The bio- and thermal lability of dissolved organic matter as revealed by high-resolution mass spectrometry and thermal chemical analyses
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The bio- and thermal lability of dissolved organic matter as revealed by high-resolution mass spectrometry and thermal chemical analyses

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  • Journal Title:
    Marine Chemistry
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  • Description:
    It is critical to understand the chemical structures and lability of dissolved organic matter (DOM) in aquatic environments, as DOM represents one of the largest reduced carbon pools on earth. To achieve a comprehensive view of its composition and reactivity, DOM from both riverine and coastal waters were concurrently extracted via both ultrafiltration and modified styrene divinyl benzene polymer (PPL) based solid-phase-extraction (SPE), and further compared through multi-dimensional angles, including elemental analysis, total hydrolyzable amino acid composition, high-resolution liquid chromatography mass spectrometry (under both electrospray ionization modes), and thermochemical analysis. With a very low percentage (< 5%) of shared molecules, ultrafiltered-DOM (UDOM) and SPE-extracted DOM (SPEDOM) showed distinct differences in their bio- and thermal labilities. SPEDOM not only contained more “degraded” biomarkers, such as glycine, β-alanine, and γ-aminobutyric acid, but was also dominated by a higher abundance of more bio-recalcitrant lignin-like structures. Furthermore, thermogravimetric analysis revealed a higher activation energy of SPEDOM (138.8 ± 0.5 kJ·mol−1) than that of UDOM (125.4 ± 2.8 kJ·mol−1), suggesting that SPEDOM is more thermally recalcitrant than UDOM. Consistently, thermal slicing ramped pyrolysis showed a lower percentage of recalcitrant pyrolyzates (e.g., aromatic and phenol structures), but a higher contribution of labile compound classes (e.g., aliphatic structures) in UDOM, as well as a higher diversity of pyrolyzates from UDOM than SPEDOM. Taken together, our results demonstrated a highly heterogeneous nature in DOM composition and distinctly different bio- and thermal labilities between UDOM and SPEDOM, indicating that characterization of different fractions of DOM is needed for a comprehensive evaluation of natural DOM.
  • Source:
    Marine Chemistry, 250, 104184
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  • ISSN:
    0304-4203
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    Accepted Manuscript
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    Submitted
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