The biochemical composition of dissolved organic matter (DOM) strongly influences its biogeochemical role in freshwater ecosystems, yet DOM composition measurements are not routinely incorporated into ecological studies. To date, the majority of studies of freshwater ecosystems have relied on bulk analyses of dissolved organic carbon and nitrogen to obtain information about DOM cycling. The problem with this approach is that the biogeochemical significance of DOM can only partially be elucidated using bulk analyses alone because bulk measures cannot detect most carbon and nitrogen transformations. Advances in fluorescence spectroscopy provide an alternative to traditional approaches for characterizing aquatic DOM, and allow for the rapid and precise characterization of DOM necessary to more comprehensively trace DOM dynamics. It is within this context that we discuss the use of fluorescence spectroscopy to provide a novel approach to tackling a longstanding problem: understanding the dynamics and biogeochemical role of DOM. We highlight the utility of fluorescence characterization of DOM and provide examples of the potential range of applications for incorporating DOM fluorescence into ecological studies in the hope that this rapidly evolving technique will further our understanding of the biogeochemical role of DOM in freshwater ecosystems.

Congo River water was filtered and then irradiated for 57 d in a solar simulator, resulting in extensive photodegradation of dissolved organic matter (DOM). Whole‐water (i.e., unfractionated) DOM was analyzed pre‐ and post‐irradiation using ultrahigh resolution Fourier transform ion cyclotron mass spectrometry (FT‐ICR MS), revealing the following three pools of DOM classified based upon their photoreactivity: (1) photo‐resistant, (2) photo‐labile, and (3) photo‐produced. Photo‐resistant DOM was heterogeneous, with most molecular classes represented, although only a small number of aromatics and no condensed aromatics were identified. The photoproduced pool was dominated by aliphatic compounds, although it included a small number of aromatics, including condensed aromatics. Aromatic compounds were the most photoreactive, with > 90% being lost upon irradiation. Photochemistry also resulted in a significant drop in the number of molecules identified and a decrease in their structural diversity. The FT‐ICR MS signatures of two classes of refractory organic matter, black carbon and carboxylic‐rich alicyclic molecules (CRAM), were present in the sample prior to irradiation, indicating that the Congo River could be a significant exporter of recalcitrant DOM to the ocean. All black carbon‐like molecules identified in the initial sample were lost during irradiation. Molecular signatures consistent with CRAM were also highly photo‐labile, demonstrating that environmental solar irradiation levels are capable of removing these refractory compounds from aquatic systems. Irradiation also shifted the molecular signature of terrestrial DOM toward that of marine DOM, thereby complicating the task of tracking terrestrial DOM in the ocean.

Riverine organic matter supports of the order of one-fifth of estuarine metabolism. Coastal ecosystems are therefore sensitive to alteration of both the quantity and lability of terrigenous dissolved organic matter (DOM) delivered by rivers. The lability of DOM is thought to vary with age, with younger, relatively unaltered organic matter being more easily metabolized by aquatic heterotrophs than older, heavily modified material. This view is developed exclusively from work in watersheds where terrestrial plant and soil sources dominate streamwater DOM. Here we characterize streamwater DOM from 11 coastal watersheds on the Gulf of Alaska that vary widely in glacier coverage (0-64 per cent). In contrast to non-glacial rivers, we find that the bioavailability of DOM to marine microorganisms is significantly correlated with increasing (14)C age. Moreover, the most heavily glaciated watersheds are the source of the oldest ( approximately 4 kyr (14)C age) and most labile (66 per cent bioavailable) DOM. These glacial watersheds have extreme runoff rates, in part because they are subject to some of the highest rates of glacier volume loss on Earth. We estimate the cumulative flux of dissolved organic carbon derived from glaciers contributing runoff to the Gulf of Alaska at 0.13 +/- 0.01 Tg yr(-1) (1 Tg = 10(12) g), of which approximately 0.10 Tg is highly labile. This indicates that glacial runoff is a quantitatively important source of labile reduced carbon to marine ecosystems. Moreover, because glaciers and ice sheets represent the second largest reservoir of water in the global hydrologic system, our findings indicate that climatically driven changes in glacier volume could alter the age, quantity and reactivity of DOM entering coastal oceans.

Global biomass burning generates 40 million to 250 million tons of charcoal every year, part of which is preserved for millennia in soils and sediments. We have quantified dissolution products of charcoal in a wide range of rivers worldwide and show that globally, a major portion of the annual charcoal production is lost from soils via dissolution and subsequent transport to the ocean. The global flux of soluble charcoal accounts to 26.5 ± 1.8 million tons per year, which is ~10% of the global riverine flux of dissolved organic carbon (DOC). We suggest that the mobilization of charcoal and DOC out of soils is mechanistically coupled. This study closes a major gap in the global charcoal budget and provides critical information in the context of geoengineering.

