Origin-specific molecular signatures of dissolved organic matter in the Lena Delta

Large Arctic rivers discharge significant amounts of dissolved organic matter (DOM) into the Arctic Ocean. We sampled natural waters of the Lena River, the Buor-Khaya Bay (Laptev Sea), permafrost melt water creeks, ice complex melt water creeks and a lake. The goal of this study was to characterize the molecular DOM composition with respect to different water bodies within the Lena Delta. We aimed at an identification of source-specific DOM molecular markers and their relative contribution to DOM of different origin. The molecular characterization was performed for solid-phase extracted DOM by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Average dissolved organic carbon concentrations in the original samples were 490 ± 75 µmol C L−1 for riverine and bay samples and 399 ± 115 µmol C L−1 for permafrost melt water creeks. Average TDN concentrations were elevated in the permafrost melt waters (19.7 ± 7.1 µmol N L−1) in comparison to the river and the bay (both 13.2 ± 2.6 µmol N L−1). FT-ICR MS and statistical tools demonstrated that the origin of DOM in the Lena Delta was systematically reflected in its molecular composition. Magnitude weighted parameters calculated from MS data (O/Cwa, H/Cwa, C/Nwa) highlighted preliminary sample discrimination. The highest H/Cwa of 1.315 was found for DOM in melt water creeks in comparison to 1.281 for river and 1.230 for the bay samples. In the bay samples we observed a higher fraction of oxygen-rich components which was reflected in an O/Cwa ratio of 0.445 in comparison to 0.425 and 0.427 in the river and creeks, respectively. From the southernmost location to the bay a relative depletion of nitrogenous molecular markers and an enrichment of oxidized DOM components occurred. The highest contribution of nitrogenous components was indicative for creeks reflected in a C/Nwa of 104 in comparison to 143 and 176 in the river and bay, respectively. These observations were studied on a molecular formula level using principal component and indicator value analyses. The results showed systematic differences with respect to water origin and constitute an important basis for a better mechanistic understanding of DOM transformations in the changing Arctic rivers

Molecular Mapping of Sorbent Selectivities with Respect to Isolation of Arctic Dissolved Organic Matter as Measured by Fourier Transform Mass Spectrometry

The objectives of this study were to identify molecular features characteristic to arctic DOM from the Kolyma River basin and to elucidate structural imprints induced by a choice of the sorption technique. To achieve this goal, DOM was isolated from the Kolyma River basin with a use of three nonionic sorbents: Amberlite XAD-8 resin, PPL- and C18 - SPE cartridges, and one anion exchanging resin–diethylaminoethyl (DEAE) -cellulose. The structural studies were conducted with a use of electrospray ionization Fourier Transform Ion Cyclotron Resonance (ESI FT-ICR) mass spectrometry and liquid state ¹H NMR spectroscopy. The DOM isolates obtained with a use of PPL and C18 cartridges were characterized with higher content of aliphatic compounds as compared to XAD-8 and DEAE-isolates. In total, for all arctic DOM isolates we observed predominance of hydrogen saturated compounds with high H/C values of identified formulas from FT-ICR MS data. ¹H NMR spectroscopy studies have confirmed this trend and revealed high contribution of alkyl-chain protons into the spectral density of the arctic DOM reaching 43% for PPL isolates