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Storm events lead to mobilization of particles as well as organic contaminants that can pose a risk to river ecosystems. Assessment of total loads of particle-bound and dissolved contaminants in rivers is challenging, especially during rain events since multiple, often unknown contamination sources may be triggered, among them tributaries, combined sewer overflows, direct soil and road runoff, and the riverbed sediment. We investigated whether cytotoxicity (i.e., reduction of the cell viability of human cell lines) could be used as a proxy for the total chemical mixture to assess the transport of organic contaminant mixtures either in particle-associated form or in the aqueous phase. Time-proportional composite samples were collected in the Ammer River (Southwestern Germany) during two storm events in June 2021. All samples were screened for 127 organic contaminants and cytotoxicity in the water and particle phase separately. In total, 56 organic compounds were found, of which 14 and 34 were detected only in the water and particle extracts, respectively, and eight compounds were present in both phases. Thermodynamic equilibrium between the aqueous phase and suspended solids was observed for four compounds namely triphenyl phosphate, octocrylene, galaxolide, and p-chlorocresol. Substances that were not in equilibrium were mainly constituents of plastics and tire rubber, and their high concentrations in the particle phase were probably due to extractions from the particles themselves. Linear correlations between TSS and total compound concentrations were found for 17 PAHs and two musk fragrances, suggesting stable particle loadings and aqueous concentrations over the course of the rain event, most likely due to particle delivery from a particle source with a constant degree of contamination. The total cytotoxicity of water plus particles in the river correlated linearly with TSS during storm events. Inflowing water and particles from all sources appeared to be integra

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The presence of anthropogenic organic micropollutants in rivers poses a long-term threat to surface water quality. To describe and quantify the in-stream fate of single micropollutants, the advection–dispersion–reaction (ADR) equation has been used previously. Understanding the dynamics of the mixture effects and cytotoxicity that are cumulatively caused by micropollutant mixtures along their flow path in rivers requires a new concept. Thus, we extended the ADR equation from single micropollutants to defined mixtures and then to the measured mixture effects of micropollutants extracted from the same river water samples. Effects (single and mixture) are expressed as effect units and toxic units, the inverse of effect concentrations and inhibitory concentrations, respectively, quantified using a panel of in vitro bioassays. We performed a Lagrangian sampling campaign under unsteady flow, collecting river water that was impacted by a wastewater treatment plant (WWTP) effluent. To reduce the computational time, the solution of the ADR equation was expressed by a convolution-based reactive transport approach, which was used to simulate the dynamics of the effects. The dissipation dynamics of the individual micropollutants were reproduced by the deterministic model following first-order kinetics. The dynamics of experimental mixture effects without known compositions were captured by the model ensemble obtained through Bayesian calibration. The highly fluctuating WWTP effluent discharge dominated the temporal patterns of the effect fluxes in the river. Minor inputs likely from surface runoff and pesticide diffusion might contribute to the general effect and cytotoxicity pattern but could not be confirmed by the model-based analysis of the available effect and chemical data.

Non-technical summary There has been a long history of conflicts, studies, and debate over how to both protect rivers and develop them sustainably. With a pause in new developments caused by the global pandemic, anticipated further implementation of the Paris Agreement and high-level global climate and biodiversity meetings in 2021, now is an opportune moment to consider the current trajectory of development and policy options for reconciling dams with freshwater system health. Technical summary We calculate potential loss of free-flowing rivers (FFRs) if proposed hydropower projects are built globally. Over 260,000 km of rivers, including Amazon, Congo, Irrawaddy, and Salween mainstem rivers, would lose free-flowing status if all dams were built. We propose a set of tested and proven solutions to navigate trade-offs associated with river conservation and dam development. These solution pathways are framed within the mitigation hierarchy and include (1) avoidance through either formal river protection or through exploration of alternative development options; (2) minimization of impacts through strategic or system-scale planning or re-regulation of downstream flows; (3) restoration of rivers through dam removal; and (4) mitigation of dam impacts through biodiversity offsets that include restoration and protection of FFRs. A series of examples illustrate how avoiding or reducing impacts on rivers is possible - particularly when implemented at a system scale - and can be achieved while maintaining or expanding benefits for climate resilience, water, food, and energy security. Social media summary Policy solutions and development pathways exist to navigate trade-offs to meet climate resilience, water, food, and energy security goals while safeguarding FFRs.

