Particulate Organic Matter Mobilization and Transformation Along a Himalayan River Revealed by ESI‐FT‐ICR‐MS

TL;DR: In this paper , Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT‐ICR•MS) was used to identify source tracers in the solvent extractable lipid fraction of riverine POM, finding up to 102 indicative molecular formulas for individual sources.

Abstract: Tracing pathways and transformations of particulate organic carbon from landscape sources to oceanic sinks is commonly done using the isotopic composition or biomarker content of particulate organic matter (POM). However, similarity of source characteristics and complex mixing in rivers often preclude a robust deconvolution of individual contributions. Moreover, these approaches are limited in detecting organic matter transformations. This impedes understanding of carbon cycling. Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT‐ICR‐MS) can simultaneously identify many molecular formulas from mixtures of organic matter, and provide direct information on its compositional variability. Here, we investigate how FT‐ICR‐MS can give insight into POM dynamics on a landscape scale, focusing on the trans‐Himalayan Kali Gandaki River, Nepal. Using molecular information, we identify source tracers in the solvent extractable lipid fraction of riverine POM, finding up to 102 indicative molecular formulas for individual sources. Further, we assess molecular transformations of the lipid fraction of POM during its transfer from litter into topsoil, and onwards into the river. A large number of shared mass formulas and a well‐preserved isoprenoidal patterns suggest efficient incorporation of litter into topsoil. In contrast, we observe a selective loss of mass formulas and a preferential export of formulas with low double bond equivalents and a low nominal oxidation state of carbon after organic matter entrainment in the river. Our results demonstrate the potential of FT‐ICR‐MS for source‐to‐sink studies, allowing detailed organic matter source characterization and discrimination, and tracking of molecular transformations along organic matter pathways spanning different spatial and temporal scales.