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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.

Summary Stream ecosystem metabolism integrates production and respiration of organic matter and plays a fundamental role in the global carbon (C) cycle. Several studies have identified distal and proximal physical controls, for example, land use and transient storage, or the effects of water chemistry, that is, organic matter and nutrient availability, on stream metabolism. In parallel, research on organic matter quality has identified conspicuous gradients of chemical composition, yet mostly without demonstrating any functional implications. We hypothesise that organic matter holds a key position in a more comprehensive causal framework of stream ecosystem metabolism, and that a concurrent study can improve mechanistic understanding. Specifically, we here postulate that dissolved organic matter (DOM) quality, that is, its chemical composition, acts as a control of ecosystem respiration (ER) as much as it is a result of gross primary production (GPP). As such, DOM quality likely forms a central link between land use and stream metabolism, besides known physical controls including transient storage and light availability. To examine these hypotheses, we studied 33 streams in north‐eastern Austria, a region with diverse land use ranging from semi‐natural, forested areas to agricultural areas and settlements. We analysed DOM composition by absorbance and fluorescence spectroscopy, including modelling excitation–emission matrices with parallel factor analysis. We then opposed these data to GPP and ER estimated by fitting a metabolism model to single‐station diurnal oxygen records. Structural equation modelling revealed land use as a control on light conditions, DOM composition and concentration and nutrient concentrations, which together ultimately shaped GPP and ER. In particular, humified, coloured and aromatic DOM of predominantly terrestrial origin was prevalent in coniferous forest catchments and increased stream ER. Agricultural and urban areas enriched streams with phosphorous and nitrogen, which increased ER and GPP. Besides nutrients, GPP seemed to be weakly correlated with light availability and – in contrast to our hypothesis – left only a weak imprint on DOM composition. Land‐use change is rated as the most pervasive human influence on natural ecosystems and our results highlight its impact on aquatic GPP and ER in streams. To understand the role of inland waters in the global C cycle will require mechanistic understanding of ecosystem metabolism, which notably includes organic matter quality as a hitherto underappreciated key player.

Globally, inland waters emit over 2 Pg of carbon per year as carbon dioxide, of which the majority originates from streams and rivers. Despite the global significance of fluvial carbon dioxide emissions, little is known about their diel dynamics. Here we present a large-scale assessment of day- and night-time carbon dioxide fluxes at the water-air interface across 34 European streams. We directly measured fluxes four times between October 2016 and July 2017 using drifting chambers. Median fluxes are 1.4 and 2.1 mmol m−2 h−1 at midday and midnight, respectively, with night fluxes exceeding those during the day by 39%. We attribute diel carbon dioxide flux variability mainly to changes in the water partial pressure of carbon dioxide. However, no consistent drivers could be identified across sites. Our findings highlight widespread day-night changes in fluvial carbon dioxide fluxes and suggest that the time of day greatly influences measured carbon dioxide fluxes across European streams.

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Aim Although running waters are getting recognized as important methane sources, large‐scale geographical patterns of microorganisms controlling the net methane balance of streams are still unknown. Here we aim at describing community compositions of methanogenic and methanotrophic microorganisms at large spatial scales and at linking their abundances to potential sediment methane production (PMP) and oxidation rates (PMO). Location The study spans across 16 European streams from northern Spain to northern Sweden and from western Ireland to western Bulgaria. Taxon Methanogenic archaea and methane‐oxidizing microorganisms. Methods To provide a geographical overview of both groups in a single approach, microbial communities and abundances were investigated via 16S rRNA gene sequencing, extracting relevant OTUs based on literature; both groups were quantified via quantitative PCR targeting mcrA and pmoA genes and studied in relation to environmental parameters, sediment PMP and PMO, and land use. Results Diversity of methanogenic archaea was higher in warmer streams and of methanotrophic communities in southern sampling sites and in larger streams. Anthropogenically altered, warm and oxygen‐poor streams were dominated by the highly efficient methanogenic families Methanospirillaceae, Methanosarcinaceae and Methanobacteriaceae, but did not harbour any specific methanotrophic organisms. Contrastingly, sediment communities in colder, oxygen‐rich waters with little anthropogenic impact were characterized by methanogenic Methanosaetaceae, Methanocellaceae and Methanoflorentaceae and methanotrophic Methylococcaceae and Cd. Methanoperedens. Representatives of the methanotrophic Crenotrichaceae and Methylococcaceae as well as the methanogenic Methanoregulaceae were characteristic for environments with larger catchment area and higher discharge. PMP increased with increasing abundance of methanogenic archaea, while PMO rates did not show correlations with abundances of methane‐oxidizing bacteria. Main conclusions Methanogenic and methanotrophic communities grouping into three habitat types suggest that future climate‐ and land use changes may influence the prevailing microbes involved in the large‐scale stream‐related methane cycle, favouring the growth of highly efficient hydrogenotrophic methane producers. Based on these results, we expect global change effect on PMP rates to especially impact rivers adjacent to anthropogenically disturbed land uses.