Suspended particulate matter (SPM) plays an important role in the fate of organic micropollutants in rivers during rain events, when sediments are remobilized and turbid runoff components enter the rivers. Under baseflow conditions, the SPM concentration is low and the contribution of SPM-bound contaminants to the overall risk of organic contaminants in rivers is assumed to be negligible. To challenge this assumption, we explored if SPM may act as a source or sink for all or specific groups of organic chemicals in a small river. The concentrations of over 600 contaminants and the mixture effects stemming from all chemicals in in vitro bioassays were measured for river water, SPM, and the surface sediment after solid-phase extraction or exhaustive solvent extraction. The bioavailable fractions of chemicals and mixture effects were estimated after passive equilibrium sampling of enriched SPM slurries and sediments in the lab. Dissolved compounds dominated the total chemical burden in the water column (water plus SPM) of the river, whereas SPM-bound chemicals contributed up to 46% of the effect burden even if the SPM concentration in rivers was merely 1 mg/L. The equilibrium between water and SPM was still not reached under low-flow conditions with SPM as a source of water contamination. The ratios of SPM-associated to sediment-associated neutral and hydrophobic chemicals as well as the ratios of the mixture effects expressed as bioanalytical equivalent concentrations were close to 1, suggesting that the surface sediment can be used as a proxy for SPM under baseflow conditions when the sampling of a large amount of water to obtain sufficient SPM cannot be realized.

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Megafauna species are intrinsically vulnerable to human impact. Freshwater megafauna (i.e., freshwater animals ≥30 kg, including fishes, mammals, reptiles, and amphibians) are subject to intensive and increasing threats. Thirty‐four species are listed as critically endangered on the International Union for Conservation of Nature (IUCN). Red List of Threatened Species, the assessments for which are an important basis for conservation actions but remain incomplete for 49 (24%) freshwater megafauna species. Consequently, the window of opportunity for protecting these species could be missed. Identifying the factors that predispose freshwater megafauna to extinction can help predict their extinction risk and facilitate more effective and proactive conservation actions. Thus, we collated 8 life‐history traits for 206 freshwater megafauna species. We used generalized linear mixed models to examine the relationships between extinction risk based on the IUCN Red List categories and the combined effect of multiple traits, as well as the effect of human impact on these relationships for 157 classified species. The most parsimonious model included human impact and traits related to species’ recovery potential including life span, age at maturity, and fecundity. Applying the most parsimonious model to 49 unclassified species predicted that 17 of them are threatened. Accounting for model predictions together with IUCN Red List assessments, 50% of all freshwater megafauna species are considered threatened. The Amazon and Yangtze basins emerged as global diversity hotspots of threatened freshwater megafauna, in addition to existing hotspots, including the Ganges‐Brahmaputra and Mekong basins and the Caspian Sea region. Assessment and monitoring of those species predicted to be threatened are needed, especially in the Amazon and Yangtze basins. Investigation of life‐history traits and trends in population and distribution, regulation of overexploitation, maintaining river connectiv

