum\":1,\"RegionCategory\":\"环境科学与生态学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"ENGINEERING, ENVIRONMENTAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"环境科学与技术","FirstCategoryId":"1","ListUrlMain":"https://doi.org/10.1021/acs.est.4c06133","RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"ENGINEERING, ENVIRONMENTAL","Score":null,"Total":0}
Identification and Quantification of Multiphase U(VI) Speciation on Gibbsite with pH Using TRLFS and PARAFAC of Excitation Emission Matrices.
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), (UO22+) 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 ≡AlO2-UO2(OH) and ≡AlO2-UO2(CO3)24- 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.
期刊介绍:
Environmental Science & Technology (ES&T) is a co-sponsored academic and technical magazine by the Hubei Provincial Environmental Protection Bureau and the Hubei Provincial Academy of Environmental Sciences.
Environmental Science & Technology (ES&T) holds the status of Chinese core journals, scientific papers source journals of China, Chinese Science Citation Database source journals, and Chinese Academic Journal Comprehensive Evaluation Database source journals. This publication focuses on the academic field of environmental protection, featuring articles related to environmental protection and technical advancements.