This thesis was motivated by the need to advance the knowledge on the variability and dynamics of energy fluxes in lakes and reservoirs, as well as about the physical processes that regulate the fluxes at both the air and water side of the air-water interface. In the first part, I re-examine how mechanical energy, resulting from its major source – the vertical wind energy flux - distributes into the various types of water motions, including turbulent flows and surface and internal waves. Although only a small fraction of the wind energy flux from the atmosphere is transferred to the water, it is crucial for physical, biogeochemical and ecological processes in lentic ecosystems. Based on extensive air- and water-side measurements collected at two small water bodies (< 10 km2), we estimated the energy fluxes and energy content in surface and in internal waves. Overall, the estimated energy fluxes and energy content agree well with results reported for larger water bodies, suggesting that the energetics driving the water motions in enclosed basins is similar, independently of the basin size. Our findings highlight the importance of the surface waves that receive the largest fraction of the wind energy flux, which strongly nonlinearly increases for wind speeds exceeding 3 m s-1. We found that the existing parameterization of the wave height as a function of wind speed and fetch length did not reproduce the measured wave amplitude in lakes. On average, the highest energy content was observed in basin-scale internal waves, together with high-frequency internal waves exhibiting seasonal variability and varies among the aquatic systems. During our analysis, we discovered the diurnal variability of the energy dissipation rates in the studied lake, suggesting biogenic turbulence generation, which appears to be a widespread phenomenon in lakes and reservoirs. In the second part of the thesis, I addressed current knowledge gaps related to the bulk transfer coefficients (also known as the drag coefficient, the Stanton number and the Dalton number), which are of a particular importance for the bulk estimation of the surface turbulent fluxes of momentum, sensible and latent heat in the atmospheric boundary layer. Their inaccurate representation may lead to significant errors in flux estimates, affecting, for example, the weather and climate predictions or estimations of the near-surface current velocities in lake hydrodynamic models. Although the bulk transfer coefficients have been extensively studied over the past several decades (mainly in marine and large-lake environments), there has been no systematic analysis of measurements obtained at lakes of different size. A significant increase of the transfer coefficients at low wind speeds (< 3 m s-1) has been observed in several studies, but, to date, it has remained unexplained. We evaluated the bulk transfer coefficients using flux measurements from 31 lakes and reservoirs. The estimates were generally within the range reported in previous studies for large lakes and oceans. All transfer coefficients increased substantially at low wind speeds, which was found to be associated with the presence of gusts and capillary waves (except the Dalton number). We found that the Stanton number is systematically higher than the Dalton number. This challenges the assumption made in the Bowen-ratio method, which is widely used for estimating evaporation rates from micrometeorological measurements. We found that the variability of the transfer coefficients among the lakes could be associated with lake surface area. In flux parameterizations at lake surfaces, it is recommended to consider variations in the drag coefficient and the Stanton number due to wind gustiness and capillary wave roughness while the Dalton number could be considered as constant at all wind speeds. In the third part of the thesis, I address the key drivers of the near-surface turbulence that control the gas exchange in a large regulated river. As all inland waters, rivers are an important natural source of greenhouse gases. The effects of the widespread alteration and regulation of river flow for human demands on gas exchange is largely unknown. In particular, the near-surface turbulence in regulated rivers has been rarely measured and its drivers have not been identified. While in lakes and reservoirs, near-surface turbulence is mainly related to atmospheric forcing, in shallow rivers and streams it is generated by bottom friction of the gravity-forced flow. The studied large regulated river represents a transition between these two cases. Atmospheric forcing and gravity were the dominant drivers of the near-surface turbulence for a similar fraction of the measurement period. Based on validated scalings, we derived a simple model for estimating the relative contributions of wind and bottom friction to near-surface turbulence in lotic ecosystems with different flow depths. Large diel variability in the near-surface energy dissipation rates due to flow regulation leads to the same variability in gas exchange. This suggests that estimates of gas fluxes from rivers are biased by measurements performed predominantly during daytime. In addition, the novelty in all the analyses described above is the use of the turbulent surface fluxes measured directly by the eddy-covariance technique – at the moment of writing, the most advanced method. Overall, this thesis is of a potential interest for a broad range of scientific disciplines, including limnology, micrometeorology and open channel hydraulics.