Organic micropollutants of anthropogenic origin in river waters may impair aquatic ecosystem health and drinking water quality. To evaluate micropollutant fate and turnover on a catchment scale, information on input source characteristics as well as spatial and temporal variability are required. The influence of tributaries from agricultural and urban areas and the input of wastewater were investigated by grab and Lagrangian sampling under base flow conditions within a 7.7 km long stretch of the Ammer River (Southwest Germany) using target screening for 83 organic micropollutants and four in‐vitro bioassays with environmentally relevant modes of action. In total 9 pesticides and transformation products, 13 pharmaceuticals and 6 industrial and household chemicals were detected. Further, aryl hydrocarbon receptor induction, peroxisome proliferator‐activated receptor activity, estrogenicity and oxidative stress response was measured in the river. The vast majority of the compounds and mixture effects were introduced by the effluent of a wastewater treatment plant, which contributed 50% of the total flow rate of the river on the sampling day. The tributaries contributed little to the overall load of organic micropollutants and mixture effects due to their relatively low discharge but showed a different chemical and toxicological pattern than the Ammer River. Though, a comparison to effect‐based trigger values pointed towards unacceptable surface water quality in the main stem and in some of the tributaries. Chemical analysis and in‐vitro bioassays covered different windows of analyte properties but reflected the same picture.

Chemicals emitted into the environment are typically present at low concentrations but may act together in mixtures. Concentration‐response curves of in vitro bioassays were often linear <30% effect and the predictions for concentration addition (CA) of similarly acting chemicals and for independent action (IA) of dissimilarly acting chemicals overlapped. We derived a joint CA/IA mixture model for the low‐effect level portion of concentration‐response curves. In a first case study, we evaluated the cytotoxicity of over 200 mixtures of up to 17 components that were mixed in concentration ratios as they occurred in river water. The predictions of the full IA model were indistinguishable from the predictions of the full CA model up to the 10% effect level confirming the applicability of the joint CA/IA mixture model at low effect levels. In a second case study, we evaluated if environmental concentrations trigger effects at levels low enough for the joint CA/IA mixture model to apply. The detected concentrations were scaled by their toxic potencies to estimate the mixture effect of the detected chemicals in a complex mixture. In 86% of 156 samples the effects fell in the validity range of the joint CA/IA mixture model (<10% effect level) confirming the CA assumption for toxic unit summation. The joint CA/IA mixture model is not suitable for testing specific mixture hypotheses and interactions of chemicals in mixtures, where more refined models are required, but it is helpful for the interpretation of effects of complex (multicomponent) environmental mixtures, especially for water samples with relatively low effect level.

Intermittent rivers and ephemeral streams (IRES) may represent over half the global stream network, but their contribution to respiration and carbon dioxide (CO2) emissions is largely undetermined. In particular, little is known about the variability and drivers of respiration in IRES sediments upon rewetting, which could result in large pulses of CO2. We present a global study examining sediments from 200 dry IRES reaches spanning multiple biomes. Results from standardized assays show that mean respiration increased 32-fold to 66-fold upon sediment rewetting. Structural equation modeling indicates that this response was driven by sediment texture and organic matter quantity and quality, which, in turn, were influenced by climate, land use, and riparian plant cover. Our estimates suggest that respiration pulses resulting from rewetting of IRES sediments could contribute significantly to annual CO2 emissions from the global stream network, with a single respiration pulse potentially increasing emission by 0.2-0.7%. As the spatial and temporal extent of IRES increases globally, our results highlight the importance of recognizing the influence of wetting-drying cycles on respiration and CO2 emissions in stream networks.

Intermittent rivers and ephemeral streams (IRES) may represent over half the global stream network, but their contribution to respiration and carbon dioxide (CO2) emissions is largely undetermined. In particular, little is known about the variability and drivers of respiration in IRES sediments upon rewetting, which could result in large pulses of CO2. We present a global study examining sediments from 200 dry IRES reaches spanning multiple biomes. Results from standardized assays show that mean respiration increased 32-fold to 66-fold upon sediment rewetting. Structural equation modeling indicates that this response was driven by sediment texture and organic matter quantity and quality, which, in turn, were influenced by climate, land use, and riparian plant cover. Our estimates suggest that respiration pulses resulting from rewetting of IRES sediments could contribute significantly to annual CO2 emissions from the global stream network, with a single respiration pulse potentially increasing emission by 0.2 0.7%. As the spatial and temporal extent of IRES increases globally, our results highlight the importance of recognizing the influence of wetting-drying cycles on respiration and CO2 emissions in stream networks. (c)2019. American Geophysical Union. All Rights Reserved.

