Abstract
Understanding dissolved organic matter (DOM) export to the ocean is needed to assess the impact of climate change on the global carbon cycle. The molecular-level characterization of DOM compositional variability and complexity in aquatic ecosystems has been analytically challenging. Advanced analytical studies based on ultra-high resolution mass spectrometry (FT ICR MS) have proven highly successful to better understand the dynamics of DOM in coastal ecosystems. In this work, the molecular signature of DOM along a freshwater-to-estuarine gradient in the Harney River, Florida Everglades was analyzed for the first time using a novel approach based on tandem high resolution ion mobility and ultra-high resolution mass spectrometry (ESI-TIMS-FT ICR MS). This method enhances traditional DOM molecular characterization by including the molecular isomeric complexity. An average of six and up to 12 isomers were observed per chemical formula and characteristic isomers to each section of the freshwater-to-estuarine gradient were successfully identified. We measured a decrease in the chemical complexity and diversity (both in the number of molecular formulas and number of isomers per chemical formula) with increasing salinity; this trend is representative of the biogeochemical transformations of DOM during transport and along source variations, showing both clear degradation products and formation of new components along the salinity transect. The inclusion of the isomeric content at the molecular formula allowed to differentiate isomeric species that are present along the transect (mainly lignin-type components) and responsible for the DOM refractory nature. DOM isomeric fingerprints characteristic of the molecular variability along the Everglades freshwater-to-estuarine gradient are also described.
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Data availability
The TIMS-FT-ICR MS raw data from the SPE-DOM samples is freely accessible at https://doi.org/10.34703/gzx1-9v95/ZW5RIM.
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Acknowledgements
This work was supported by the National Science Foundation Division of Chemistry, under CAREER award CHE-1654274, with co-funding from the Division of Molecular and Cellular Biosciences to FFL. DL acknowledges the fellowship provided by the National Science Foundation award (HRD-1547798) to Florida International University as part of the Centers for Research Excellence in Science and Technology (CREST) Program. DL also would like to acknowledge Edward Castañeda, and Ryan Bremen and Kenny Anderson from the Ecosystem Ecology Laboratory at Florida International University (FIU) for their field and laboratory support, as well as Michael G Rugge from the Institute of Environment at FIU for his help on generating the map. This is contribution number xxxx from the Institute of Environment at Florida International University. This material was developed in collaboration with the Florida Coastal Everglades Long Term Ecological Research program under National Science Foundation Grant No. DEB-2025954. The authors acknowledge the personnel of the Advance Mass Spectrometry Facility at Florida International University as well as David Stranz and Sierra Analytics, Inc. for their support with the Composer software.
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Supplementary material 1 Figure S1 describes 2D van Krevelen plots highlighting the unsaturation level of common and unique chemical compounds found across the DOM samples at the Harney River. Figure S2 highlights the isomeric complexity and compositional pattern15of the molecular formulas shared for all samples (A) and filtered by heteroatom classes (B–D). Figure S3 depicts the van Krevelen plot of compounds shared across samples HR-2, HR-3, HR-4, and HR-5. Figure S5 illustrates the change in isomeric diversity along the salinity transect of two chemical formulas (C14H10O7 and C15H14O6) found in all sites (PDF 776.0 kb)
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Leyva, D., Jaffé, R., Courson, J. et al. Molecular level characterization of DOM along a freshwater-to-estuarine coastal gradient in the Florida Everglades. Aquat Sci 84, 63 (2022). https://doi.org/10.1007/s00027-022-00887-y
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DOI: https://doi.org/10.1007/s00027-022-00887-y