Large world rivers are significant sources of dissolved organic matter (DOM) to the oceans. Watershed geomorphology and land use can drive the quality and reactivity of DOM. Determining the molecular composition of riverine DOM is essential for understanding its source, mobility and fate across landscapes. In this study, DOM from the main stem of 10 global rivers covering a wide climatic range and land use features was molecularly characterized via ultrahigh-resolution Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). FT-ICR mass spectral data revealed an overall similarity in molecular components among the rivers. However, when focusing specifically on the contribution of nonoxygen heteroatomic molecular formulas (CHON, CHOS, CHOP, etc.) to the bulk molecular signature, patterns relating DOM composition and watershed land use became apparent. Greater abundances of N- and S-containing molecular formulas were identified as unique to rivers influenced by anthropogenic inputs, whereas rivers with primarily forested watersheds had DOM signatures relatively depleted in heteroatomic content. A strong correlation between cropland cover and dissolved black nitrogen was established when focusing specifically on the pyrogenic class of compounds. This study demonstrated how changes in land use directly affect downstream DOM quality and could impact C and nutrient cycling on a global scale.

The incomplete combustion of organic molecules produces a chemically diverse suite of pyrogenic residues termed black carbon (BC). The significance of BC cycling on land has long been recognized, and the recognition of dissolved BC (DBC) as a major component of the aquatic carbon cycle is developing rapidly. As we seek a greater understanding of DBC cycling, our interpretation of environmental DBC concentrations and molecular composition should take into account both the formation conditions of charred residues, and the physico-chemical transformation of DBC that occurs during transit within aquatic systems. We present the current state of knowledge concerning sources, processing, and sinks of DBC in inland, coastal/estuarine, and ocean waters. We feature studies and new methodologies which focus specifically on the aquatic cycling of DBC, explore the relationship between particulate and dissolved BC, and highlight research gaps which should be targeted to advance our current knowledge of DBC biogeochemistry.Fire has been an integral component of terrestrial ecosystems and biogeochemical cycles since the emergence of land plants some 420 million years ago (Bowman et al. 2009). Contemporary fire regimes are increasingly influenced by human activities, including the use of fire for agricultural practices, land management, vegetation control, and industry (Bowman et al. 2011). Black carbon (BC) is the organic residue formed during the incomplete combustion of organic matter, which occurs during both natural (wildfire) and anthropogenic (biomass burning, fossil fuel combustion) burning. Wildfires are the predominant source of BC to the environment and the vast majority of BC Scientific Significance StatementFire, both natural and anthropogenic, alters organic molecules into many chemical forms, all termed black carbon. Although well studied in soils and the atmosphere, black carbon in natural waters has only recently been identified as important. For example, 10% of dissolved organic carbon in rivers is in the form of dissolved black carbon. In this article, we present our emerging understanding of the chemistry, reactivity, fate, and ecological influence of dissolved black carbon in natural waters as well as the research challenges and opportunities.168 Limnology and Oceanography Letters 3, 2018, 168-185

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A portion of the charcoal and soot produced during combustion processes on land (e.g., wildfire, burning of fossil fuels) enters aquatic systems as dissolved black carbon (DBC). In terms of mass flux, rivers are the main identified source of DBC to the oceans. Since DBC is believed to be representative of the refractory carbon pool, constraining sources of marine DBC is key to understanding the long-term persistence of carbon in our global oceans. Here, we use compound-specific stable carbon isotopes (δ13C) to reveal that DBC in the oceans is ~6‰ enriched in 13C compared to DBC exported by major rivers. This isotopic discrepancy indicates most riverine DBC is sequestered and/or rapidly degraded before it reaches the open ocean. Thus, we suggest that oceanic DBC does not predominantly originate from rivers and instead may be derived from another source with an isotopic signature similar to that of marine phytoplankton.

Optical properties are easy-to-measure proxies for dissolved organic matter (DOM) composition, source, and reactivity. However, the molecular signature of DOM associated with such optical parameters remains poorly defined. The Florida coastal Everglades is a subtropical wetland with diverse vegetation (e.g., sawgrass prairies, mangrove forests, seagrass meadows) and DOM sources (e.g., terrestrial, microbial, and marine). As such, the Everglades is an excellent model system from which to draw samples of diverse origin and composition to allow classically-defined optical properties to be linked to molecular properties of the DOM pool. We characterized a suite of seasonally- and spatially-collected DOM samples using optical measurements (EEM-PARAFAC, SUVA254, S275−295, S350−400, SR, FI, freshness index, and HIX) and ultrahigh resolution mass spectrometry (FTICR-MS). Spearman's rank correlations between FTICR-MS signal intensities of individual molecular formulae and optical properties determined which molecular formulae were associated with each PARAFAC component and optical index. The molecular families that tracked with the optical indices were generally in agreement with conventional biogeochemical interpretations. Therefore, although they represent only a small portion of the bulk DOM pool, absorbance, and fluorescence measurements appear to be appropriate proxies for the aquatic cycling of both optically-active and associated optically-inactive DOM in coastal wetlands.