Climate change and human pressures are changing the global distribution and the extent of intermittent rivers and ephemeral streams (IRES), which comprise half of the global river network area. IRES are characterized by periods of flow cessation, during which channel substrates accumulate and undergo physico-chemical changes (preconditioning), and periods of flow resumption, when these substrates are rewetted and release pulses of dissolved nutrients and organic matter (OM). However, there are no estimates of the amounts and quality of leached substances, nor is there information on the underlying environmental constraints operating at the global scale. We experimentally simulated, under standard laboratory conditions, rewetting of leaves, riverbed sediments, and epilithic biofilms collected during the dry phase across 205 IRES from five major climate zones. We determined the amounts and qualitative characteristics of the leached nutrients and OM, and estimated their areal fluxes from riverbeds. In addition, we evaluated the variance in leachate characteristics in relation to selected environmental variables and substrate characteristics. We found that sediments, due to their large quantities within riverbeds, contribute most to the overall flux of dissolved substances during rewetting events (56% 98%), and that flux rates distinctly differ among climate zones. Dissolved organic carbon, phenolics, and nitrate contributed most to the areal fluxes. The largest amounts of leached substances were found in the continental climate zone, coinciding with the lowest potential bioavailability of the leached OM. The opposite pattern was found in the arid zone. Environmental variables expected to be modified under climate change (i.e. potential evapotranspiration, aridity, dry period duration, land use) were correlated with the amount of leached substances, with the strongest relationship found for sediments. These results show that the role of IRES should be accounted for in g

Climate change and human pressures are changing the global distribution and the extent of intermittent rivers and ephemeral streams (IRES), which comprise half of the global river network area. IRES are characterized by periods of flow cessation, during which channel substrates accumulate and undergo physico-chemical changes (preconditioning), and periods of flow resumption, when these substrates are rewetted and release pulses of dissolved nutrients and organic matter (OM). However, there are no estimates of the amounts and quality of leached substances, nor is there information on the underlying environmental constraints operating at the global scale. We experimentally simulated, under standard laboratory conditions, rewetting of leaves, riverbed sediments, and epilithic biofilms collected during the dry phase across 205 IRES from five major climate zones. We determined the amounts and qualitative characteristics of the leached nutrients and OM, and estimated their areal fluxes from riverbeds. In addition, we evaluated the variance in leachate characteristics in relation to selected environmental variables and substrate characteristics. We found that sediments, due to their large quantities within riverbeds, contribute most to the overall flux of dissolved substances during rewetting events (56%–98%), and that flux rates distinctly differ among climate zones. Dissolved organic carbon, phenolics, and nitrate contributed most to the areal fluxes. The largest amounts of leached substances were found in the continental climate zone, coinciding with the lowest potential bioavailability of the leached OM. The opposite pattern was found in the arid zone. Environmental variables expected to be modified under climate change (i.e. potential evapotranspiration, aridity, dry period duration, land use) were correlated with the amount of leached substances, with the strongest relationship found for sediments. These results show that the role of IRES should be accounted for in g

Intermittent rivers and ephemeral streams (IRES) may represent over half the global stream network, but their contribution to respiration and carbon dioxide (CO2) emissions is largely undetermined. In particular, little is known about the variability and drivers of respiration in IRES sediments upon rewetting, which could result in large pulses of CO2. We present a global study examining sediments from 200 dry IRES reaches spanning multiple biomes. Results from standardized assays show that mean respiration increased 32-fold to 66-fold upon sediment rewetting. Structural equation modeling indicates that this response was driven by sediment texture and organic matter quantity and quality, which, in turn, were influenced by climate, land use, and riparian plant cover. Our estimates suggest that respiration pulses resulting from rewetting of IRES sediments could contribute significantly to annual CO2 emissions from the global stream network, with a single respiration pulse potentially increasing emission by 0.2–0.7%. As the spatial and temporal extent of IRES increases globally, our results highlight the importance of recognizing the influence of wetting-drying cycles on respiration and CO2 emissions in stream networks.

