DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

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]
  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.
Holden, William M., Seidler, Gerald T., & Cheah, Singfoong. Sulfur Speciation in Biochars by Very High Resolution Benchtop Kα X-ray Emission Spectroscopy. United States. https://doi.org/10.1021/acs.jpca.8b02816
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. https://doi.org/10.1021/acs.jpca.8b02816. https://www.osti.gov/servlets/purl/1454908.
@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}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 9 works
Citation information provided by
Web of Science

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.

Save / Share:

Works referenced in this record:

Biochar effects on soil biota – A review
journal, September 2011


Biochar and its effects on plant productivity and nutrient cycling: a meta-analysis
journal, December 2012

  • Biederman, Lori A.; Harpole, W. Stanley
  • GCB Bioenergy, Vol. 5, Issue 2
  • DOI: 10.1111/gcbb.12037

Agronomic and remedial benefits and risks of applying biochar to soil: Current knowledge and future research directions
journal, February 2016


Sulfur forms in organic substrates affecting S mineralization in soil
journal, June 2013


Direct Determination of Sulfur Forms in Green River Oil Shale.
journal, March 1964

  • Smith, J. W.; Young, N. B.; Lawlor, D. L.
  • Analytical Chemistry, Vol. 36, Issue 3
  • DOI: 10.1021/ac60209a019

The behaviour of sulphur forms during pyrolysis of low-rank coal
journal, November 1992


Investigation of Sulfur Retention and the Effect of Inorganic Matter during Pyrolysis of South Australian Low-Rank Coals
journal, September 1998

  • Telfer, M. A.; Zhang, D. K.
  • Energy & Fuels, Vol. 12, Issue 6
  • DOI: 10.1021/ef980117x

Speciation of Sulfur in Biochar Produced from Pyrolysis and Gasification of Oak and Corn Stover
journal, July 2014

  • Cheah, Singfoong; Malone, Shealyn C.; Feik, Calvin J.
  • Environmental Science & Technology, Vol. 48, Issue 15
  • DOI: 10.1021/es500073r

Sulfur K-edge x-ray absorption spectroscopy of petroleum asphaltenes and model compounds
journal, April 1989

  • George, Graham N.; Gorbaty, Martin L.
  • Journal of the American Chemical Society, Vol. 111, Issue 9
  • DOI: 10.1021/ja00191a012

Sulfur Speciation in Soil by S K -Edge XANES Spectroscopy: Comparison of Spectral Deconvolution and Linear Combination Fitting
journal, April 2011

  • Prietzel, Jörg; Botzaki, Anna; Tyufekchieva, Nora
  • Environmental Science & Technology, Vol. 45, Issue 7
  • DOI: 10.1021/es102180a

Introduction to XAFS
book, January 2010


An efficient X-ray spectrometer based on thin mosaic crystal films and its application in various fields of X-ray spectroscopy
journal, May 2009

  • Legall, Herbert; Stiel, Holger; Schnürer, Matthias
  • Journal of Applied Crystallography, Vol. 42, Issue 4
  • DOI: 10.1107/S0021889809006803

Laboratory von Hámos X-ray spectroscopy for routine sample characterization
journal, October 2016

  • Németh, Zoltán; Szlachetko, Jakub; Bajnóczi, Éva G.
  • Review of Scientific Instruments, Vol. 87, Issue 10
  • DOI: 10.1063/1.4964098

A laboratory-based hard x-ray monochromator for high-resolution x-ray emission spectroscopy and x-ray absorption near edge structure measurements
journal, November 2014

  • Seidler, G. T.; Mortensen, D. R.; Remesnik, A. J.
  • Review of Scientific Instruments, Vol. 85, Issue 11
  • DOI: 10.1063/1.4901599

High-resolution Laue-type DuMond curved crystal spectrometer
journal, September 2013

  • Szlachetko, M.; Berset, M.; Dousse, J. -Cl.
  • Review of Scientific Instruments, Vol. 84, Issue 9
  • DOI: 10.1063/1.4821621

Development of a new in-laboratory XAFS apparatus based on new concept
journal, March 2001

  • Taguchi, Takeyoshi; Harada, Jimpei; Kiku, Atsunori
  • Journal of Synchrotron Radiation, Vol. 8, Issue 2
  • DOI: 10.1107/S0909049500018458

