Constraining instantaneous fluxes and integrated compositions of fluvially discharged organic matter

Author Posting. © American Geophysical Union, 2018. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Freymond, C. V., Lupker, M., Peterse, F., Haghipour, N., Wacker, L., Filip, F., et al. (2018). Constraining instantaneous fluxes and integrated compositions of fluvially discharged organic matter. Geochemistry, Geophysics, Geosystems, 19, 2453 2462. doi: 10.1029/2018GC007539.Fluvial export of organic carbon (OC) and burial in ocean sediments comprises an important carbon sink, but fluxes remain poorly constrained, particularly for specific organic components. Here OC and lipid biomarker contents and isotopic characteristics of suspended matter determined in depth profiles across an active channel close to the terminus of the Danube River are used to constrain instantaneous OC and biomarker fluxes and integrated compositions during high to moderate discharges. During high (moderate) discharge, the total Danube exports 8 (7) kg/s OC, 7 (3) g/s higher plant‐derived long‐chain fatty acids (LCFA), 34 (21) g/s short‐chain fatty acids (SCFA), and 0.5 (0.2) g/s soil bacterial membrane lipids (brGDGTs). Integrated stable carbon isotopic compositions were TOC: −28.0 (−27.6)‰, LCFA: −33.5 (−32.8)‰ and Δ14C TOC: −129 (−38)‰, LCFA: −134 (−143)‰, respectively. Such estimates will aid in establishing quantitative links between production, export, and burial of OC from the terrestrial biosphere.This project was funded by the Swiss National Science Foundation SNF. Grant Number: 200021_140850. F.P. acknowledges funding from NWO‐VENI grant 863.13.016. We thank the sampling crews from both field campaigns (Björn Buggle, James Saenz, Alissa Zuijdgeest, Marilu Tavagna, Stefan Eugen Filip, Silvia Lavinia Filip, Mihai, Clayton Magill, Thomas Blattmann, and Michael Albani), Daniel Montluçon for lab support and Hannah Gies for PCGC work. Figures, tables, and equations can be found in supporting information

Global-scale evidence for the refractory nature of riverine black carbon

Author Posting. © The Author(s), 2018. This is the author's version of the work. It is posted here under a nonexclusive, irrevocable, paid-up, worldwide license granted to WHOI. It is made available for personal use, not for redistribution. The definitive version was published in Nature Geoscience 11 (2018): 584-588, doi:10.1038/s41561-018-0159-8.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 (∆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.A.C. acknowledges financial support from the University of Zurich Forschungskredit Fellowship and the University of Zurich (grant No. STWF-18-026). M.R., S.A. and M.S. acknowledge support from the University Research Priority Projection Global Change and Biodiversity (URPP-GCB). M.Z. acknowledges support from the National Natural Science Foundation of China (No. 41521064). T.E. acknowledges support from the Swiss National Science Foundation (“CAPS-LOCK” and “CAPS-LOCK2” #200021_140850). V.G. acknowledges financial support from an Independent Study Award from the Woods Hole Oceanographic Institution

Transport and evolution of terrestrial organic carbon signals along the Danube River basin

Rivers are the main land-to-ocean transport mechanism for transfer of particulate organic carbon (OC) mobilized on the continents to the ocean. Steady deposition and burial of terrigenous OC on continental margins act as a net sink for carbon, including that additionally mobilized by human intervention in the global carbon cycle. At the same time, valuable and continuous archives of environmental conditions on the continents are built up through the accumulation of sediment in front of river systems. However, the evolution of OC as it moves through river basins from biological source to the depositional sink, and the corresponding timescales of this carbon transfer are not well constrained. In this thesis, these questions are addressed with a detailed basin-wide investigation of the Danube River system, the second largest river basin in Europe. River sediment was collected along the Danube mainstem from headwaters to the Black Sea and at 12 tributaries close to their confluences with the Danube. The fine fraction (2,700 years. These calculations suggest that the majority of the upstream OC signal would be degraded by the time it reaches the terminus of the river. It is concluded that the combined effect of loss due to degradation and loess OC addition leads to the observed decrease in OC and biomarker loadings as well as to the gradual aging trend along the river. Additionally to the longitudinal investigation of river sediment along the Danube, an in-depth study of the bulk and molecular composition of suspended particulate matter in depth profiles across a river cross- section close to the outflow of the Danube was performed. Instantaneous OC and biomarker fluxes to the Black Sea were determined with this ‘picket-fence’ approach. Comparing brGDGT and FA-derived proxies and bulk and compound-specific stable isotope values from suspended matter in the cross-section to sediment deposited on riverbanks reveals that the fine fraction of freshly deposited sediment on riverbanks may serve as a proxy for the suspended particulate matter in a well mixed river such as the Danube. The finding that about 8 kg particulate OC per second are discharged by the Danube underlines the importance of global riverine OC export as a transport mechanism for terrestrial OC to the ocean. Further, this thesis shows that the OC load in a river evolves during transport, and highlights the importance of provenance studies and consideration of continental residence times for robust interpretation of paleo- environmental signals preserved in sedimentary records

Corrigendum to “Branched GDGT signals in fluvial sediments of the Danube River basin : Method comparison and longitudinal evolution” [Organic Geochem. 103 (2017) 88–96] (S0146638016303151) (10.1016/j.orggeochem.2016.11.002)

In the above article, an incorrect figure (Fig. 3) was published. This issue is rectified here with the correct Fig. 3. We would like to apologize for the inconvenience

Branched GDGT signals in fluvial sediments of the Danube River basin: Method comparison and longitudinal evolution

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 5-methyl-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

Long-chain diols in rivers

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