[1] The seasonal and spatial variability of dissolved organic matter (DOM) quantity and chemical composition were investigated in the Yukon River basin of Alaska, United States, and northwestern Canada. Dissolved organic carbon (DOC), chromophoric DOM (CDOM), and dissolved lignin phenols were measured across a range of source waters and the seasonal hydrograph. Strong relationships were determined between CDOM and both DOC and lignin phenols, highlighting the potential for deriving detailed spatial and temporal distributions of DOM composition from CDOM monitoring. Maximum concentrations of measured parameters were observed during the spring flush, when DOM had a remarkably high content of aromatic vascular plant material derived from surface soil and litter layers. A larger portion of riverine DOM was attributed to vascular plant sources than previously believed by utilizing representative vegetation leachates and a soil pore water as end-members. In combination with recent studies highlighting export of young, labile DOM during the spring flush in northern high-latitude river systems, our results suggest riverine DOM is less degraded and more labile than previously thought with clear ramifications for its biomineralization or photo-oxidation in marine environments.Citation: Spencer, R. G. M., G. R. Aiken, K. P. Wickland, R. G. Striegl, and P. J. Hernes (2008), Seasonal and spatial variability in dissolved organic matter quantity and composition from the Yukon River basin, Alaska, Global Biogeochem. Cycles, 22, GB4002,

Climate change induced permafrost thaw in the Arctic is mobilizing ancient dissolved organic carbon (DOC) into headwater streams; however, DOC exported from the mouth of major arctic rivers appears predominantly modern. Here we highlight that ancient (>20,000 years B.P.) permafrost DOC is rapidly utilized by microbes (~50% DOC loss in <7 days) and that permafrost DOC decay rates (0.12 to 0.19 day−1) exceed those for DOC in a major arctic river (Kolyma: 0.09 day−1). Permafrost DOC exhibited unique molecular signatures, including high levels of aliphatics that were rapidly utilized by microbes. As microbes processed permafrost DOC, its distinctive chemical signatures were degraded and converged toward those of DOC in the Kolyma River. The extreme biolability of permafrost DOC and the rapid loss of its distinct molecular signature may explain the apparent contradiction between observed permafrost DOC release to headwaters and the lack of a permafrost signal in DOC exported via major arctic rivers to the ocean.

[1] High-latitude northern rivers export globally significant quantities of dissolved organic carbon (DOC) to the Arctic Ocean. Climate change, and its associated impacts on hydrology and potential mobilization of ancient organic matter from permafrost, is likely to modify the flux, composition, and thus biogeochemical cycling and fate of exported DOC in the Arctic. This study examined DOC concentration and the composition of dissolved organic matter (DOM) across the hydrograph in Siberia's Kolyma River, with a particular focus on the spring freshet period when the majority of the annual DOC load is exported. The composition of DOM within the Kolyma basin was characterized using absorbance-derived measurements (absorbance coefficient a 330 , specific UV absorbance (SUVA 254 ), and spectral slope ratio S R ) and fluorescence spectroscopy (fluorescence index and excitation-emission matrices (EEMs)), including parallel factor analyses of EEMs. Increased surface runoff during the spring freshet led to DOM optical properties indicative of terrestrial soil inputs with high humic-like fluorescence, SUVA 254, and low S R and fluorescence index (FI). Under-ice waters, in contrast, displayed opposing trends in optical properties representing less aromatic, lower molecular weight DOM. We demonstrate that substantial losses of DOC can occur via biological ($30% over 28 days) and photochemical pathways (>29% over 14 days), particularly in samples collected during the spring freshet. The emerging view is therefore that of a more dynamic and labile carbon pool than previously thought, where DOM composition plays a fundamental role in controlling the fate and removal of DOC at a pan-Arctic scale.

[1] Photochemical degradation of Congo River dissolved organic matter (DOM) was investigated to examine the fate of terrigenous DOM derived from tropical ecosystems. Tropical riverine DOM receives greater exposure to solar radiation, particularly in large river plumes discharging directly into the open ocean. Initial Congo River DOM exhibited dissolved organic carbon (DOC) concentration and compositional characteristics typical of organic rich blackwater systems. During a 57 day irradiation experiment, Congo River DOM was shown to be highly photoreactive with a decrease in DOC, chromophoric DOM (CDOM), lignin phenol concentrations (S 8 ) and carbon-normalized yields (L 8 ), equivalent to losses of $45, 85-95, >95 and >95% of initial values, respectively, and a +3.1 % enrichment of the d C; r = 0.97, p < 0.01), highlighting the potential of CDOM absorbance measurements for delineating the photochemical degradation of lignin and thus terrigenous DOM. It is apparent that these commonly used measurements for examination of terrigenous DOM in the oceans have a higher rate of photochemical decay than the bulk DOC pool. Further process-based studies are required to determine the selective removal rates of these biomarkers for advancement of our understanding of the fate of this material in the ocean.