Vertebrate biodiversity is rapidly decreasing worldwide with amphibians being the most endangered vertebrate group. In the EU, 21 of 89 amphibian species are recognized as being endangered. The intensively used European agricultural landscape is one of the major causes for these declines. As agriculture represents an essential habitat for amphibians, exposure to pesticides can have adverse effects on amphibian populations. Currently, the European risk assessment of pesticides for vertebrates requires specific approaches for fish regarding aquatic vertebrate toxicity and birds as well as mammals for terrestrial vertebrate toxicity but does not address the unique characteristics of amphibians. Therefore, the overall goal of this thesis was to investigate the ecotoxicological effects of pesticides on Central European anuran amphibians. For this, effects on aquatic and terrestrial amphibian life stages as well as on reproduction were investigated. Then, in anticipation of a risk assessment of pesticides for amphibians, this thesis discussed potential regulatory risk assessment approaches. For the investigated pesticides and amphibian species, it was observed that the acute aquatic toxicity of pesticides can be addressed using the existing aquatic risk assessment approach based on fish toxicity data. However, lethal as well as sublethal effects were observed in terrestrial juveniles after dermal exposure to environmentally realistic pesticide concentrations, which cannot be covered using an existing risk assessment approach. Therefore, pesticides should also be evaluated for potential terrestrial toxicity using risk assessment tools before approval. Additionally, effects of co-formulants and adjuvants of pesticides need specific consideration in a future risk assessment as they can increase toxicity of pesticides to aquatic and terrestrial amphibian stages. The chronic duration of combined aquatic and terrestrial exposure was shown to affect amphibian reproduction. Currently, such effects cannot be captured by the existing risk assessment as data involving field scenarios analysing effects of multiple pesticides on amphibian reproduction are too rare to allow comparison to data of other terrestrial vertebrates such as birds and mammals. In the light of these findings, future research should not only address acute and lethal effects, but also chronic and sublethal effects on a population level. As pesticide exposure can adversely affect amphibian populations, their application should be considered even more carefully to avoid further amphibian declines. Overall, this thesis emphasizes the urgent need for a protective pesticide risk assessment for amphibians to preserve and promote stable amphibian populations in agricultural landscapes.

Stream ecosystems are one of the most threatened ecosystems worldwide due to their exposure to diverse anthropogenic stressors. Pesticides appear to be the most relevant stressor for agricultural streams. Due to the current mismatch of modelled and measured pesticide concentrations, monitoring is necessary to inform risk assessment or improve future pesticide approvals. Knowing if biotic stress responses are similar across large scales and long time frames could ultimately help in estimating protective stressor thresholds. This thesis starts with an overview of entry pathways of pesticides to streams as well as the framework of current pesticide monitoring and gives an outline of the objectives of the thesis. In chapter 2, routine monitoring data based on grab sampling from several countries is analysed to identify the most frequently occurring pesticide mixtures. These mixtures are comprised of relatively low numbers of pesticides, of which herbicides are dominating. The detected pesticide mixtures differ between regions and countries, due to differences in the spectrum of analysed compounds and limits of quantification. Current routine monitoring does not include sampling during pesticide peaks associated with heavy rainfall events which likely influences the detected pesticide mixtures. In chapter 3, sampling rates of 42 organic pesticides for passive sampling are provided together with recommendations for the monitoring of field-relevant peaks. Using this information, in chapter 4 a pesticide gradient is established in an Eastern European region where agricultural intensity adjacent to sampled streams ranges from low to high. In contrast to current routine monitoring, rainfall events were sampled and a magnitude of pesticides were analysed. This led to the simultaneous detection of numerous pesticides of which one to three drive the pesticide toxicity. The toxicity, however, showed no relationship to the agricultural intensity. Using microcosms, the stress responses of fungal communities, the hyphomycetes, and the related ecosystem function of leaf decomposition, is investigated in chapter 5. Effects of a field-relevant fungicide mixture are examined across three biogeographical regions for three consecutive cycles of microbial leaf colonisation and decomposition. Despite different initial communities, stress responses as well as recoveries were similar across biogeographical regions, indicating a general pattern. Overall, this thesis contributes to an improved understanding of occurrence and concentrations of pesticides mixtures in streams, their monitoring and impact on an ecosystem function. We showed that estimated pesticide toxicities reach levels that affect non-target organisms and thereby potentially whole ecosystems. Routine monitoring, however, likely underestimates the threat by pesticides. Effects leading to a loss in biodiversity or functions in streams ecosystems can be reduced by reassessing approved pesticides with ongoing targeted monitoring and increased knowledge of effects caused by these pesticides.

