River networks exhibit a globally important capacity to retain and process nitrogen. However direct measurement of in‐stream removal in higher order streams and rivers has been extremely limited. The recent advent of automated sensors has allowed high frequency measurements, and the development of new passive methods of quantifying nitrogen uptake which are scalable across river size. Here we extend these methods to higher order streams with anthropogenically elevated nitrogen levels, substantial tributaries, complex input signals, and multiple N species. We use a combination of two station time‐series and longitudinal profiling of nitrate to assess differences in nitrogen processing dynamics in a natural versus a channelized impounded reach with WWTP effluent impacted water chemistry. Our results suggest that net mass removal rates of nitrate were markedly higher in the unmodified reach. Additionally, seasonal variations in temperature and insolation affected the relative contribution of assimilatory versus dissimilatory uptake processes, with the latter exhibiting a stronger positive dependence on temperature. From a methodological perspective, we demonstrate that a mass balance approach based on high frequency data can be useful in deriving quantitative uptake estimates, even under dynamic inputs and lateral tributary inflow. However, uncertainty in diffuse groundwater inputs and more importantly the effects of alternative nitrogen species, in this case ammonium, pose considerable challenges to this method.
Nitrous oxide (N 2 O) is one of the most important greenhouse gases and a major sink for stratospheric ozone. Estuaries are sites of intense biological production and N 2 O emissions. We aimed to identify hot spots of N 2 O production and potential pathways contributing to N 2 O concentrations in the surface water of the tidal Elbe estuary. During two research cruises in April and June 2015, surface water N 2 O concentrations were measured along the salinity gradient of the Elbe estuary by using a laser-based on-line analyzer coupled to an equilibrator. Based on these high-resolution N 2 O profiles, N 2 O saturations, and fluxes across the surface water/atmosphere interface were calculated. Additional measurements of DIN concentrations, oxygen concentration, and salinity were performed. Highest N 2 O concentrations were determined in the Hamburg port region reaching maximum values of 32.3 nM in April 2015 and 52.2 nM in June 2015. These results identify the Hamburg port region as a significant hot spot of N 2 O production, where linear correlations of AOU-N 2 O xs indicate nitrification as an important contributor to N 2 O production in the freshwater part. However, in the region with lowest oxygen saturation, sediment denitrification obviously affected water column N 2 O saturation. The average N 2 O saturation over the entire estuary was 201% (SD: ±94%), with an average estuarine N 2 O flux density of 48 µmol m −2 d −1 and an overall emission of 0.18 Gg N 2 O y −1 . In comparison to previous studies, our data indicate that N 2 O production pathways over the whole estuarine freshwater part have changed from predominant denitrification in the 1980s toward significant production from nitrification in the present estuary. Despite a significant reduction in N 2 O saturation compared to the 1980s, N 2 O concentrations nowadays remain on a high level, comparable to the mid-90s, although a steady decrease of DIN inputs occurred over the last decades. Hence, the Elbe estuary still remains an important source of N 2 O to the atmosphere.
Anthropogenic nutrient inputs increase the N-load in many aquatic systems, leading to eutrophication and potential changes of biological N-retention capacity. In this study, nitrate inputs in a small river were investigated along a gradient of anthropogenic influence. We aimed to determine changes in nitrate load and isotope signatures in the water column and to identify the anthropogenic influence on biological nitrogen assimilation and nitrification or denitrification in sediments. In seasonal sampling campaigns, we analysed dissolved inorganic nitrogen concentrations, and stable isotopes of nitrate. To differentiate rates of nitrate production and consumption in the pristine vs. agricultural river section, intact sediment cores were incubated with N-labelled nitrate. δN values of nitrate in the pristine river section were low, reflecting natural sources, but, as expected, increased with nitrate concentration in all seasons along the gradient. In general, nitrate retention and consumption were higher in the anthropogenically impacted than in the pristine river section, and nitrate consumption exceeded production. In addition to our measurements, modelled results also show that even in a small river, the anthropogenically enhanced consumption capacity is overwhelmed by surplus N-inputs, and nitrate consumption cannot increase in turn with external loads.
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