Spatial Variability in and Hotspots of Methane Concentration in a Large Temperate River

Rivers are significant sources of greenhouse gases (GHGs; e.g., CH4 and CO2); however, our understanding of the large-scale longitudinal patterns of GHG emissions from rivers remains incomplete, representing a major challenge in upscaling. Local hotspots and moderate heterogeneities may be overlooked by conventional sampling schemes. In August 2020 and for the first time, we performed continuous (once per minute) CH4 measurements of surface water during a 584-km-long river cruise along the German Elbe to explore heterogeneities in CH4 concentration at different spatial scales and identify CH4 hotspots along the river. The median concentration of dissolved CH4 in the Elbe was 112 nmol L−1, ranging from 40 to 1,456 nmol L−1 The highest CH4 concentrations were recorded at known potential hotspots, such as weirs and harbors. These hotspots were also notable in terms of atmospheric CH4 concentrations, indicating that measurements in the atmosphere above the water are useful for hotspot detection. The median atmospheric CH4 concentration was 2,033 ppb, ranging from 1,821 to 2,796 ppb. We observed only moderate changes and fluctuations in values along the river. Tributaries did not obviously affect CH4 concentrations in the main river. The median CH4 emission was 251 μmol m−2 d−1, resulting in a total of 28,640 mol d−1 from the entire German Elbe. Similar numbers were obtained using a conventional sampling approach, indicating that continuous measurements are not essential for a large-scale budget. However, we observed considerable lateral heterogeneity, with significantly higher concentrations near the shore only in reaches with groins. Sedimentation and organic matter mineralization in groin fields evidently increase CH4 concentrations in the river, leading to considerable lateral heterogeneity. Thus, river morphology and structures determine the variability of dissolved CH4 in large rivers, resulting in smooth concentrations at the beginning of the Elbe versus a strong variability in its lower parts. In conclusion, groin construction is an additional anthropogenic modification following dam building that can significantly increase GHG emissions from rivers

Characteristics of dissolved and atmospheric methane concentrations along a freshwater-seawater transect from the River Elbe into the North Sea

Surface waters are known to be significant sources of greenhouse gases (CH4 and CO2), but our understanding of large scale patterns is still incomplete. The greenhouse gases in rivers originate both from in-stream processes and interactions with the catchment. For coastal seas, rivers are suspected to be one of the main source of greenhouse gases, while the role of the interjacent tidal flats is still ambiguous. Especially the reaction of the entire system on terrestrial hydrological extremes such as low flow situations are still under consideration. The functional understanding of such events and their impacts on the water chemistry along its transition pathway in the terrestrial and limnic compartment as well as in the coastal marine environment is crucially needed for the evaluation of its relevance in the Earth system. As part of a MOSES campaign (Modular Observation Solutions for Earth Systems) spanning disciplines as well as earth system compartments we investigated the aquatic as well as the atmospheric compartemt in and above the Elbe River from inland waters through the tidal section of the river and the estuary to the North Sea with the goal to explore spatial heterogeneity of CO2 and CH4 concentrations in the water and in ambient air above the water during a low water period in summer 2020. Overall, dissolved CH4 concentrations ranged over three orders of magnitude. Along the freshwater part of the transect, dissolved CH4 increased and weirs and harbors appeared to be hot spots of elevated CH4 concentrations both for the dissolved and atmospheric phase. We observed a longitudinal gradient of CO2 in the river which was closely linked to primary production. In the estuary and the marine part, dissolved CH4 concentrations of the transect were determined by the variability of temperature and salinity. Correlations with other water parameters revealed the complex regulation of dissolved CH4 concentrations along the freshwater-seawater continuum. For atmospheric CH4 above the North Sea, wind direction and wind speed proved to be crucial. Besides the typical diurnal fluctuations of atmospheric CO2 and CH4, an observed link between dissolved and atmospheric concentrations has to be further clarified

New Insights into the Seasonal Variation of DOM Quality of a Humic-Rich Drinking-Water Reservoir—Coupling 2D-Fluorescence and FTICR MS Measurements

Long-term changes in dissolved organic matter (DOM) quality, especially in humic-rich raw waters, may lead to intensive adaptions in drinking-water processing. However, seasonal DOM quality changes in standing waters are poorly understood. To fill this gap, the DOM quality of a German drinking water reservoir was investigated on a monthly basis by Fourier-transform ion cyclotron resonance mass spectrometry (FTICR MS) measurements and 2D fluorescence for 18 months. FTICR MS results showed seasonal changes of molecular formula (MF) intensities, indicating photochemical transformation of DOM as a significant process for DOM quality variation. For an assessment of the two humic-like components, identified by parallel factor analysis (PARAFAC) of excitation–emission matrices (EEM), their loadings were Spearman’s rank-correlated with the intensities of the FTICR MS-derived MF. One of the two PARAFAC components correlated to oxygenrich and relatively unsaturated MF identified as easily photo-degradable, also known as coagulants in flocculation processes. The other PARAFAC component showed opposite seasonal fluctuations and correlated with more saturated MF identified as photo-products with some of them being potential precursors of disinfection byproducts. Our study indicated the importance of elucidating both the chemical background and seasonal behavior of DOM if raw water-quality control is implemented by bulk optical parameters

Nutrient and carbon dynamics along the river-estuary-ocean continuum on Central European scale