LabileCompounds that experience rapid turnover within hours to days of release and do not accumulate. Environmentally persistentCompounds that resist rapid microbial degradation, accumulating on land and in the ocean for centuries to millennia.

Black carbon (BC), pyrogenic organic matter generated from the incomplete combustion of biomass, is ubiquitous in the environment. The molecular structures which comprise the BC pool of compounds are defined by their condensed aromatic core structures polysubstituted with O-containing functionalities (e.g., carboxyl groups). Despite the apparent hydrophobicity of BC molecules, a considerable portion of BC is translocated from terrestrial to aquatic systems in the form of dissolved BC (DBC). However, the specific biogeochemical mechanisms which control the transfer of BC from the land to the water remain elusive. In the current study, the apparent solubility of DBC was inferred from octanol-water partition coefficients (K ow ) modeled for proposed DBC structures with varying degrees of polycondensation and polar functionality. Modeled K ow values indicated that DBC molecules with small aromatic ring systems and high degrees of hydrophilic functionality may be truly solubilized in the aqueous phase. However, large and highly condensed DBC structures yielded high K ow values, which suggested that a considerable portion of the DBC pool which has been quantified in aquatic environments is not truly dissolved. We hypothesized that other DOM components may act as mediators in the solubilization of condensed aromatic molecules and serve to increase the solubility of DBC via hydrophobic, intermolecular associations. This hypothesis was tested through controlled leaching experiments to determine whether the mobilization of DBC from particulate soils and chars became enhanced in the presence of DOM. However, we observed that characteristics inherent to each sample type had a greater influence than added DOM on the apparent solubility of DBC. In addition, the direct comparison of molecular marker (benzenepolycarboxylic acids) and ultrahigh resolution mass spectral data (FT-ICR/MS) on leachates obtained from the same set of soils and char did not show a clear overlap in DBC quantification or characterization between the two analytical methods. Correlations between FT-ICR/MS results and BPCA were not significant possibly due to differences in the methodological windows and/or small sample size. Our results were unable to provide evidence in support of proposed hydrophobic interactions between DOM and DBC, suggesting that other physical/chemical mechanisms play important roles in the dissolution of BC.

Hydrological events, driven by rainfall, control the amount and composition of dissolved organic matter (DOM) mobilized through river networks. In forested watersheds, the concentration, composition, and reactivity of DOM exported changes as baseflow transitions to storm flow, with major implications to downstream biogeochemistry. Hysteresis describes an observed difference between in-stream solute concentration/signal and discharge. By studying the relationship between DOM and stream discharge, we refine our understanding of the environmental and hydrological factors that influence the quantity and quality of stream DOM. The main objective of this study was to track hysteretic changes in riverine DOM molecular composition during storm events. Samples were collected from nested sites within the Passumpsic River catchment (Vermont, USA), a tributary of the Connecticut River. High-resolution monitoring of fluorescent DOM (via in situ sensors) and automated collection of discrete samples captured short-term, hydrologically driven variations in DOM concentration and composition. Ultrahigh-resolution mass spectrometry revealed an enrichment in aliphatic compounds at storm onset, while aromatic and polyphenolic compounds were more enriched at peak discharge. Molecular hysteresis patterns were similar across stream orders, indicating that fresh, terrigenous DOM is quickly shunted downstream, through the river network, during pulses of high discharge.Plain Language Summary During storm events, rainfall-runoff processes mobilize large amounts of dissolved organic matter from the land and through river networks. The relationship between stream discharge and dissolved organic matter quantity and composition can vary over the course of a storm event; this variation is termed hysteresis. We examined hysteresis in a forested New England watershed (Vermont, USA) to better understand the location and timing of dissolved organic matter reactivity in river systems. In-stream sensors captured high-frequency, storm-driven changes in dissolved organic matter quantity. Discrete water samples were collected across the storm event for molecular analysis of dissolved organic matter. Molecular analyses revealed differences in dissolved organic matter composition between storm onset and peak discharge. Storm events shunt molecularly diverse organic material further downstream, potentially shifting reactivity hotspots from upper to lower reaches of the watershed.