Customization of an InHouse XAFS Spectrometer for Sulfur Measurement
journal, January 2005


Variable Rowland radius laboratory vacuum surface-sensitive x-ray absorption fine structure spectrometer
journal, February 2007

  • Yuryev, Yu. N.; Lee, Hwack-Joo; Park, Hyun-Min
  • Review of Scientific Instruments, Vol. 78, Issue 2
  • DOI: 10.1063/1.2669591

2017 atomic spectrometry update – a review of advances in X-ray fluorescence spectrometry and its special applications
journal, January 2017

  • West, Margaret; Ellis, Andrew T.; Streli, Christina
  • Journal of Analytical Atomic Spectrometry, Vol. 32, Issue 9
  • DOI: 10.1039/C7JA90035J

X-ray fluorescence determination of sulfur chemical state in sulfide ores: Sulfur chemical state determination by WDXRF analysis
journal, September 2016

  • Chubarov, Victor; Amosova, Alena; Finkelshtein, Alexander
  • X-Ray Spectrometry, Vol. 45, Issue 6
  • DOI: 10.1002/xrs.2712

Determination of forms of sulphur in plant material by x-ray fluorescence spectrometry
journal, April 1990


X-ray emission spectroscopy
journal, August 2009


High resolution 1s core hole X-ray spectroscopy in 3d transition metal complexes—electronic and structural information
journal, January 2005


Five-element Johann-type x-ray emission spectrometer with a single-photon-counting pixel detector
journal, June 2011

  • Kleymenov, Evgeny; van Bokhoven, Jeroen A.; David, Christian
  • Review of Scientific Instruments, Vol. 82, Issue 6
  • DOI: 10.1063/1.3600452

A seven-crystal Johann-type hard x-ray spectrometer at the Stanford Synchrotron Radiation Lightsource
journal, May 2013

  • Sokaras, D.; Weng, T. -C.; Nordlund, D.
  • Review of Scientific Instruments, Vol. 84, Issue 5
  • DOI: 10.1063/1.4803669

Energy-dispersive X-ray emission spectroscopy using an X-ray free-electron laser in a shot-by-shot mode
journal, November 2012

  • Alonso-Mori, R.; Kern, J.; Gildea, R. J.
  • Proceedings of the National Academy of Sciences, Vol. 109, Issue 47, p. 19103-19107
  • DOI: 10.1073/pnas.1211384109

Design and performance of a versatile curved-crystal spectrometer for high-resolution spectroscopy in the tender x-ray range
journal, March 2012

  • Kavčič, M.; Budnar, M.; Mühleisen, A.
  • Review of Scientific Instruments, Vol. 83, Issue 3
  • DOI: 10.1063/1.3697862

Insights into the Geometric and Electronic Structure of Transition Metal Centers from Valence-to-Core X-ray Emission Spectroscopy
journal, September 2015


The role of X-ray spectroscopy in understanding the geometric and electronic structure of nitrogenase
journal, June 2015

  • Kowalska, Joanna; DeBeer, Serena
  • Biochimica et Biophysica Acta (BBA) - Molecular Cell Research, Vol. 1853, Issue 6
  • DOI: 10.1016/j.bbamcr.2014.11.027

Valence-to-Core X-Ray Emission Spectroscopy of Iron-Carbonyl Complexes: Implications for the Examination of Catalytic Intermediates
journal, October 2013

  • Delgado-Jaime, Mario Ulises; DeBeer , Serena; Bauer, Matthias
  • Chemistry - A European Journal, Vol. 19, Issue 47
  • DOI: 10.1002/chem.201301913

X-ray Emission Spectroscopy Evidences a Central Carbon in the Nitrogenase Iron-Molybdenum Cofactor
journal, November 2011


Valence-state speciation of sulfur by x-ray fluorescence spectometry and Kalman filtering
journal, July 1991


Chemical speciation via X-ray emission spectroscopy in the tender X-ray range
journal, January 2016

  • Petric, Marko; Kavčič, Matjaž
  • Journal of Analytical Atomic Spectrometry, Vol. 31, Issue 2
  • DOI: 10.1039/C5JA00394F

Electronic Structure of Sulfur Studied by X-ray Absorption and Emission Spectroscopy
journal, August 2009

  • Alonso Mori, R.; Paris, E.; Giuli, G.
  • Analytical Chemistry, Vol. 81, Issue 15
  • DOI: 10.1021/ac900970z

