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The potential for rivers to alter the flux of dissolved organic matter (DOM) from land to ocean is widely accepted. Yet anticipating when and where rivers behave as active reactors vs. passive pipes of DOM stands as a major knowledge gap in river biogeochemistry, resulting in uncertainties for global carbon models. Here, we investigate the controls on in-stream DOM dynamics by evaluating changes in DOM concentration and composition along several reaches of a medium-sized river network over one full hydrological year. Roughly half of the observations over time and space showed active reactor conditions and, among these, similar proportion of gains and losses was measured. High water residence times promoted the active over passive behavior of the reaches, while DOM properties and nitrate availability determined whether they supplied or removed DOM from the river. Among different DOM fractions, protein-like DOM both of terrestrial and aquatic origin seemed to drive bulk DOM patterns. Our study emphasizes the role of water residence time as a physical constraint for in-stream processes, and provides new insights into the key factors governing the net balance between in-stream gains and losses of DOM in rivers.

Temporary watercourses that naturally cease to flow and run dry comprise a notable fraction of the world's river networks, yet estimates of global carbon dioxide (CO 2 ) emissions from watercourses do not consider emissions from these systems when they are dry. Using data from a sampling campaign in a Mediterranean river during the summer drought period, we demonstrate that the CO 2 efflux from dry watercourses can be substantial, comparable to that from adjacent terrestrial soils and higher than from running or stagnant waters. With an up-scaling approach, we show that including emissions from dry watercourses could increase the estimate of CO 2 emissions from watercourses in our study region by 0.6-15%. Moreover, our results tentatively illustrate that emissions from dry watercourses could be especially important in arid regions, increasing the estimate of global CO 2 emissions from watercourses by 0.4-9%. Albeit relatively small, the contribution of dry watercourses could help to constrain the highly uncertain magnitude of the land carbon sink. We foresee that in many areas of the world, the expected increase in the extent of temporary watercourses associated with future global change will increase the relevance of CO 2 emissions from dry watercourses.

Most fluvial networks worldwide include watercourses that recurrently cease to flow and run dry. The spatial and temporal extent of the dry phase of these temporary watercourses is increasing as a result of global change. Yet, current estimates of carbon emissions from fluvial networks do not consider temporary watercourses when they are dry. We characterized the magnitude and variability of carbon emissions from dry watercourses by measuring the carbon dioxide (CO2) flux from 10 dry streambeds of a fluvial network during the dry period and comparing it to the CO2 flux from the same streambeds during the flowing period and to the CO2 flux from their adjacent upland soils. We also looked for potential drivers regulating the CO2 emissions by examining the main physical and chemical properties of dry streambed sediments and adjacent upland soils. The CO2 efflux from dry streambeds (mean ± SD = 781.4 ± 390.2 mmol m−2 day−1) doubled the CO2 efflux from flowing streambeds (305.6 ± 206.1 mmol m−2 day−1) and was comparable to the CO2 efflux from upland soils (896.1 ± 263.2 mmol m−2 day−1). However, dry streambed sediments and upland soils were physicochemically distinct and differed in the variables regulating their CO2 efflux. Overall, our results indicate that dry streambeds constitute a unique and biogeochemically active habitat that can emit significant amounts of CO2 to the atmosphere. Thus, omitting CO2 emissions from temporary streams when they are dry may overlook the role of a key component of the carbon balance of fluvial networksThis research was funded by the Spanish Ministry of Economy and Competitiveness through the Projects CGL2011-30474-C02-01 and CGL2014-58760-C3-1-R

Large-scale studies are needed to identify the drivers of total mercury (THg) and monomethyl-mercury (MeHg) concentrations in aquatic ecosystems. Studies attempting to link dissolved organic matter (DOM) to levels of THg or MeHg are few and geographically constrained. Additionally, stream and river systems have been understudied as compared to lakes. Hence, the aim of this study was to examine the influence of DOM concentration and composition, morphological descriptors, land uses and water chemistry on THg and MeHg concentrations and the percentage of THg as MeHg (%MeHg) in 29 streams across Europe spanning from 41°N to 64 °N. THg concentrations (0.06-2.78 ng L) were highest in streams characterized by DOM with a high terrestrial soil signature and low nutrient content. MeHg concentrations (7.8-159 pg L) varied non-systematically across systems. Relationships between DOM bulk characteristics and THg and MeHg suggest that while soil derived DOM inputs control THg concentrations, autochthonous DOM (aquatically produced) and the availability of electron acceptors for Hg methylating microorganisms (e.g. sulfate) drive %MeHg and potentially MeHg concentration. Overall, these results highlight the large spatial variability in THg and MeHg concentrations at the European scale, and underscore the importance of DOM composition on mercury cycling in fluvial systems.

