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IntroductionDissolved organic matter (DOM) composition varies over space and time, with a multitude of factors driving the presence or absence of each compound found in the complex DOM mixture. Compounds ubiquitously present across a wide range of river systems (hereafter termed core compounds) may differ in chemical composition and reactivity from compounds present in only a few settings (hereafter termed satellite compounds). Here, we investigated the spatial patterns in DOM molecular formulae presence (occupancy) in surface water and sediments across 97 river corridors at a continental scale using the “Worldwide Hydrobiogeochemical Observation Network for Dynamic River Systems—WHONDRS” research consortium. MethodsWe used a novel data-driven approach to identify core and satellite compounds and compared their molecular properties identified with Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS). ResultsWe found that core compounds clustered around intermediate hydrogen/carbon and oxygen/carbon ratios across both sediment and surface water samples, whereas the satellite compounds varied widely in their elemental composition. Within surface water samples, core compounds were dominated by lignin-like formulae, whereas protein-like formulae dominated the core pool in sediment samples. In contrast, satellite molecular formulae were more evenly distributed between compound classes in both sediment and water molecules. Core compounds found in both sediment and water exhibited lower molecular mass, lower oxidation state, and a higher degree of aromaticity, and were inferred to be more persistent than global satellite compounds. Higher putative biochemical transformations were found in core than satellite compounds, suggesting that the core pool was more processed. DiscussionThe observed differences in chemical properties of core and satellite compounds point to potential differences in their sources and contribution to DOM processing in river corridors. Overall, our work points to the potential of data-driven approaches separating rare and common compounds to reduce some of the complexity inherent in studying riverine DOM. 

Abstract Tropical floodplains are an important source of methane (CH₄) to the atmosphere, and ebullitive fluxes are likely to be important. We report direct measurements of CH₄ebullition in common habitats on the Amazon floodplain over two years based on floating chambers that allowed detection of bubbles, and submerged bubble traps. Ebullition was highly variable in space and time. Of the 840 floating chamber measurements (equivalent to 8,690 min of 10‐min deployments), 22% captured bubbles. Ebullitive CH₄fluxes, measured using bubble traps deployed for a total of approximately 230 days, ranged from 0 to 109 mmol CH₄m⁻² d⁻¹, with a mean of 4.4 mmol CH₄m⁻² d⁻¹. During falling water, a hydroacoustic echosounder detected bubbles in 24% of the 70‐m segments over 34 km. Ebullitive flux increased as the water level fell faster during falling water periods. In flooded forests, highest ebullitive fluxes occurred during falling water, while in open water and herbaceous plant habitats, higher ebullitive fluxes were measured during low water periods. The contribution of diffusive plus ebullitive CH₄flux represented by ebullition varied from 1% (high and rising water in open water of the lake) to 93% (falling water in flooded forests) based on bubble traps. Combining ebullitive and diffusive fluxes among habitats in relation to variations in water depth and areal coverage of aquatic habitats provides the basis for improved floodplain‐wide estimates of CH₄evasion.