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The interface between groundwater and surface water is a critical zone that influences ecohydrological and biogeochemical cycles within the surface water ecosystems. It is characterized by complex redox gradients. with groundwater-mediated inflow of reduced substances into the stream water. In this study, we have experimentally simulated the inflow of Fe(II)-rich groundwater with concentratrion of up to 1000 mmol L-1 into the open stream water of a flume system in order to quantify its effect on dissolved oxygen concentration in both the stream water and the hyporheic zone. The experimental setup consisted of 24 flumes, 12 of which were used for input of groundwater augumented with Fe(II), while the another 12 were used as controls, i. e., with inflow of Fe(II)-free groundwater. In addition, the experimental set-up provided the possibility to study the effects of fine sediment (coarse reference substratum (5% fine sediment content) vs. added fine sediment (35% fine sediment content) and low discharge (reference flow conditions vs. low discharge (drought) conditions within a threefold replicated, crossed design. All flumes had permanent groundwater input during the experiment. Fortnightly sampling campaigns were performed to analyze Fe(II), Fe(III), and DO, concentrations in the porewater (hyporheic zone) and the open water over five consecutive weeks. Our results clearly indicate that Fe(II) inflow resulted in a decrease of DO concentrations both in the porewater and subsequently in the open water, with distinct effects of sediment porosity and discharge. Over the five weeks, the sustained decrease between 40 and 50% of DO concentrations was more pronounced in flumes with fine sediment than in flumes with coarse sediments. Our findings suggest that increasing the Fe(II) concentration in the hyporheic zone can affect the availability of oxygen, important in controlling biogeochemical and ecological processes, microbial activities, and aquatic life. The formation of oxygen-depleted subsurface and surface waters in freshwater ecosystems has been associated with nutrient-rich waters stimulating eutrophication and the subsequent reduction of river health. In conclusion, this study highlights the importance of considering the effects of hyporheic redox processes and Fe(II) in assessing the health of stream ecosystems.

Intensification of agricultural land use leads to riparian clear cutting, which disrupts stream aquatic-terrestrial linkages through the loss of terrestrial particulate organic matter (POM)...

Benthic biofilms are often assumed to control terrestrially-derived dissolved organic carbon (tDOC) uptake in streams. We tested this by comparing 13C-enriched ryegrass leachate uptake in an agricultural and a forest stream, hypothesizing that a greater abundance of autotrophic biofilms in the agricultural stream would cause its whole-stream tDOC uptake to be comparatively low. We measured whole-stream and biofilm tDOC tracer uptake, metabolism, bacterial and algal diversity, and nutrient status of benthic epilithic biofilms, and assessed whole-stream hydromorphology. Whole-stream uptake of tDOC was six times lower in the agricultural (3.0 mg m−2 day−1) than in the forest (19.0 mg m−2 day−1) stream, and tDOC uptake velocity indicated lower tDOC demand in the agricultural (1.2 mm min−1) than in the forest (1.9 mm min−1) stream. The agricultural stream differed from the forest stream by slightly lower transient storage capacity and higher benthic biofilm bacterial abundance and production, lower biofilm biomass and lower biofilm molar C:N, C:P, and N:P ratios. Changes in epilithic biofilms contributed little to the differences in whole-stream tDOC tracer uptake between streams, as biofilm tDOC uptake only amounted to 4% and 13% of whole-stream uptake in the forest and agricultural stream, respectively. This comparison of a forest and an agricultural stream suggests that agricultural stressors have the potential to diminish both whole-stream tDOC uptake and uptake efficiency. Furthermore, the weak link between biofilm and whole-stream tDOC uptake implies that benthic biofilms characteristics are poor predictors for human impacts on tDOC uptake in agricultural streams and that hot spots of tDOC uptake are likely situated in the hyporheic zone or in the stream water column.

