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.