Background: Globally, streams emit significant amounts of methane, a highly potent greenhouse gas. However, little is known about the stream sediment microbial communities that control the net methane balance in these systems, and in particular about their distribution and composition at large spatial scales. This study investigated the diversity and abundance of methanogenic archaea and methane-oxidizing microorganisms across 16 European streams (from northern Spain to northern Sweden and from western Ireland to western Bulgaria) via 16S rRNA gene sequencing and qPCR. Furthermore, it examined environmental factors influencing both abundance and community composition and explored the link to measured potential methane production and oxidation rates of the respective sediments. Results: Our results demonstrated that the methanogenic and methanotrophic microbiomes of the studied European streams were linked to both the temperature and degree of anthropogenic alteration. The microbiomes could be separated into two to three groups according to environmental factors at both stream and catchment scales. Main methanogenic taxa found within more anthropogenically-altered, warm, and oxygen-poor environments were either Methanospirillum spp. or members of the families Methanosarcinaceae and Methanobacteriaceae . Within such environments, methane oxidizing communities were strongly characterized by members of the family Methylobacteriaceae ( Meganema spp. and Microvirga spp.). Contrastingly, communities in colder environments rich in oxygen and with relatively little anthropogenic impact at the catchment scale were characterized by the methanogenic Methanosaetaceae , Methanocellaceae and Methanoregulaceae and the methanotrophic Methyloglobulus spp ., members of the CABC2E06 group (all Methylococcaceae ) and by various Candidatus Methanoperedens. Overall, diversity of methanogenic archaea increased with increasing water temperature. Methane oxidizing communities showed higher diversities in southern sampling sites and in streams with larger stream areas and widths. Potential methane production rates significantly increased with increasing abundance of methanogenic archaea, while potential methane oxidation rates did not show significant correlations with abundances of methane oxidizing bacteria, presumably due to the more diverse physiological capabilities of this group. Conclusions: We present the first large scale overview of the large-scale microbial biogeography of two microbial groups driving the methane cycle dynamics within stream sediments and deduce the impact that future anthropogenic alterations may cause.

In many regions around the world, large populations of native wildlife have declined or been replaced by livestock grazing areas and farmlands, with consequences on terrestrial-aquatic ecosystems connectivity and trophic resources supporting food webs in aquatic ecosystems. The river continuum concept (RCC) and the riverine productivity model (RPM) predict a shift of carbon supplying aquatic food webs along the river: from terrestrial inputs in low-order streams to autochthonous production in mid-sized rivers. Here, we studied the influence of replacing large wildlife (mainly hippos) with livestock on the relative importance of C3 vegetation, C4 grasses and periphyton on macroinvertebrates in the Mara River, which is an African montane-savanna river known to receive large subsidy fluxes of terrestrial carbon and nutrients mediated by LMH, both wildlife and livestock. Using stable carbon (δ13C) and nitrogen (δ15N) isotopes, we identified spatial patterns of the relative importance of allochthonous carbon from C3 and C4 plants (woody vegetation and grasses, respectively) and autochthonous carbon from periphyton for macroinvertebrates at various sites of the Mara River and its tributaries. Potential organic carbon sources and invertebrates were sampled at 80 sites spanning stream orders 1 to 7, various catchment land uses (forest, agriculture and grasslands) and different loading rates of organic matter and nutrients by LMH (livestock and wildlife, i.e., hippopotamus). The importance of different sources of carbon along the river did not follow predictions of RCC and RPM. First, the importance of C3 and C4 carbon was not related to river order or location along the fluvial continuum but to the loading of organic matter (dung) by both wildlife and livestock. Notably, C4 carbon was important for macroinvertebrates even in large river sections inhabited by hippos. Second, even in small 1st -3rd order forested streams, autochthonous carbon was a major source of energy for macroinvertebrates, and this was fostered by livestock inputs fuelling aquatic primary production throughout the river network. Importantly, our results show that replacing wildlife (hippos) with livestock shifts river systems towards greater reliance on autochthonous carbon through an algae-grazer pathway as opposed to reliance on allochthonous inputs of C4 carbon through a detrital pathway.