Multi-year time series of daily solute and isotope measurements from three Swiss pre-Alpine catchments.

Time series analyses of solute concentrations in streamwater and precipitation are powerful tools for unraveling the interplay of hydrological and biogeochemical processes at the catchment scale. While such datasets are available for many sites around the world, they often lack the necessary temporal resolution or are limited in the number of solutes they encompass. Here we present a multi-year dataset encompassing daily records of major ions and a range of trace metals in both streamwater and precipitation in three catchments in the northern Swiss Pre-Alps. These time series capture the temporal variability observed in solute concentrations in response to storm events, snow melt, and dry summer conditions. This dataset additionally includes stable water isotope data as an extension of a publicly available isotope dataset collected concurrently at the same locations, and together these data can provide insights into a range of ecohydrological processes and enable a suite of analyses into hydrologic and biogeochemical catchment functioning.

The method controls the story - Sampling method impacts on the detection of pore-water nitrogen concentrations in streambeds.

Biogeochemical gradients in streambeds are steep and can vary over short distances often making adequate characterisation of sediment biogeochemical processes challenging. This paper provides an overview and comparison of streambed pore-water sampling methods, highlighting their capacity to address gaps in our understanding of streambed biogeochemical processes. This work reviews and critiques available pore-water sampling techniques to characterise streambed biogeochemical conditions, including their characteristic spatial and temporal resolutions, and associated advantages and limitations. A field study comparing three commonly-used pore-water sampling techniques (multilevel mini-piezometers, miniature drivepoint samplers and diffusive equilibrium in thin-film gels) was conducted to assess differences in observed nitrate and ammonium concentration profiles. Pore-water nitrate concentrations did not differ significantly between sampling methods (p-value = 0.54) with mean concentrations of 2.53, 4.08 and 4.02 mg l-1 observed with the multilevel mini-piezometers, miniature drivepoint samplers and diffusive equilibrium in thin-film gel samplers, respectively. Pore-water ammonium concentrations, however, were significantly higher in pore-water extracted by multilevel mini-piezometers (3.83 mg l-1) and significantly lower where sampled with miniature drivepoint samplers (1.05 mg l-1, p-values <0.01). Differences in observed pore-water ammonium concentration profiles between active (suction: multilevel mini-piezometers) and passive (equilibrium; diffusive equilibrium in thin-film gels) samplers were further explored under laboratory conditions. Measured pore-water ammonium concentrations were significantly greater when sampled by diffusive equilibrium in thin-film gels than with multilevel mini-piezometers (all p-values ≤0.02). The findings of this study have critical implications for the interpretation of field-based research on hyporheic zone biogeochemical cycling and highlight the need for more systematic testing of sampling protocols. For the first time, the impact of different active and passive pore-water sampling methods is addressed systematically here, highlighting to what degree the choice of pore-water sampling methods affects research outcomes, with relevance for the interpretation of previously published work as well as future studies.

Fate of wastewater contaminants in rivers: Using conservative-tracer based transfer functions to assess reactive transport.

Interpreting the fate of wastewater contaminants in streams is difficult because their inputs vary in time and several processes synchronously affect reactive transport. We present a method to disentangle the various influences by performing a conservative-tracer test while sampling a stream section at various locations for chemical analysis of micropollutants. By comparing the outflow concentrations of contaminants with the tracer signal convoluted by the inflow time series, we estimated reaction rate coefficients and calculated the contaminant removal along a river section. The method was tested at River Steinlach, Germany, where 38 contaminants were monitored. Comparing day-time and night-time experiments allowed distinguishing photo-dependent degradation from other elimination processes. While photo-dependent degradation showed to be highly efficient for the removal of metroprolol, bisoprolol, and venlafaxine, its impact on contaminant removal was on a similar scale to the photo-independent processes when averaged over 24 h. For a selection of compounds analyzed in the present study, bio- and photodegradation were higher than in previous field studies. In the Steinlach study, we observed extraordinarily effective removal processes that may be due to the higher proportion of treated wastewater, temperature, DOC and nitrate concentrations, but also a higher surface to volume ratio from low flow conditions that favorizes photodegradation through the shallow water column and a larger transient storage than observed in comparable studies.

In-situ mass spectrometry improves the estimation of stream reaeration from gas-tracer tests.

The estimation of gas-exchange rates between streams and the atmosphere is of great importance for the fate of volatile compounds in rivers. For dissolved oxygen, this exchange process is called reaeration, and its accurate and precise estimation is essential for the quantification of metabolic rates. A common method for the determination of gas-exchange rates is through artificial gas-tracer tests with a proxy gas. We present the implementation of a portable gas-equilibrium membrane inlet mass spectrometer (GE-MIMS) to record concentrations of krypton and propane injected as tracer compound in the context of a gas-tracer test. The field-compatible GE-MIMS uses signals of atmospheric measurements for concentration standardization, and allows recording the dissolved-gas concentrations at a high temporal resolution, leading to overall low measurement uncertainty. Furthermore, the in-situ approach avoids loss of gas during the steps of sampling, transport, storage, and analysis required for ex-situ gas measurements. We compare obtained gas-exchange rate coefficients, reaeration and derived metabolic rates from the in-situ measurements to results obtained from head-space sampling of propane followed by laboratory analysis, and find much lower uncertainties with the in-situ method.

Impact of non-idealities in gas-tracer tests on the estimation of reaeration, respiration, and photosynthesis rates in streams.

Estimating respiration and photosynthesis rates in streams usually requires good knowledge of reaeration at the given locations. For this purpose, gas-tracer tests can be conducted, and reaeration rate coefficients are determined from the decrease in gas concentration along the river stretch. The typical procedure for analysis of such tests is based on simplifying assumptions, as it neglects dispersion altogether and does not consider possible fluctuations and trends in the input signal. We mathematically derive the influence of these non-idealities on estimated reaeration rates and how they are propagated onto the evaluation of aerobic respiration and photosynthesis rates from oxygen monitoring. We apply the approach to field data obtained from a gas-tracer test using propane in a second-order stream in Southwest Germany. We calculate the reaeration rate coefficients accounting for dispersion as well as trends and uncertainty in the input signals and compare them to the standard approach. We show that neglecting dispersion significantly underestimates reaeration, and results between sections cannot be compared if trends in the input signal of the gas tracer are disregarded. Using time series of dissolved oxygen and the various estimates of reaeration, we infer respiration and photosynthesis rates for the same stream section, demonstrating that the bias and uncertainty of reaeration using the different approaches significantly affects the calculation of metabolic rates.