Quantifying the role that freshwater ecosystems play in the global carbon cycle requires accurate measurement and scaling of dissolved organic carbon (DOC) removal in river networks. We reviewed reach‐scale measurements of DOC uptake from experimental additions of simple organic compounds or leachates to inform development of aquatic DOC models that operate at the river network, regional, or continental scale. Median DOC uptake velocity (vf) across all measurements was 2.28 mm min−1. Measurements using simple compound additions resulted in faster vf (2.94 mm min−1) than additions of leachates (1.11 mm min−1). We also reviewed published data of DOC bioavailability for ambient stream water and leaf leachate DOC from laboratory experiments. We used these data to calculate and apply a correction factor to leaf leachate uptake velocity to estimate ambient stream water DOC uptake rates at the reach scale. Using this approach, we estimated a median ambient stream DOC vf of 0.26 mm min−1. Applying these DOC vf values (0.26, 1.11, 2.28, and 2.94 mm min−1) in a river network inverse model in seven watersheds revealed that our estimated ambient DOC vf value is plausible at the network scale and 27 to 45% of DOC input was removed. Applying the median measured simple compound or leachate vf in whole river networks would require unjustifiably high terrestrial DOC inputs to match observed DOC concentrations at the basin mouth. To improve the understanding and importance of DOC uptake in fluvial systems, we recommend using a multiscale approach coupling laboratory assays, with reach‐scale measurements, and modeling.

Soil organic matter (SOM) is involved in many important soil processes such as carbon sequestration and the solubility of plant nutrients and metals. Ultrahigh resolution mass spectrometry was used to determine the influence of forest vegetation type and soil depth on the molecular composition of the water-extractable organic matter (WEOM) fraction. Contrasting the upper 0-5 cm with the 25-50 cm B horizon depth increment, the relative abundance of lipids and carbohydrates significantly increased, whereas condensed aromatics and tannins significantly decreased for the deciduous stand WEOM. No significant abundance changes were found for the coniferous stand DOM. Kendrick mass defect analysis showed that the WEOM of the 25-50 cm B horizon was depleted in oxygen-rich and higher mass components as compared to the 0-5 cm B horizon WEOM, suggesting that higher mass WEOM components with oxygen-containing functionality show greater reactivity in abiotic and/or biotic reactions. Furthermore, using an inoculated 14-day laboratory incubation study and multivariate ordination methods, we identified the WEOM components with H:C > 1.2 and O:C > 0.5 as being correlated most strongly with biodegradability. Our findings highlight the importance of understanding soil depth differences for various forest types in the chemical composition of SOM and the processes governing SOM production and transformations to fully understand the ecological implications of changes in forest composition and function in a changing climate.

Population growth in cities has resulted in the rapid expansion of urbanized land. Most research and management of stream ecosystems affected by urban expansion has focused on the maintenance and restoration of biotic communities rather than their basal resources. We examined the potential for urbanization to induce bottom-up ecosystem effects by looking at its influence on dissolved organic matter (DOM) composition and bioavailability and microbial enzyme activity. We selected 113 headwater streams across a gradient of urbanization in central and southern Maine and used elemental and optical analyses, including parallel factor analysis of excitation-emission matrices, to characterize DOM composition. Results show that fluorescent and stoichiometric DOM composition changed significantly across the rural to urban gradient. Specifically, the proportion of humic-like allochthonous DOM decreased while that of more bioavailable autochthonous DOM increased in the more urbanized streams. In laboratory incubations, increased autochthonous DOM was associated with a doubling in the decay rate of dissolved organic carbon as well as increased activity of C-acquiring enzymes. These results suggest that urbanization replaces upstream humic material with more local sources of DOM that turnover more rapidly and may drive bottom-up changes in microbial communities and affect the quality and quantity of downstream DOM delivery.

The adsorption of dissolved organic matter (DOM) to metal (oxy)hydroxide mineral surfaces is a critical step for C sequestration in soils. Although equilibrium studies have described some of the factors controlling this process, the molecular-scale description of the adsorption process has been more limited. Chemical force spectroscopy revealed differing adhesion strengths of DOM extracted from three soils and a reference peat soil material to an iron (oxy)hydroxide mineral surface. The DOM was characterized using ultrahigh-resolution negative ion mode electrospray ionization Fourier Transform ion cyclotron resonance mass spectrometry. The results indicate that carboxyl-rich aromatic and N-containing aliphatic molecules of DOM are correlated with high adhesion forces. Increasing molecular mass was shown to decrease the adhesion force between the mineral surface and the DOM. Kendrick mass defect analysis suggests that mechanisms involving two carboxyl groups result in the most stable bond to the mineral surface. We conceptualize these results using a layer-by-layer "onion" model of organic matter stabilization on soil mineral surfaces.

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Although lasting only a fraction of the year, large storms may represent a significant, but highly variable, control on watershed nitrogen (N) fluxes. We determined the exports of particulate N (PN) and total dissolved N including nitrate-N (NO 3 -N) and dissolved organic N (DON) in streamflow from a 12 ha temperate forested watershed. Sampling was performed for 15 storms over September 2010 to December 2012 and included four large tropical storms-Nicole (2010) , respectively. Nitrate-N concentrations displayed a dilution trajectory for peak stormflows suggesting supply limitation, a response that was not as strong for PN. These results underscore the importance of large storms for PN export which is significant given that climate-change predictions indicate an increasing intensity of large tropical storms for the northeast U.S.. Elevated PN exports could further exacerbate water quality and eutrophication problems in sensitive aquatic ecosystems already subjected to excess dissolved nitrogen loads.

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The structural order and ordering conditions of the self-assembled monolayers (SAMs) of HSCH2CH2CH2O(EO)xCH3, where EO = CH2CH2O and x = 3-9, on polycrystalline gold (Au) were determined by reflection-absorption infrared spectroscopy (RAIRS), spectroscopic ellipsometry (SE), and electrochemical impedance spectroscopy. For x = 5-7, RAIRS and SE data show that the oligo(ethylene oxide) [OEO] segments adopt the near single phase, 7/2 helical conformation of the folded-chain crystal polymorph of crystalline poly(ethylene oxide), oriented normal to the substrate. These SAMs exhibit OEO segment structure and orientation identical to that found in a previous isostructural series [HS(CH2CH2O)6-8C18H37 SAMs. Vanderah, D. J., et al. Langmuir 2003, 19, 3752] and are anisotropic films for surface science metrology where structure is constant and thickness increases in 0.30 nm increments. In addition, this is the first example of OEO SAMs to attain this highly ordered, helical conformation where the (EO)x segment is separated from the Au-sulfur headgroup by a polymethylene chain. For x = 4, 8, and 9, the SAMs are largely helical but show evidence of nonhelical conformations and establish the upper and lower limits of the isostructural set. For x = 3, the SAMs are largely disordered containing some all-trans conformation. SAM order as a function of immersion time from 100% water and 95% ethanol indicates that the HSCH2CH2CH2O(EO)5-7CH3 SAMs order faster and under a wider range of conditions than omega-alkyl 1-thiaolio(ethylene oxide) [HS(EO)xCH3] SAMs, reported earlier (Vanderah, D. J., et al. Langmuir 2002, 18, 4674 and Vanderah, D. J., et al. Langmuir 2003, 19, 2612).