Controls on the degradation of dissolved organic matter (DOM) are complex but key to understand the role of freshwaters in the carbon cycle. Both the origin and previous degradation history have been suggested to determine DOM reactivity, but it is still a major challenge to understand the links between DOM composition and biodegradation kinetics. An appropriate context to study these links are intermittent rivers, as summer drought naturally diversifies DOM sources and sinks. Here we investigated the biodegradation kinetics of DOM in the main aquatic environments present in a temporary river. During dark incubations we traced the dynamics of bulk DOM and its main chromatographic fractions defined using LC‐OCD: high molecular weight substances (HMWS), low molecular weight substances (LMWS), and humic substances and building blocks. Bulk DOM decay patterns were successfully fitted to the reactivity continuum (RC) biodegradation model. The RC parameters depicted running waters as the sites presenting a more reactive DOM, and temporary pools, enriched in leaf litter, as the ones with slowest DOM decay. The decay patterns of each DOM fraction were consistent throughout sites. LMWS and HMWS decayed in all cases and could be modeled using the RC model. Notably, the dynamics of LMWS controlled the bulk DOM kinetics. We discuss the mechanistic basis for the chromatographic fractions' kinetics during biodegradation and the implications that preconditioning and summer drought can have for DOM biodegradation in intermittent rivers.

Large variability in dissolved organic carbon (DOC) uptake rates has been reported for headwater streams, but the causes of this variability are still not well understood. Here we assessed acetate uptake rates across 11 European streams comprising different ecoregions by using whole‐reach pulse acetate additions. We evaluated the main climatic and biogeochemical drivers of acetate uptake during two seasonal periods. Our results show a minor influence of sampling periods but a strong effect of climate and dissolved organic matter (DOM) composition on acetate uptake. In particular, mean annual precipitation explained half of the variability of the acetate uptake velocities (VfAcetate) across streams. Temperate streams presented the lowest VfAcetate, together with humic‐like DOM and the highest stream respiration rates. In contrast, higher VfAcetate were found in semiarid streams, with protein‐like DOM, indicating a dominance of reactive, labile compounds. This, together with lower stream respiration rates and molar ratios of DOC to nitrate, suggests a strong C limitation in semiarid streams, likely due to reduced inputs from the catchment. Overall, this study highlights the interplay of climate and DOM composition and its relevance to understand the biogeochemical mechanisms controlling DOC uptake in streams.

The composition of dissolved organic matter (DOM) in rivers results from the different sources and in-stream transformations along the land to ocean aquatic continuum. Riverine DOM sources are highly dependent on the hydrological connection between the river channel and the surrounding terrestrial ecosystems, but how the lack of this connectivity (e.g., during drought episodes) affects the sources and biodegradation of DOM in rivers remains unclear. Here we identified the DOM sources as well as the different DOM pools that are respired along a Mediterranean river during drought by combining absorbance-fluorescence spectroscopy, size-exclusion chromatography, biodegradation assays, and stable and radiocarbon isotopes. DOM composition was highly heterogeneous along the river in response to different sources and in-stream processes in each distinct aquatic environment (i.e., isolated water pools, running waters, and impounded waters in weirs). The reduced hydrological connectivity with terrestrial ecosystems promoted the influence of autochthonous DOM sources. Still, tree leaves from overhanging canopies stood out as an important terrestrial DOM source, especially in sites where water residence time was high such as isolated pools and weirs. Degradation of leaf leachates was a relevant process in these sites, whereas autochthonous DOM and groundwater millennial DOM (>1300 year B.P.) seemed to be degraded in running waters. Overall, our results highlight that the drought-induced hydrological disconnection entails a great spatial heterogeneity in the sources of DOM, which at the same time determines the different DOM pools that are respired in each environment along the riverThis research was funded by the Spanish Ministry of Economy and Competitiveness through the project CARBONET (CGL2011-30474-C02-01). J. P. Casas-Ruiz and Ll. Gómez-Gener were additionally supported by FPI predoctoral grants (BES-2012-059655 and BES-2012-059743), and D. von Schiller by a “Juan de la Cierva” postdoctoral grant (JCI-2010-06397). N. Catalán held a Wenner-Gren foundation stipend (Sweden). Authors also acknowledge the support from the Economy and Knowledge Department of the Catalan Government through Consolidated Research Group (2014 SGR 291)—Catalan Institute for Water Researc