Chemical speciation of sulfur in activated carbon by wavelength-dispersive PIXE technique
journal, May 2009

  • Tada, T.; Fukuda, H.; Hasegawa, J.
  • X-Ray Spectrometry, Vol. 38, Issue 3
  • DOI: 10.1002/xrs.1147

A compact dispersive refocusing Rowland circle X-ray emission spectrometer for laboratory, synchrotron, and XFEL applications
journal, July 2017

  • Holden, William M.; Hoidn, Oliver R.; Ditter, Alexander S.
  • Review of Scientific Instruments, Vol. 88, Issue 7
  • DOI: 10.1063/1.4994739

Note: A disposable x-ray camera based on mass produced complementary metal-oxide-semiconductor sensors and single-board computers
journal, August 2015

  • Hoidn, Oliver R.; Seidler, Gerald T.
  • Review of Scientific Instruments, Vol. 86, Issue 8
  • DOI: 10.1063/1.4929713

Nonlocal heat transport and improved target design for x-ray heating studies at x-ray free electron lasers
journal, January 2018


Chemical state analysis of sulfur in samples of environmental interest using high resolution measurement of Kα diagram line
journal, August 2004

  • Kavčič, Matjaž; Karydas, A. G.; Zarkadas, Ch
  • Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 222, Issue 3-4
  • DOI: 10.1016/j.nimb.2004.04.161

Chemical speciation using high energy resolution PIXE spectroscopy in the tender X-ray range
journal, February 2018

  • Kavčič, Matjaž; Petric, Marko; Vogel-Mikuš, Katarina
  • Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 417
  • DOI: 10.1016/j.nimb.2017.06.009

IFEFFIT  : interactive XAFS analysis and FEFF fitting
journal, March 2001


Progress towards an x-ray emission method for the speciation of sulphur in coal using S Kβ emission
journal, February 1994


Determination of oxidation states of aluminium, silicon and sulfur
journal, January 2002

  • Perino, Ernesto; Deluigi, Mar�a Torres; Olsina, Roberto
  • X-Ray Spectrometry, Vol. 31, Issue 2
  • DOI: 10.1002/xrs.561

Theoretical approaches to x-ray absorption fine structure
journal, July 2000


Electronic Structure of Third-Row Elements in Different Local Symmetries Studied by Valence-to-Core X-ray Emission Spectroscopy
journal, May 2016


Probing Valence Orbital Composition with Iron Kβ X-ray Emission Spectroscopy
journal, July 2010

  • Lee, Nicole; Petrenko, Taras; Bergmann, Uwe
  • Journal of the American Chemical Society, Vol. 132, Issue 28
  • DOI: 10.1021/ja101281e

Valence-to-Core X-ray Emission Spectroscopy: A Sensitive Probe of the Nature of a Bound Ligand
journal, April 2011

  • Pollock, Christopher J.; DeBeer, Serena
  • Journal of the American Chemical Society, Vol. 133, Issue 14
  • DOI: 10.1021/ja200560z

Rapid chemical state analysis in air by highly sensitive high-resolution PIXE using a v. Hamos crystal spectrometer
journal, January 2005

  • Maeda, Kuniko; Hasegawa, Kenichi; Maeda, Masaru
  • X-Ray Spectrometry, Vol. 34, Issue 4
  • DOI: 10.1002/xrs.853

Sulfur-Metal Orbital Hybridization in Sulfur-Bearing Compounds Studied by X-ray Emission Spectroscopy
journal, July 2010

  • Mori, R. Alonso; Paris, E.; Giuli, G.
  • Inorganic Chemistry, Vol. 49, Issue 14
  • DOI: 10.1021/ic100304z

Sulphur Kβ emission spectra reveal protonation states of aqueous sulfuric acid
journal, February 2016

  • Niskanen, Johannes; Sahle, Christoph J.; Ruotsalainen, Kari O.
  • Scientific Reports, Vol. 6, Issue 1
  • DOI: 10.1038/srep21012

Chromatographic and electrophoretic separation of inorganic sulfur and sulfur–oxygen species
journal, March 2001


Sulfur Transformation during Microwave and Conventional Pyrolysis of Sewage Sludge
journal, December 2016


Works referencing / citing this record:

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

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

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

Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.