High Energy Resolution Fluorescence Detected X-ray Absorption Spectroscopy : An Analytical Method for Selenium Speciation
(2021) In Analytical Chemistry 93(26). p.9235-9243- Abstract
Selenium is in many ways an enigmatic element. It is essential for health but toxic in excess, with the difference between the two doses being narrower than for any other element. Environmentally, selenium is of concern due to its toxicity. As the rarest of the essential elements, its low levels often provide challenges to the analytical chemist. X-ray absorption spectroscopy (XAS) provides a powerful tool for in situ chemical speciation but is severely limited by poor spectroscopic resolution arising from core-hole lifetime broadening. Here we explore selenium Kα1 high energy resolution fluorescence detected XAS (HERFD-XAS) as a novel approach for chemical speciation of selenium, in comparison with conventional Se K-edge XAS. We... (More)
Selenium is in many ways an enigmatic element. It is essential for health but toxic in excess, with the difference between the two doses being narrower than for any other element. Environmentally, selenium is of concern due to its toxicity. As the rarest of the essential elements, its low levels often provide challenges to the analytical chemist. X-ray absorption spectroscopy (XAS) provides a powerful tool for in situ chemical speciation but is severely limited by poor spectroscopic resolution arising from core-hole lifetime broadening. Here we explore selenium Kα1 high energy resolution fluorescence detected XAS (HERFD-XAS) as a novel approach for chemical speciation of selenium, in comparison with conventional Se K-edge XAS. We present spectra of a range of selenium species relevant to environmental and life science studies, including spectra of seleno-amino acids, which show strong similarities with S K-edge XAS of their sulfur congeners. We discuss strengths and limitations of HERFD-XAS, showing improvements in both speciation performance and low concentration detection. We also develop a simple method to correct fluorescence self-absorption artifacts, which is generally applicable to any HERFD-XAS experiment.
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- author
- Nehzati, Susan LU ; Dolgova, Natalia V. ; James, Ashley K. ; Cotelesage, Julien J.H. ; Sokaras, Dimosthenis ; Kroll, Thomas ; George, Graham N. and Pickering, Ingrid J.
- publishing date
- 2021-07-06
- type
- Contribution to journal
- publication status
- published
- subject
- in
- Analytical Chemistry
- volume
- 93
- issue
- 26
- pages
- 9 pages
- publisher
- The American Chemical Society (ACS)
- external identifiers
-
- pmid:34164981
- scopus:85110385500
- ISSN
- 0003-2700
- DOI
- 10.1021/acs.analchem.1c01503
- language
- English
- LU publication?
- no
- additional info
- Funding Information: We acknowledge support from the Natural Sciences and Engineering Research Council of Canada (IJP, GNG), Canada Foundation for Innovation (IJP), Canada Research Chairs (IJP, GNG), and a Dr. Rui Feng Scholarship (SN); A.K.J. and S.N. were Fellows and NVD an Associate in Canadian Institutes of Health Research-Training grant in Health Research Using Synchrotron Techniques (CIHR-THRUST). We thank the Max Planck Institute for Chemical Energy Conversion in Mülheim, Germany, for making a set of Si(844) analyzer crystals available to us. Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE-AC02-76SF00515. The SSRL Structural Molecular Biology Program is supported by the DOE Office of Biological and Environmental Research, and by the National Institutes of Health, National Institute of General Medical Sciences (including P41GM103393 and P30GM133894). Publisher Copyright: © 2021 American Chemical Society Copyright: Copyright 2021 Elsevier B.V., All rights reserved.
- id
- 4a750b33-b109-4460-b139-4a03ba27ecaf
- date added to LUP
- 2021-09-07 21:19:26
- date last changed
- 2024-05-04 11:52:49
@article{4a750b33-b109-4460-b139-4a03ba27ecaf,
abstract = {{<p>Selenium is in many ways an enigmatic element. It is essential for health but toxic in excess, with the difference between the two doses being narrower than for any other element. Environmentally, selenium is of concern due to its toxicity. As the rarest of the essential elements, its low levels often provide challenges to the analytical chemist. X-ray absorption spectroscopy (XAS) provides a powerful tool for in situ chemical speciation but is severely limited by poor spectroscopic resolution arising from core-hole lifetime broadening. Here we explore selenium Kα1 high energy resolution fluorescence detected XAS (HERFD-XAS) as a novel approach for chemical speciation of selenium, in comparison with conventional Se K-edge XAS. We present spectra of a range of selenium species relevant to environmental and life science studies, including spectra of seleno-amino acids, which show strong similarities with S K-edge XAS of their sulfur congeners. We discuss strengths and limitations of HERFD-XAS, showing improvements in both speciation performance and low concentration detection. We also develop a simple method to correct fluorescence self-absorption artifacts, which is generally applicable to any HERFD-XAS experiment.</p>}},
author = {{Nehzati, Susan and Dolgova, Natalia V. and James, Ashley K. and Cotelesage, Julien J.H. and Sokaras, Dimosthenis and Kroll, Thomas and George, Graham N. and Pickering, Ingrid J.}},
issn = {{0003-2700}},
language = {{eng}},
month = {{07}},
number = {{26}},
pages = {{9235--9243}},
publisher = {{The American Chemical Society (ACS)}},
series = {{Analytical Chemistry}},
title = {{High Energy Resolution Fluorescence Detected X-ray Absorption Spectroscopy : An Analytical Method for Selenium Speciation}},
url = {{http://dx.doi.org/10.1021/acs.analchem.1c01503}},
doi = {{10.1021/acs.analchem.1c01503}},
volume = {{93}},
year = {{2021}},
}