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

In situ Biofilm Quantification in Bioelectrochemical Systems by using Optical Coherence Tomography

Detailed studies of microbial growth in bioelectrochemical systems (BESs) are required for their suitable design and operation. Here, we report the use of optical coherence tomography (OCT) as a tool for in situ and noninvasive quantification of biofilm growth on electrodes (bioanodes). An experimental platform is designed and described in which transparent electrodes are used to allow real‐time, 3D biofilm imaging. The accuracy and precision of the developed method is assessed by relating the OCT results to well‐established standards for biofilm quantification (chemical oxygen demand (COD) and total N content) and show high correspondence to these standards. Biofilm thickness observed by OCT ranged between 3 and 90 μm for experimental durations ranging from 1 to 24 days. This translated to growth yields between 38 and 42 mgurn:x-wiley:18645631:media:cssc201800589:cssc201800589-math-0001  gurn:x-wiley:18645631:media:cssc201800589:cssc201800589-math-0002 −1 at an anode potential of −0.35 V versus Ag/AgCl. Time‐lapse observations of an experimental run performed in duplicate show high reproducibility in obtained microbial growth yield by the developed method. As such, we identify OCT as a powerful tool for conducting in‐depth characterizations of microbial growth dynamics in BESs. Additionally, the presented platform allows concomitant application of this method with various optical and electrochemical techniques

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

Diurnal versus spatial variability of greenhouse gas emissions from an anthropogenically modified lowland river in Germany

Greenhouse gas (GHG) emissions from rivers are globally relevant, but quantification of these emissions comes with considerable uncertainty. Quantification of ecosystem-scale emissions is challenged by both spatial and short-term temporal variability. We measured spatio-temporal variability of CO2 and CH4 fluxes from a 1 km long reach of the lowland river Elbe in Germany over 3 d to establish which factor is more relevant to be taken into consideration: small-scale spatial variability or short-term temporal variability of CO2 and CH4 fluxes. GHG emissions from the river reach studied were dominated by CO2, and 90 % of total emissions were from the water surface, while 10 % of emissions were from dry fallen sediment at the side of the river. Aquatic CO2 fluxes were similar at different habitats, while aquatic CH4 fluxes were higher at the side of the river. Artificial structures to improve navigability (groynes) created still water areas with elevated CH4 fluxes and lower CO2 fluxes. CO2 fluxes exhibited a clear diurnal pattern, but the exact shape and timing of this pattern differed between habitats. By contrast, CH4 fluxes did not change diurnally. Our data confirm our hypothesis that spatial variability is especially important for CH4, while diurnal variability is more relevant for CO2 emissions from our study reach of the Elbe in summer. Continuous measurements or at least sampling at different times of the day is most likely necessary for reliable quantification of river GHG emissions.</p

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

Dietary Essential Amino Acids Affect the Reproduction of the Keystone Herbivore Daphnia pulex

Recent studies have indicated that nitrogen availability can be an important determinant of primary production in freshwater lakes and that herbivore growth can be limited by low dietary nitrogen availability. Furthermore, a lack of specific essential nitrogenous biochemicals (such as essential amino acids) might be another important constraint on the fitness of consumers. This might be of particular importance for cladoceran zooplankton, which can switch between two alternative reproductive strategies – the production of subitaneously developing and resting eggs. Here, we hypothesize that both the somatic growth and the type of reproduction of the aquatic keystone herbivore Daphnia is limited by the availability of specific essential amino acids in the diet. In laboratory experiments, we investigated this hypothesis by feeding a high quality phytoplankton organism (Cryptomonas) and a green alga of moderate nutritional quality (Chlamydomonas) to a clone of Daphnia pulex with and without the addition of essential amino acids. The somatic growth of D. pulex differed between the algae of different nutritional quality, but not dependent on the addition of dissolved amino acids. However, in reproduction experiments, where moderate crowding conditions at saturating food quantities were applied, addition of the essential amino acids arginine and histidine (but not lysine and threonine) increased the total number and the developmental stage of subitaneous eggs. While D. pulex did not produce resting eggs on Cryptomonas, relatively high numbers of resting eggs were released on Chlamydomonas. When arginine and histidine were added to the green algal diet, the production of resting eggs was effectively suppressed. This demonstrates the high, but previously overlooked importance of single essential amino acids for the reproductive strategy of the aquatic keystone herbivore Daphnia