Dissolved oxygen (DO) in the hyporheic zone (HZ) is a crucial parameter for the survival of many stream organisms and is involved in a multitude of aerobic chemical reactions. However, HZ DO budgets are easily perturbed by climate change and anthropogenic processes that have caused increased deposition of fine sediments (< 2 mm) in many stream beds. The fine sediment fraction hampers exchange of DO-rich stream water with the HZ. In this study we performed a raster sampling approach (0.90 cm length x 1.50 cm width; 30 cm distance between sampling points) at sediment depths of 10 and 25 cm with a focus on DO and its stable isotopes (δ18ODO). The aim was to analyze small-scale turnover patterns in a forested (site 1) and an anthropogenically influenced stream section (site 2) in a 3rd order stream in southern Germany. Grain size analyses showed similar average fine sediment fractions at site 1 (42.5 ±13.7 %) and site 2 (46.3 ±10.8 %). They increased with depth at both sites (38.5 ± 6.3 %, 0-15 cm; 46.5 ± 17.4 %, 15-30 cm at site 1 and 40.6 ±4.5 %, 0-15 cm; 52.0 ±12.2 %, 15-30 cm at site 2). DO concentrations in the HZ ranged from 1.4 to 4.5 mg L-1 (2.0 ±0.7 mg L-1) and 1.5 to 1.8 mg L-1 (1.7 ±0.1 mg L-1) at site 1 and from 1.2 to 2.9 mg L-1 (1.6 ±0.5) and 1.0 to 2.4 mg L-1 (1.6 ±0.4) at site 2 at 10 and 25 cm depth, respectively. The low DO concentrations in the HZ suggest high DO consumption rates and reduced exchange with stream water. This is possibly a result of increased fine sediment proportions. However, other factors such as organic carbon contents and increased respiration rates may also influence DO gradients. In contrast, the stream water had an average DO concentration of 9.8 ±0.2 mg L-1. Associated δ18ODO values of the open water (23.4 ±0.1 ‰) differed from those of sediment waters that showed averages of +22.5 ±0.5 ‰ and +22.4 ±0.3 ‰ at site 1 and +22.5 ±0.4 ‰ and +22.3 ±0.2 ‰ at site 2 at 10 and 25 cm depth, respectively. These sedimentary values indicated dominant photosynthesis, even though due to absence of light in the subsurface this process seems unlikely. Therefore, kinetically-driven processes such as diffusion, interactions with Fe or unknown DO sources within the HZ might have caused such 16O-enriched values. Our findings suggest that the analyses of DO, δ18ODO and fine sediment gradients in the HZ should be combined with stable carbon isotope measurements to further our understanding of hyporheic processes relevant for stream biota.

The science of the total environment 769, 144324 (2021). doi:10.1016/j.scitotenv.2020.144324, Published by Elsevier Science, Amsterdam [u.a.]

The assessment of the exposure of aquatic wildlife to complex environmental mixtures of chemicals originating from both point and diffuse sources and evaluating the potential impact thereof constitutes a significant step towards mitigating toxic pressure and the improvement of ecological status. In the current proof-of-concept study, we demonstrate the potential of a novel Aggregated Biomarker Response (ABR) approach involving a comprehensive set of biomarkers to identify complex exposure and impacts on wild brown trout (Salmo trutta fario). Our scenario used a small lowland river in Germany (Holtemme river in the Elbe river catchment) impacted by two wastewater treatment plants (WWTP) and diffuse agricultural runoff as a case study. The trout were collected along a pollution gradient (characterised in a parallel study) in the river. Compared to fish from the reference site upstream of the first WWTP, the trout collected downstream of the WWTPs showed a significant increase in micronucleus formation, phase I and II enzyme activities, and oxidative stress parameters in agreement with increasing exposure to various chemicals. By integrating single biomarker responses into an aggregated biomarker response, the two WWTPs' contribution to the observed toxicity could be clearly differentiated. The ABR results were supported by chemical analyses and whole transcriptome data, which revealed alterations of steroid biosynthesis and associated pathways, including an anti-androgenic effect, as some of the key drivers of the observed toxicity. Overall, this combined approach of in situ biomarker responses complemented with molecular pathway analysis allowed for a comprehensive ecotoxicological assessment of fish along the river. This study provides evidence for specific hazard potentials caused by mixtures of agricultural and WWTP derived chemicals at sublethal concentrations. Using aggregated biomarker responses combined with chemical analyses enabled an evidence-based ranking of sites with different degrees of pollution according to toxic stress and observed effects.

Emerging pollutants are ubiquitous in the aquatic system and may pose risks to aquatic ecosystems. The quantification and prediction of environmental partitioning of these chemicals in aquatic systems between water, sediment and biota is an important step in the comprehensive assessment of their sources and final fates in the environment. In this multi-compartment field study, we applied equilibrium partitioning theory and chemical activity estimates to investigate the predictability of concentrations in Gammarus pulex as a model invertebrate from water and sediment in a typical small central European river. Furthermore, K OW -based and LSER approaches were assessed for the calculation of sediment organic carbon-, lipid-, and protein-water partitioning coefficients and activity ratios between the different compartments. Gammarid-water activity ratios close to unity have been observed for many chemicals, while sediment-water and sediment-biota chemical activity ratios exceeded unity by up to six orders of magnitudes. Causes may be: disequilibrium due to slow desorption kinetics and/or an underestimation of partition coefficients due to the presence of strongly adsorbing phases in the sediments. Water concentrations, particularly when using LSER for prediction of partition coefficients were good predictors of internal concentrations in gammarids for most emerging pollutants. Some hydrophilic chemicals such as the neonicotinoid imidacloprid tend to accumulate more in G. pulex than expected from equilibrium partitioning. This conclusion holds both for K OW as well as for LSER-based predictions and suggests previously unidentified mechanisms of bio-accumulation which may include binding to specific protein structures.

