Alicyclic carboxylic acids in soil humic acid as detected with ultrahigh resolution mass spectrometry and multi-dimensional NMR
Abstract
It has been well accepted that humic acids in soils comprise both aromatic and aliphatic structural units that harbor mainly oxygenated functional groups such as carboxylic acids, aldehydes, ketones, and hydroxyl groups. Recent mass spectral data obtained from electrospray ionization-Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICRMS) suggest that the main functional groups in humic acids are carboxylic acids bound to both alicyclic and condensed aromatic molecules. It was suggested that these structural entities originate from oxidation of lignin. To provide additional support, detailed structural characteristics were obtained here using several multi-dimensional nuclear magnetic resonance (NMR) techniques to observe the molecular connectivity of humic acid components, with a focus on carboxylic acids in particular. The humic acid sample examined had been shown to exhibit structural characteristics similar to a larger set of soil humic acids. Here in this study, many carboxylic acid resonances were found to correlate with protons that could be assigned to aliphatic and alicyclic chemical shift regions. Functional groups with heteroatoms such as alcohols, some olefins and an assortment of methyl groups were found to correlate within 2–3 bonds of carboxylic acid groups. The collection of structural components and their proximity to a variety of carboxylic groupsmore »
- Authors:
-
- Old Dominion University, Norfolk, VA (United States)
- Publication Date:
- Research Org.:
- Texas A & M University at Galveston, TX (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC); Old Dominion University
- OSTI Identifier:
- 1538699
- Alternate Identifier(s):
- OSTI ID: 1549567
- Grant/Contract Number:
- SC0014152; ER64567-1031562-0014364
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Organic Geochemistry
- Additional Journal Information:
- Journal Volume: 112; Journal Issue: C; Journal ID: ISSN 0146-6380
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 58 GEOSCIENCES; soil humic acid; alicyclic; ESI-FTICRMS; lignin; heteronuclear multiple bond coherence; carboxyl
Citation Formats
DiDonato, Nicole, and Hatcher, Patrick G. Alicyclic carboxylic acids in soil humic acid as detected with ultrahigh resolution mass spectrometry and multi-dimensional NMR. United States: N. p., 2017.
Web. doi:10.1016/j.orggeochem.2017.06.010.
DiDonato, Nicole, & Hatcher, Patrick G. Alicyclic carboxylic acids in soil humic acid as detected with ultrahigh resolution mass spectrometry and multi-dimensional NMR. United States. https://doi.org/10.1016/j.orggeochem.2017.06.010
DiDonato, Nicole, and Hatcher, Patrick G. Thu .
"Alicyclic carboxylic acids in soil humic acid as detected with ultrahigh resolution mass spectrometry and multi-dimensional NMR". United States. https://doi.org/10.1016/j.orggeochem.2017.06.010. https://www.osti.gov/servlets/purl/1538699.
@article{osti_1538699,
title = {Alicyclic carboxylic acids in soil humic acid as detected with ultrahigh resolution mass spectrometry and multi-dimensional NMR},
author = {DiDonato, Nicole and Hatcher, Patrick G.},
abstractNote = {It has been well accepted that humic acids in soils comprise both aromatic and aliphatic structural units that harbor mainly oxygenated functional groups such as carboxylic acids, aldehydes, ketones, and hydroxyl groups. Recent mass spectral data obtained from electrospray ionization-Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICRMS) suggest that the main functional groups in humic acids are carboxylic acids bound to both alicyclic and condensed aromatic molecules. It was suggested that these structural entities originate from oxidation of lignin. To provide additional support, detailed structural characteristics were obtained here using several multi-dimensional nuclear magnetic resonance (NMR) techniques to observe the molecular connectivity of humic acid components, with a focus on carboxylic acids in particular. The humic acid sample examined had been shown to exhibit structural characteristics similar to a larger set of soil humic acids. Here in this study, many carboxylic acid resonances were found to correlate with protons that could be assigned to aliphatic and alicyclic chemical shift regions. Functional groups with heteroatoms such as alcohols, some olefins and an assortment of methyl groups were found to correlate within 2–3 bonds of carboxylic acid groups. The collection of structural components and their proximity to a variety of carboxylic groups supports the occurrence of carboxylated alicyclic molecules as important elements of the aliphatic portion of soil humic acids and a pathway from lignin is consistent with recent findings.},
doi = {10.1016/j.orggeochem.2017.06.010},
journal = {Organic Geochemistry},
number = C,
volume = 112,
place = {United States},
year = {Thu Jul 20 00:00:00 EDT 2017},
month = {Thu Jul 20 00:00:00 EDT 2017}
}
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Works referencing / citing this record:
Validation and Evaluation of High-Resolution Orbitrap Mass Spectrometry on Molecular Characterization of Dissolved Organic Matter
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