Wildfires and incomplete combustion of fossil fuel produce large amounts of black carbon. Black carbon production and transport are essential components of the carbon cycle. Constraining estimates of black carbon exported from land to ocean is critical, given ongoing changes in land use and climate, which affect fire occurrence and black carbon dynamics. Here, we present an inventory of the concentration and radiocarbon content (Δ 14C) of particulate black carbon for 18 rivers around the globe. We find that particulate black carbon accounts for about 15.8 ± 0.9% of river particulate organic carbon, and that fluxes of particulate black carbon co-vary with river-suspended sediment, indicating that particulate black carbon export is primarily controlled by erosion. River particulate black carbon is not exclusively from modern sources but is also aged in intermediate terrestrial carbon pools in several high-latitude rivers, with ages of up to 17,000 14C years. The flux-weighted 14C average age of particulate black carbon exported to oceans is 3,700 ± 400 14C years. We estimate that the annual global flux of particulate black carbon to the ocean is 0.017 to 0.037 Pg, accounting for 4 to 32% of the annually produced black carbon. When buried in marine sediments, particulate black carbon is sequestered to form a long-term sink for CO2.

Understanding the transport history and fate of organic carbon (OC) within river systems is crucial in order to constrain the dynamics and significance of land-ocean interactions as a component of the global carbon cycle. Fluvial export and burial of terrestrial OC in marine sediments influences atmospheric CO 2 over a range of timescales, while river-dominated sedimentary sequences can provide valuable archives of paleoenvironmental information. While there is abundant evidence that the association of organic matter (OM) with minerals exerts an important influence on its stability as well as hydrodynamic behavior in aquatic systems, there is a paucity of information on where such associations form and how they evolve during fluvial transport. Here, we track total organic carbon (TOC) and terrestrial biomarker concentrations (plant wax-derived long-chain fatty acids (FA), branched glycerol dialkyl glycerol tetraethers (brGDGTs) and lignin-derived phenols) in sediments collected along the entire course of the Danube River system in the context of sedimentological parameters. Mineral-specific surface area-normalized biomarker and TOC concentrations show a systematic decrease from the upper to the lower Danube basin. Changes in OM loading of the available mineral phase correspond to a net decrease of 70-80% of different biomolecular components. Ranges for biomarker loadings on Danube River sediments, corresponding to 0.4-1.5 lg FA /m 2 for long-chain (n-C 24-32) fatty acids and 17-71 ng brGDGT /m 2 for brGDGTs, are proposed as a benchmark for comparison with other systems. We propose that normalizing TOC as well as biomarker concentrations to mineral surface area provides valuable quantitative constraints on OM dynamics and organo-mineral interactions during fluvial transport from terrigenous source to oceanic sink.

Abundances and distributional changes of branched glycerol dialkyl glycerol tetraethers (brGDGTs) in fluvially influenced sediments are used in various paleoclimate studies to reconstruct variations in soil export, continental air temperature and soil pH in corresponding river basins. For accurate interpretation of these records, it is important to understand the provenance and the evolution of biomarker signals as they move through the river system. Here we investigate the brGDGT composition of modern river sediments of the Danube River, the second largest river in Europe. BrGDGT-based mean annual air temperature and soil pH parallel the actual values of air temperature and soil pH from the upper to the lower basin, showing that signals predominantly reflect local as opposed to basin-wide environmental conditions. Furthermore, data generated using the recently developed method with improved chromatography, separating the 6-methyl-isomers from the 5methyl-isomers, was compared with that resulting from the conventional method. We show that the temperatures and pH values reconstructed using the data obtained by improved chromatography best resemble the local environmental conditions throughout the Danube river basin. Our results highlight the importance of in-depth studies within river systems to better understand the provenance of biomarker signals in fluvially derived sedimentary archives.

Abstract. Long-chain diols (LCDs) occur widespread in marine environments and also in lakes and rivers. Transport of LCDs from rivers may impact the distribution of LCDs in coastal environments, however relatively little is known about the distribution and biological sources of LCDs in river systems. In this study, we investigated the distribution of LCDs in suspended particulate matter (SPM) of three river systems (Godavari, Danube, and Rhine) in relation with precipitation, temperature, and source catchments. The dominant long-chain diol is the C32 1,15-diol followed by the C30 1,15-diol in all studied river systems. In regions influenced by marine waters, such as delta systems, the fractional abundance of the C30 1,15-diol is substantially higher than in the river itself, suggesting different LCD producers in marine and freshwater environments. A change in the LCD distribution along the downstream transects of the rivers studied was not observed. However, an effect of river flow is observed; i.e., the concentration of the C32 1,15-diol is higher in stagnant waters such as reservoirs and during seasons with river low stands. A seasonal change in the LCD distribution was observed in the Rhine, likely due to a change in the producers. Eukaryotic diversity analysis by 18S rRNA gene sequencing of SPM from the Rhine showed extremely low abundances of sequences (i.e., < 0.32 % of total reads) related to known algal LCD producers. Furthermore, incubation of the river water with 13C-labeled bicarbonate did not result in 13C incorporation into LCDs. This indicates that the LCDs present are mainly of fossil origin in the fast-flowing part of the Rhine. Overall, our results suggest that the LCD producers in rivers predominantly reside in lakes or side ponds that are part of the river system.

Abstract. Nitrous oxide (N 2 O) is a potent greenhouse gas, generated through microbial nitrogen (N) turnover processes, such as nitrification, nitrifier denitrification, and denitrification. Previous studies quantifying natural sources have mainly focused on soils and the ocean, but the potential role of terrestrial water bodies in the global N 2 O budget has been widely neglected. Furthermore, the biogeochemical controls on the production rates and the microbial pathways that produce benthic N 2 O in lakes are essentially unknown. In this study, benthic N 2 O fluxes and the contributions of the microbial pathways that produce N 2 O were assessed using 15 N label flow-through sediment incubations in the eutrophic, monomictic south basin of Lake Lugano in Switzerland. The sediments were a significant source of N 2 O throughout the year, with production rates ranging between 140 and 2605 nmol N 2 O h −1 m −2 , and the highest observed rates coinciding with periods of water column stratification and stably anoxic conditions in the overlying bottom water. Nitrate (NO − 3 ) reduction via denitrification was found to be the major N 2 O production pathway in the sediments under both oxygen-depleted and oxygen-replete conditions in the overlying water, while ammonium oxidation did not contribute significantly to the benthic N 2 O flux. A marked portion (up to 15 %) of the total NO − 3 consumed by denitrification was reduced only to N 2 O, without complete denitrification to N 2 . These fluxes were highest when the bottom water had stabilized to a low-oxygen state, in contrast with the notion that stable anoxia is particularly conducive to complete denitrification without accumulation of N 2 O. This study provides evidence that lake sediments are a significant source of N 2 O to the overlying water and may produce large N 2 O fluxes to the atmosphere during seasonal mixing events.