Oxygen is one of the most crucial elements on earth and equally affects life and inorganic redox processes. After its transition to water with moderate solubility and slow diffusion rates, most aquatic organisms depend on permanent renewal of dissolved oxygen (DO). Recharge of this pivotal aqueous gas may become hampered by anthropogenic and climatic influences with so far unknown consequences for surface freshwater systems and entire ecosystems. Because rivers integrate biogeochemical information of catchments, their oxygen dynamics may also reflect ecosystem and landscape health. Here we summarize the most important sources and sinks of DO and its role in river systems. These considerations also extend to associated water compartments and fluxes including lakes, reservoirs, soils, groundwater and the hyporheic zone. In addition, for continental-scale considerations, we analysed the GLObal RIver CHemistry (GLORICH) database with 170,369 DO measurements. These analyses revealed that DO in rivers relates to water temperature, pH and nutrient availability. On larger scales, it is also influenced by catchment area, slope, ratios of forests to managed land and population density. Our review also highlights important links between physical and biological influences on DO transfer as well as its sources and sinks in streams and rivers. We conclude that DO monitoring should be combined with novel interdisciplinary tracing techniques such as stable isotope ratios, radon gas and biological analyses. Such combined analyses have the potential to improve our understanding of transfer and transformations of oxygen in rivers as essential integrators of landscapes.

Agricultural and urban land use has dramatically increased over the last century and one consequence is the release of anthropogenic chemicals into aquatic ecosystems. One of the rarely studied consequences is the effect of land use change on internal concentrations of organic micropollutants (OMPs) in aquatic invertebrates and its effects on their genotype diversity. Here, we applied population genetic and internal concentrations of OMPs analyses to determine evolutionary implications of chemical pollution on Gammarus pulex populations from a natural and two agricultural streams. Along 14 consecutive months sampled, 26 different OMPs were quantified in G. pulex extracts with the highest number, concentration, and toxic pressure in the anthropogenically stressed stream ecosystems. Our results indicate distinct internal OMP profiles and changes in both genetic variation and genetic structure in streams affected by anthropogenic activity. Genetic variation was attributed to chemical pollution whereas changes in the genetic structure were attributed to environmental disturbances, such as changes in discharge in the impacted stream ecosystems, which worked both independently and in tandem. Finally, we conclude that human-impacted streams are subjected to severe alterations in their population genetic patterns compared to nonimpacted stream ecosystems.

Impacts of invasive species are context dependent and linked to the ecosystem they occur within. To broaden the understanding of the impact of a globally widespread invasive oyster, Crassostrea (Magallana) gigas, intertidal surveys were carried out at 15 different sites in Europe. The impact of C. gigas on macro- (taxa surrounding oyster > 1 cm) and epifaunal (taxa on oyster

Stream substratum restoration is a widely applied tool to improve spawning habitat quality for salmonid fishes. However, there is a lack of studies which comprehensively assess effects of the restoration on site, as well as on downstream habitats. Our study addressed effects at both locations and compared abiotic (analyses of texture, penetration resistance, oxygen concentration, redox, nitrite, nitrate, ammonium, pH, electric conductivity, temperature) with biotic (depth-specific macroinvertrebrate abundance and diversity, brown trout hatching success) indicators before and after excavation of the substratum in a highly colmated brown trout spawning site. Strong improvements of hyporheic water conditions (increased oxygen supply and redox potential, reduced concentrations of nitrite and ammonium) as well as ~50 % reductions of substratum compaction and fine sediment content were observed 1 day after the restoration measure. Improvements of habitat quality were still detectable 3 months after treatment. Consequently, the hatching success of Salmo trutta eggs increased from 0 % to 77 % after the restoration. Short-term decrease of macroinvertebrate abundance (from 13.1 to 3.9 macroinvertebrates/kg substratum) was observed within the hyporheic zone of the restoration site, but after 3 months, the number of taxa increased from 13 to 22 taxa and abundance reached 17.9 macroinvertebrates/kg. Significantly increased fine sediment deposition was detected within 1 km downstream of the restoration site and may negatively affect these habitats. Trade-offs between positive effects at restored sites and negative effects in downstream habitats need to be considered for a comprehensive evaluation of stream substratum restoration.

The Bode catchment (Germany) shows strong land use gradients from forested parts of the National Park (23 % of total land cover) to agricultural (70 %) and urbanised areas (7 %). It is part of the Terrestrial Environmental Observatories of the German Helmholtz association. We performed a biogeochemical analysis of the entire river network. Surface water was sampled at 21 headwaters and at ten downstream sites, before (in early spring) and during the growing season (in late summer). Many parameters showed lower concentrations in headwaters than in downstream reaches, among them nutrients (ammonium, nitrate and phosphorus), dissolved copper and seston dry mass. Nitrate and phosphorus concentrations were positively related to the proportion of agricultural area within the catchment. Punctual anthropogenic loads affected some parameters such as chloride and arsenic. Chlorophyll a concentration and total phosphorus in surface waters were positively related. The concentration of dissolved organic carbon (DOC) was higher in summer than in spring, whereas the molecular size of DOC was lower in summer. The specific UV absorption at 254 nm, indicating the content of humic substances, was higher in headwaters than in downstream reaches and was positively related to the proportion of forest within the catchment. CO2 oversaturation of the water was higher downstream compared with headwaters and was higher in summer than in spring. It was correlated negatively with oxygen saturation and positively with DOC concentration but negatively with DOC quality (molecular size and humic content). A principle component analysis clearly separated the effects of site (44 %) and season (15 %), demonstrating the strong effect of land use on biogeochemical parameters.