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Title: Sulfur Speciation in Biochars by Very High Resolution Benchtop Kα X-ray Emission Spectroscopy

Abstract

The analytical chemistry of sulfur-containing materials poses substantial technical challenges, especially due to the limitations of 33S NMR and the time-intensive preparations required for wet-chemistry analyses. A number of prior studies have found that synchrotron-based X-ray absorption near edge structure (XANES) measurements can give detailed speciation of sulfur chemistry in such cases. However, due to the obvious access limitations, synchrotron XANES of sulfur cannot be part of routine analytical practice across the chemical sciences community. Here, in a study of the sulfur chemistry in biochars, we compare and contrast the chemical inferences available from synchrotron XANES with that given by benchtop, extremely high resolution wavelength-dispersive X-ray fluorescence (WD-XRF) spectroscopy, also often called X-ray emission spectroscopy (XES). While the XANES spectra have higher total information content, often giving differentiation between different moieties having the same oxidation state, the lower sensitivity of the S Ka XES to coordination and local structure provides pragmatic benefit for the more limited goal of quantifying the S oxidation state distribution. Within that constrained metric, we find good agreement between the two methods. As the sulfur concentrations were as low as 150 ppm, these measurements provide proof-of-principle for characterization of the sulfur chemistry of biochars and potentialmore » applications to other areas such as soils, batteries, catalysts, and fossil fuels and their combustion products.« less

Authors:
 [1];  [1];  [2]
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  1. Univ. of Washington, Seattle, WA (United States)
  2. National Renewable Energy Lab. (NREL), Golden, CO (United States)
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1454908
Report Number(s):
NREL/JA-5100-71758
Journal ID: ISSN 1089-5639
Grant/Contract Number:  
AC36-08GO28308
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 122; Journal Issue: 23; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; sulfur chemistry; biochars; spectroscopy

Citation Formats

Holden, William M., Seidler, Gerald T., and Cheah, Singfoong. Sulfur Speciation in Biochars by Very High Resolution Benchtop Kα X-ray Emission Spectroscopy. United States: N. p., 2018. Web. doi:10.1021/acs.jpca.8b02816.
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Holden, William M., Seidler, Gerald T., & Cheah, Singfoong. Sulfur Speciation in Biochars by Very High Resolution Benchtop Kα X-ray Emission Spectroscopy. United States. doi:https://doi.org/10.1021/acs.jpca.8b02816
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Holden, William M., Seidler, Gerald T., and Cheah, Singfoong. Mon . "Sulfur Speciation in Biochars by Very High Resolution Benchtop Kα X-ray Emission Spectroscopy". United States. doi:https://doi.org/10.1021/acs.jpca.8b02816. https://www.osti.gov/servlets/purl/1454908.
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@article{osti_1454908,
title = {Sulfur Speciation in Biochars by Very High Resolution Benchtop Kα X-ray Emission Spectroscopy},
author = {Holden, William M. and Seidler, Gerald T. and Cheah, Singfoong},
abstractNote = {The analytical chemistry of sulfur-containing materials poses substantial technical challenges, especially due to the limitations of 33S NMR and the time-intensive preparations required for wet-chemistry analyses. A number of prior studies have found that synchrotron-based X-ray absorption near edge structure (XANES) measurements can give detailed speciation of sulfur chemistry in such cases. However, due to the obvious access limitations, synchrotron XANES of sulfur cannot be part of routine analytical practice across the chemical sciences community. Here, in a study of the sulfur chemistry in biochars, we compare and contrast the chemical inferences available from synchrotron XANES with that given by benchtop, extremely high resolution wavelength-dispersive X-ray fluorescence (WD-XRF) spectroscopy, also often called X-ray emission spectroscopy (XES). While the XANES spectra have higher total information content, often giving differentiation between different moieties having the same oxidation state, the lower sensitivity of the S Ka XES to coordination and local structure provides pragmatic benefit for the more limited goal of quantifying the S oxidation state distribution. Within that constrained metric, we find good agreement between the two methods. As the sulfur concentrations were as low as 150 ppm, these measurements provide proof-of-principle for characterization of the sulfur chemistry of biochars and potential applications to other areas such as soils, batteries, catalysts, and fossil fuels and their combustion products.},
doi = {10.1021/acs.jpca.8b02816},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 23,
volume = 122,
place = {United States},
year = {2018},
month = {5}
}
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Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI:  https://doi.org/10.1021/acs.jpca.8b02816
Copyright Statement
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Cited by: 9 works
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Figures / Tables:

Figure 1 Figure 1: S Kα XES spectrum obtained from four different biochar samples processed under different conditions. The decrease of the shoulder near 2309.15 eV with increasing temperature shows a decrease in the amount of oxidized sulfur species.
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Works referencing / citing this record:

A von Hamos spectrometer for in situ sulfur speciation by non-resonant sulfur Kα emission spectroscopy
journal, January 2019

  • Kuzmenko, Dzulija; Vogelsang, Urs; Hitz, Stephan
  • Journal of Analytical Atomic Spectrometry, Vol. 34, Issue 10
  • DOI: 10.1039/c9ja00195f

A color x-ray camera for 2–6 keV using a mass produced back illuminated complementary metal oxide semiconductor sensor
journal, September 2018

  • Holden, William M.; Hoidn, Oliver R.; Seidler, Gerald T.
  • Review of Scientific Instruments, Vol. 89, Issue 9
  • DOI: 10.1063/1.5047934

An improved laboratory-based x-ray absorption fine structure and x-ray emission spectrometer for analytical applications in materials chemistry research
journal, February 2019

  • Jahrman, Evan P.; Holden, William M.; Ditter, Alexander S.
  • Review of Scientific Instruments, Vol. 90, Issue 2
  • DOI: 10.1063/1.5049383

Vacuum formed temporary spherically and toroidally bent crystal analyzers for x-ray absorption and x-ray emission spectroscopy
journal, January 2019

  • Jahrman, Evan P.; Holden, William M.; Ditter, Alexander S.
  • Review of Scientific Instruments, Vol. 90, Issue 1
  • DOI: 10.1063/1.5057231
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