Some environmental pollutants impair mitochondria, which are of vital importance as energy factories in eukaryotic cells. Mitochondrial toxicity was quantified by measuring the change of the oxygen consumption rate (OCR) of HepG2 cells with the Agilent Seahorse XFe96 Analyzer. Various mechanisms of mitochondrial toxicity, including inhibition of the electron transport chain or the ATP‐synthase as well as uncoupling of oxidative phosphorylation, were differentiated by dosing the sample in parallel with reference compounds following the OCR over time. These time‐OCR traces were used to derive effect concentrations EC10 for 10% inhibition of the electron transport chain or 10% of uncoupling. The low effect level of 10% was necessary because environmental mixtures contain thousands of chemicals, only few of them interfering with mitochondria but the others causing cytotoxicity. The OCR bioassay was validated with environmental pollutants of known mechanism of mitochondrial toxicity. Binary mixtures of uncouplers or inhibitors acted according to the mixture model of concentration addition. Uncoupling and/or inhibitory effects were detected in extracts of river water samples without apparent cytotoxicity. Uncoupling effects could only be quantified in water samples if inhibitory effects occurred at lower concentrations because no uncoupling can be detected without an appreciable membrane potential built up. The OCR bioassay can thus complement chemical analysis and in‐vitro bioassays for monitoring micropollutants in water.

Ionizable organic chemicals (IOCs) such as organic acids and bases are an important substance class requiring aquatic hazard evaluation. While the aquatic toxicity of IOCs is highly dependent on the water pH, many toxicity studies in the literature cannot be interpreted because pH was not reported or not kept constant during the experiment, calling for an adaptation and improvement of testing guidelines. The modulating influence of pH on toxicity is mainly caused by pH‐dependent uptake and bioaccumulation of IOCs, which can be described by ion‐trapping and toxicokinetic models. The internal effect concentrations of IOCs were found to be independent of the external pH due to organisms’ and cells’ ability to maintain a stable internal pH milieu. If the external pH is close to the internal pH, existing Quantitative Structure‐Activity Relationships (QSAR) for neutral organics can be adapted by substituting the octanol‐water partition coefficient by the ionization‐corrected liposome‐water distribution ratio as the hydrophobicity descriptor, demonstrated by modification of the target lipid model. Charged, zwitterionic and neutral species of an IOC can all contribute to observed toxicity, either through concentration‐additive mixture effects or by interaction of different species, as is the case for uncoupling of mitochondrial respiration. For specifically acting IOCs, we recommend a two‐step screening procedure with ion‐trapping/QSAR models used to predict the baseline toxicity, followed by adjustment using the toxic ratio derived from in vitro systems. Receptor or plasma binding models also show promise for elucidating IOC toxicity. This review is intended to help demystify ecotoxicity of IOCs and provide recommendations for their hazard and risk assessment.

The aim of the current study was to understand and develop models to predict the pH-dependent toxicity of ionizable pharmaceuticals in embryos of the zebrafish Danio rerio. We found a higher uptake and toxicity with increasing neutral fraction of acids (diclofenac, genistein, naproxen, torasemide, and warfarin) and bases (metoprolol and propranolol). Simple mass balance models accounting for the partitioning to lipids and proteins in the zebrafish embryo were found to be suitable to predict the bioconcentration after 96 h of exposure if pH values did not differ much from the internal pH of 7.55. For other pH values, a kinetic ion-trap model for the zebrafish embryo explained the pH dependence of biouptake and toxicity. The total internal lethal concentrations killing 50% of the zebrafish embryos (ILC50) were calculated from the measured BCF and LC50. The resulting ILC50 were independent of external pH. Critical membrane concentrations were deduced by an internal mass balance model, and apart from diclofenac, whose specific toxicity in fish had already been established, all pharmaceuticals were confirmed to act as baseline toxicants in zebrafish.

