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Title: Signatures of Biologically Driven Hemicellulose Modification Quantified by Analytical Pyrolysis Coupled with Multidimensional Gas Chromatography Mass Spectrometry

Abstract

Biomass storage operation is one major source of feedstock quality variability that impacts on downstream preprocessing, feeding, handling and conversion into biofuels, chemicals and products. In field Ccorn stover biomass bales undergoes degradation and cell wall components modification resulting from microbial biological heating occurring during storage. A molecular characterization of the modification was achieved to unveil and understand the changes of structural cell wall modification in corn stover samples by conducting low temperature (400°C) pyrolysis, comparing samples that were mildly biologicallyun heated to those that had been subjected to microbial severe biological heating (~60°C). Pyrolysis of the samples originating from biomass that had been heated during storage generated small oxygenates such as furfural, 5-methylfurfural and 2-(5H)-furanone with efficiencies that were as much as ten times greater than those measured for the mildly unheated samples. Most of the compounds having enhanced efficiencies were C5 oxygenates, suggesting that the pyrolysis products may be formed from hemicellulosic precursor polymers in the corn stover. The findings suggest that microbial heating may be disrupting the cell wall structure, fragmenting the hemicellulose or cellulose chains, generating more polymer termini that have higher efficiency for generating the oxygenates at lower temperatures. Pyrolysis variability with temperature may bemore » a beneficial strategy for improved biomass cell wall characterization, and for guiding control strategies for enhanced control over product distributions , providing insights to understand and manage the feedstock variability as well as to inform harvest and storage best management practices.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1];  [1]; ORCiD logo [1]
  1. Idaho National Lab. (INL), Idaho Falls, ID (United States)
Publication Date:
Research Org.:
Idaho National Lab. (INL), Idaho Falls, ID (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
OSTI Identifier:
1631151
Report Number(s):
INL/JOU-19-56314-Rev000
Journal ID: ISSN 2168-0485
Grant/Contract Number:  
AC07-05ID14517
Resource Type:
Accepted Manuscript
Journal Name:
ACS Sustainable Chemistry & Engineering
Additional Journal Information:
Journal Volume: 8; Journal Issue: 4; Journal ID: ISSN 2168-0485
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Biomass; Characterization; mass spectrometry; pyrolysis; microbial heating; corn stover; hemicellulose; gas chromatography

Citation Formats

Groenewold, Gary S., Li, Chenlin, Zarzana, Christopher A, Hoover, Amber N., Rigg, Kyle, and Ray, Allison E.. Signatures of Biologically Driven Hemicellulose Modification Quantified by Analytical Pyrolysis Coupled with Multidimensional Gas Chromatography Mass Spectrometry. United States: N. p., 2019. Web. https://doi.org/10.1021/acssuschemeng.9b06524.
Groenewold, Gary S., Li, Chenlin, Zarzana, Christopher A, Hoover, Amber N., Rigg, Kyle, & Ray, Allison E.. Signatures of Biologically Driven Hemicellulose Modification Quantified by Analytical Pyrolysis Coupled with Multidimensional Gas Chromatography Mass Spectrometry. United States. https://doi.org/10.1021/acssuschemeng.9b06524
Groenewold, Gary S., Li, Chenlin, Zarzana, Christopher A, Hoover, Amber N., Rigg, Kyle, and Ray, Allison E.. Tue . "Signatures of Biologically Driven Hemicellulose Modification Quantified by Analytical Pyrolysis Coupled with Multidimensional Gas Chromatography Mass Spectrometry". United States. https://doi.org/10.1021/acssuschemeng.9b06524. https://www.osti.gov/servlets/purl/1631151.
@article{osti_1631151,
title = {Signatures of Biologically Driven Hemicellulose Modification Quantified by Analytical Pyrolysis Coupled with Multidimensional Gas Chromatography Mass Spectrometry},
author = {Groenewold, Gary S. and Li, Chenlin and Zarzana, Christopher A and Hoover, Amber N. and Rigg, Kyle and Ray, Allison E.},
abstractNote = {Biomass storage operation is one major source of feedstock quality variability that impacts on downstream preprocessing, feeding, handling and conversion into biofuels, chemicals and products. In field Ccorn stover biomass bales undergoes degradation and cell wall components modification resulting from microbial biological heating occurring during storage. A molecular characterization of the modification was achieved to unveil and understand the changes of structural cell wall modification in corn stover samples by conducting low temperature (400°C) pyrolysis, comparing samples that were mildly biologicallyun heated to those that had been subjected to microbial severe biological heating (~60°C). Pyrolysis of the samples originating from biomass that had been heated during storage generated small oxygenates such as furfural, 5-methylfurfural and 2-(5H)-furanone with efficiencies that were as much as ten times greater than those measured for the mildly unheated samples. Most of the compounds having enhanced efficiencies were C5 oxygenates, suggesting that the pyrolysis products may be formed from hemicellulosic precursor polymers in the corn stover. The findings suggest that microbial heating may be disrupting the cell wall structure, fragmenting the hemicellulose or cellulose chains, generating more polymer termini that have higher efficiency for generating the oxygenates at lower temperatures. Pyrolysis variability with temperature may be a beneficial strategy for improved biomass cell wall characterization, and for guiding control strategies for enhanced control over product distributions , providing insights to understand and manage the feedstock variability as well as to inform harvest and storage best management practices.},
doi = {10.1021/acssuschemeng.9b06524},
journal = {ACS Sustainable Chemistry & Engineering},
number = 4,
volume = 8,
place = {United States},
year = {2019},
month = {12}
}

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