Nutrient and carbon dynamics within the river-estuary-coastal water systems are key processes to understand the matter fluxes from the terrestrial environment to the ocean. In a large-scale study we analysed those dynamics with the focus of the prevailing low water conditions by following a sampling approach based on the travel time of water. We started with a nearly Lagrangian sampling along the River Elbe (German part; 580 km within 8 days travel time). After a subsequent investigation of the estuary, the plume of the river was followed by raster sampling the German Bight (North Sea) using three ships simultaneously. In the river, intensive growth of phytoplankton was determined connected with high oxygen saturation and pH values as well as under-saturation of CO2, whereas concentrations of dissolved nutrients declined. In the estuary, the Elbe shifted from an autotrophic to a heterotrophic system: Phytoplankton died off upstream of the salinity gradient causing minima in oxygen saturation and pH, supersaturation of CO2, and a release of nutrients. In the coastal region, phytoplankton and nutrient concentrations were low, oxygen close to saturation, and pH in a typical marine range. We detected a positive relationship between pH values and oxygen saturation and a negative one between pCO2 and oxygen saturation. Corresponding to the significant particulate nutrient flux via phytoplankton, flux rates of dissolved nutrients from the river into the estuary were low and determined by depleted concentrations. In contrast, fluxes from the estuary to the coastal waters were higher and the pattern was determined by tidal currents. Overall, the presented observation approach is appropriate to better understand land-ocean fluxes, particularly if it is performed under different hydrological conditions including extremes and seems to be suitable to investigate the impact of such events in freshwater on coastal systems in future. The study was conducted within the frame of the Helmholtz MOSES initiative (Modular Observation Solutions for Earth Systems) targeting processes and impacts of hydrological extremes

Quality of Dissolved Organic Matter Driven by Autotrophic and Heterotrophic Microbial Processes in a Large River

Rivers are regarded as important sites for processing of dissolved organic matter (DOM) from terrestrial sources on its way to the ocean. However, little is known about the longitudinal change of DOM molecular composition in large rivers. Here we performed a Lagrangian sampling in the lower part of the Middle Elbe at low discharge conditions to test how DOM composition changes along the river stretch and how this is related to microbial processes. The concentration of dissolved organic carbon and fluorescence indices showed only subtle longitudinal differences. In contrast, ultra-high-resolution mass spectrometry analysis of riverine DOM detected pronounced changes in molecular composition. Also, chlorophyll a concentration, bacterial abundance, and bacterial production all increased downstream. The three microbial parameters were positively related to intensities of CHO and CHNO molecular formulas with high hydrogen/carbon and low oxygen/carbon ratios but negatively to several CHOS surfactants. To disentangle the role of autotrophic and heterotrophic processes, we developed a new approach and compared slopes from linear regression of DOM compound intensities versus chlorophyll a concentration and bacteria abundance. As a result, most of the positive related DOM compounds were produced by bacteria. In conclusion, longitudinal changes of river DOM seemed to be largely driven by microbial processes

Response of heterotrophic bacteria, autotrophic picoplankton andheterotrophic nanoflagellates to re-oligotrophication

We investigated the response of the microbial components of the pelagic food web to re-oligotrophication of large, deep Lake Constance where total phosphorus concentrations during mixing decreased from a maximum of 2.81 μmol L-1 in 1979 via 1.87 μmol L-1 in 1987 to 0.26 μmol L-1 in 2007. Measurements of heterotrophic bacteria, autotrophic picoplankton (APP) and heterotrophic nanoflagellates (HNF) in 2006 and 2007 were compared to values from 1987 to 1997. We hypothesized that the biomass and seasonal variability of all groups will decrease under more oligotrophic conditions due to reduced resource availability, particularly for APP and HNF but less for the competitively stronger bacteria. Average bacterial biomass between spring and autumn was unrelated to phosphorus, whereas the ratio of bacterial biomass to chlorophyll a concentration increased with decreasing trophy due to declining chlorophyll concentrations. In contrast, a unimodal relationship was found between APP and phosphorus with low biomass at low and high phosphorus concentrations and maximum biomass in between. Average HNF biomass decreased strongly by a factor of 10 30 with decreasing trophy, and chlorophyll-specific HNF biomass was unimodally related to phosphorus. The relative seasonal biomass variability did not change for any group during re-oligotrophication. To conclude, HNF responded much more strongly and bacteria less so than chlorophyll concentrations to oligotrophication, whereas APP exhibited a more complex pattern

Utilisation of dissolved organic carbon from different sources by pelagic bacteria in an acidic mining lake

We compared growth rates and efficiencies of pelagic bacteria from an extremely acidic mining lake (pH 2.6, mean depth 4.6 m) supplied with different sources of carbon: (1) excreted by phytoplankton, (2) derived from benthic algae, (3) entering the lake via ground water, and (4) leached from leaf litter. Bacteria exhibited high growth rate and efficiency on exudates of pelagic and benthic algae. In contrast, they showed a lower growth rate and efficiency with organic carbon from ground water, and grew at a very high rate but a very low efficiency on leaf leachate. Results from stable isotope analyses indicate a greater importance of benthic exudates and leaf leachate for bacteria in the epilimnion, and a higher impact of ground water sources in the hypolimnion. Given the magnitude of differential source inputs into the lake, we suggest that benthic primary production was the most important carbon source for pelagic bacteria. The benthic-pelagic coupling seems to be more relevant in this shallow acidic lake with low pelagic carbon dioxide concentrations than in neutral lakes

Water chemistry of Lagrangian samplings of Inland Elbe 2021 (MOSES Hydrological Extremes)

Four sampling campaigns were performed in the middle part of River Elbe between Elster (river km 199) and Dömitz (km 506). Measurements were done at different seasons and discharge conditions in April, June, August, and October 2021. The sampling was conducted in a Lagrangian way according to travel time using the research vessel Albis. For each campaign, data files of the multiparameter probe and of waterchemical analyses are provided