Alicyclic carboxylic acids in soil humic acid as detected with ultrahigh resolution mass spectrometry and multi-dimensional NMR

DiDonato, Nicole; Hatcher, Patrick G.

doi:10.1016/j.orggeochem.2017.06.010

Alicyclic carboxylic acids in soil humic acid as detected with ultrahigh resolution mass spectrometry and multi-dimensional NMR

Journal Article · Thu Jul 20 00:00:00 EDT 2017 · Organic Geochemistry

DOI:https://doi.org/10.1016/j.orggeochem.2017.06.010· OSTI ID:1538699

DiDonato, Nicole ^[1]; Hatcher, Patrick G. ^[2]

Old Dominion University, Norfolk, VA (United States); DOE/OSTI
Old Dominion University, Norfolk, VA (United States)

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.

View Accepted Manuscript (DOE)

Research Organization:: Texas A & M University at Galveston, TX (United States)

Sponsoring Organization:: Old Dominion University; USDOE; USDOE Office of Science (SC)

Grant/Contract Number:: SC0014152

OSTI ID:: 1538699

Alternate ID(s):: OSTI ID: 1549567

Journal Information:: Organic Geochemistry, Journal Name: Organic Geochemistry Journal Issue: C Vol. 112; ISSN 0146-6380

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
58 GEOSCIENCES
ESI-FTICRMS
alicyclic
carboxyl
heteronuclear multiple bond coherence
lignin
soil humic acid

Alicyclic carboxylic acids in soil humic acid as detected with ultrahigh resolution mass spectrometry and multi-dimensional NMR

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References (35)

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