Aim: Freshwater megafauna remain underrepresented in research and conservation, despite a disproportionately high risk of extinction due to multiple human threats. Therefore, our aims are threefold; (i) identify global patterns of freshwater megafauna richness and endemism, (ii) assess the conservation status of freshwater megafauna and (iii) demonstrate spatial and temporal patterns of human pressure throughout their distribution ranges. Location: Global. Methods: We identified 207 extant freshwater megafauna species, based on a 30 kg weight threshold, and mapped their distributions using HydroBASINS subcatchments (level 8). Information on conservation status and population trends for each species was extracted from the IUCN Red List website. We investigated human impacts on freshwater megafauna in space and time by examining spatial congruence between their distributions and human pressures, described by the Incident Biodiversity Threat Index and Temporal Human Pressure Index. Results: Freshwater megafauna occur in 76% of the world s main river basins (level 3 HydroBASINS), with species richness peaking in the Amazon, Congo, Orinoco, Mekong and Ganges-Brahmaputra basins. Freshwater megafauna are more threatened than their smaller counterparts within the specific taxonomic groups (i.e., fishes, mammals, reptiles and amphibians). Out of the 93 freshwater megafauna species with known population trends, 71% are in decline. Meanwhile, IUCN Red List assessments reported insufficient or outdated data for 43% of all freshwater megafauna species. Since the early 1990s, human pressure has increased throughout 63% of their distribution ranges, with particularly intense impacts occurring in the Mekong and Ganges-Brahmaputra basins. Main conclusions: Freshwater megafauna species are threatened globally, with intense and increasing human pressures occurring in many of their biodiversity hotspots. We call for research and conservation actions for freshwater megafauna, as they ar

BackgroundRivers receive water and associated organic micropollutants from their entire catchment, including from urban, agricultural and natural sources, and constitute an important environmental component for catalyzing pollutant turnover. Environmental removal processes were extensively investigated under laboratory conditions in the past but there is still a lack of information on how organic micropollutants attenuate on the catchment scale. The aim of this study was to describe the chemical and toxicological profile of a 4th order river and to characterize in-stream processes. We propose indicator chemicals and indicator in vitro bioassays as screening methods to evaluate micropollutant input and transport and transformation processes of the chemical burden in a river. Carbamazepine and sulfamethoxazole were selected as indicators for dilution processes and the moderately degradable chemicals tramadol and sotalol as indicators for potential in-stream attenuation processes. The battery of bioassays covers seven environmentally relevant modes of action, namely estrogenicity, glucocorticogenic activity, androgenicity progestagenic activity and oxidative stress response, as well as activation of the peroxisome proliferator-activated receptor and the aryl hydrocarbon receptor, using the GeneBLAzer test battery and the AhR-CALUX and AREc32 assays.ResultsBoth approaches, targeted chemical analysis and in vitro bioassays, identified a wastewater treatment plant (WWTP) as a major input source of organic micropollutants that dominantly influenced the water quality of the river. Downstream of the WWTP the amount of detected chemicals and biological effects decreased along the river flow. The organic indicator chemicals of known degradability uncovered dilution and potential loss processes in certain river stretches. The average cytotoxic potency of the river water decreased in a similar fashion as compounds of medium degradability such as the pharmaceutical sotalol.Conclu

von Schiller, D., Datry, T., Corti, R., Foulquier, A., Tockner, K., Marcé, R., ... Zoppini, A. (2019). Sediment respiration pulses in intermittent rivers and ephemeral streams. Global Biogeochemical Cycles, 33(10), 1251-1263. Available here