Lakes and reservoirs are important sources of methane, a potent greenhouse gas. Although freshwaters cover only a small fraction of the global surface, their contribution to global methane emission is significant and this is expected to increase, as a positive feedback to climate warming and exacerbated eutrophication. Yet, global estimates of methane emission from freshwaters are often based on point measurements that are spatio-temporally biased. To better constrain the uncertainties in quantifying methane fluxes from inland waters, a closer examination of the processes transporting methane from sediment to atmosphere is necessary. Among these processes, ebullition (bubbling) is an important transport pathway and is a primary source of uncertainty in quantifying methane emissions from freshwaters. This thesis aims to improve our understanding of ebullition in freshwaters by studying the processes of methane bubble formation, storage and release in aquatic sediments. The laboratory experiments demonstrate that aquatic sediments can store up to ~20% (volumetric content) gas and the storage capacity varies with sediment properties. The methane produced is stored as gas bubbles in sediment with minimal ebullition until the storage capacity is reached. Once the sediment void spaces are created by gas bubble formation, they are stable and available for future bubble storage and transport. Controlled water level drawdown experiments showed that the amounts of gas released from the sediment scaled with the total volume of sediment gas storage and correlated linearly to the drop in hydrostatic pressure. It was hypothesized that not only the timing of ebullition is controlled by sediment gas storage, but also the spatial distribution of ebullition. A newly developed freeze corer, capable of characterizing sediment gas content under in situ environments, enabled the possibility to test the hypothesis in a large subtropical lake (Lake Kinneret, Israel). The results showed that gas content was variable both vertically and horizontally in the lake sediment. Sediment methane production rate and sediment characteristics could explain these variabilities. The spatial distribution of ebullition generally was in a good agreement with the horizontal distribution of depth-averaged (surface 1 m) sediment gas content. While discrepancies were found between sediment depth-integrated methane production and the snapshot ebullition rate, they were consistent in a long term (multiyear average). These findings provide a solid basis for the future development of a process-based ebullition model. By coupling a sediment transport model with a sediment diagenetic model, general patterns of ebullition hotspots can be predicted at a system level and the uncertainties in ebullition flux measurements can be better constrained both on long-term (months to years) and short-term (minutes to hours) scales.

Systemic neonicotinoids are one of the most widely used insecticide classes worldwide. In addition to their use in agriculture, they are increasingly applied on forest trees as a protective measure against insect pests. However, senescent leaves containing neonicotinoids might, inter alia during autumn leaf fall, enter nearby streams. There, the hydrophilic neonicotinoids may be remobilized from leaves to water resulting in waterborne exposure of aquatic non-target organisms. Despite the insensitivity of the standard test species Daphnia magna (Crustacea, Cladocera) toward neonicotinoids, a potential risk for aquatic organisms is evident as many other aquatic invertebrates (in particular insects and amphipods) display adverse effects when exposed to neonicotinoids in the ng/L- to low µg/L-range. In addition to waterborne exposure, in particular leaf-shredding invertebrates (= shredders) might be adversely affected by the introduction of neonicotinoid-contaminated leaves into the aquatic environment since they heavily rely on leaf litter as food source. However, dietary neonicotinoid exposure of aquatic shredders has hardly received any attention from researchers and is not considered during aquatic environmental risk assessment. The primary aim of this thesis is, therefore, (1) to characterize foliar neonicotinoid residues and exposure pathways relevant for aquatic shredders, (2) to investigate ecotoxicological effects of waterborne and dietary exposure on two model shredders, namely Gammarus fossarum (Crustacea, Amphipoda) and Chaetopteryx villosa (Insecta, Trichoptera), and (3) to identify biotic and abiotic factors potentially modulating exposure under field conditions. During the course of this thesis, ecotoxicologically relevant foliar residues of the neonicotinoids imidacloprid, thiacloprid and acetamiprid were quantified in black alder trees treated at field relevant levels. A worst-case model – developed to simulate imidacloprid water concentrations resulting from an input of contaminated leaves into a stream – predicted only low aqueous imidacloprid concentrations (i.e., ng/L-range). However, the model identified dietary uptake as an additional exposure pathway relevant for shredders up to a few days after the leaves’ introduction into the stream. When test organisms were simultaneously exposed (= combined exposure) to neonicotinoids leaching from leaves into the water and via the consumption of contaminated leaves, adverse effects exceeded those observed under waterborne exposure alone. When exposure pathways were separated using a flow-through system, dietary exposure towards thiacloprid-contaminated leaves caused similar sublethal adverse effects in G. fossarum as observed under waterborne exposure. Moreover, the effect sizes observed under combined exposure were largely predictable using the reference model “independent action”, which assumes different molecular target sites to be affected. Dietary toxicity for shredders might, however, be reduced under field conditions since UV-induced photodegradation and leaching decreased imidacloprid residues in leaves and thereby the toxicity for G. fossarum. In contrast, both shredders were found unable to actively avoid dietary exposure. This thesis thus recommends considering dietary exposure towards systemic insecticides, such as neonicotinoids, already during their registration to safeguard aquatic shredders, associated ecosystem functions (e.g., leaf litter breakdown) and ultimately ecosystem integrity.