Virginia Institute of Marine Science
Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) has proven to be a powerful technique revealing complexity and diversity of natural DOM molecules, but its application to DOM analysis in grazing-impacted agricultural systems remains scarce. In the present study, we presented a case study of using ESI-FTICR-MS in analyzing DOM from four headwater streams draining forest-or pasture-dominated watersheds in Virginia, USA. In all samples, most formulas were CHO compounds (71.8-87.9%), with other molecular series (CHOS, CHON, CHONS, and CHOP (N, S)) accounting for only minor fractions. All samples were dominated by molecules falling in the lignin-like region (H/C = 0.7-1.5, O/C = 0.1-0.67), suggesting the predominance of allochthonous, terrestrial plant-derived DOM. Relative to the two pasture streams, DOM formulas in the two forest streams were more similar, based on Jaccard similarity coefficients and nonmetric multidimensional scaling calculated from Bray-Curtis distance. Formulas from the pasture streams were characterized by lower proportions of aromatic formulas and lower unsaturation, suggesting that the allochthonous versus autochthonous contributions of organic matter to streams were modified by pasture land use. The number of condensed aromatic structures (CAS) was higher for the forest streams, which is possibly due to the controlled burning in the forest-dominated watersheds and suggests that black carbon was mobilized from soils to streams. During 15-day biodegradation experiments, DOM from the two pasture streams was altered to a greater extent than DOM from the forest streams, with formulas with H/C and O/C ranges similar to protein (H/C = 1.5-2.2, O/C = 0.3-0.67), lipid (H/C = 1.5-2.0, O/C = 0-0.3), and unsaturated hydrocarbon (H/C = 0.7-1.5, O/C = 0-0.1) being the most bioreactive groups. Aromatic compound formulas including CAS were preferentially removed during combined light+bacterial incubations, supporting the contention that black carbon is labile to light alterations. Collectively, our data demonstrate that head-water DOM composition contains integrative information on watershed sources and processes, and the application of ESI-FTICR-MS technique offers additional insights into compound composition and reactivity unrevealed by fluorescence and stable carbon isotopic measurements.
RESOLUTION MASS-SPECTROMETRY; LAND-USE; BLACK CARBON; MOLECULAR CHARACTERIZATION; PHOTOCHEMICAL DEGRADATION; ELECTROSPRAY; SOIL; BIOAVAILABILITY; DOM; SPECTRA
This work was supported by a start-up analytical fund to YL from the Department of Geological Science at the University of Alabama and a Mellon Foundation Postdoctoral Fellow Grant from the College of William and Mary. The authors also acknowledge the HOOK's research fund and the Johnson travel fund from the Department of Geological Sciences, the University of Alabama, for providing student research and travel funds.; We thank Dr. B. Zhang for providing support for statistical analysis. This work was supported by a start-up analytical fund to Y. L. from the Department of Geological Science at the University of Alabama, in collaboration with a Mellon Foundation Postdoctoral Fellow Grant from the College of William and Mary. We also acknowledge the HOOK's research fund and the Johnson travel fund from the Department of Geological Sciences, the University of Alabama, for providing student research and travel funds.
Lu Y, Li X, Mesfioui R, Bauer JE, Chambers RM, Canuel EA, et al. (2015) Use of ESI-FTICR-MS to Characterize Dissolved Organic Matter in Headwater Streams Draining Forest-Dominated and Pasture-Dominated Watersheds. PLoS ONE 10(12): e0145639. doi:10.1371/journal.pone.0145639