German Rivers Research Articles

Downstream Effects of the Pandemic? Spatiotemporal Trends of Quaternary Ammonium Compounds in Suspended Particulate Matter of German Rivers

During the SARS-CoV-2 pandemic, the preventive use of antimicrobials such as quaternary ammonium compounds (QACs) surged worldwide. As cationic and surface-active biocides, QACs are only partly removed during wastewater treatment and may cause adverse ecological effects in the downstream environment. To understand the environmental consequences of increased disinfectant use during the pandemic, we investigated spatiotemporal QAC concentration trends in the suspended particulate matter (SPM) of three diverse German rivers. Covering pooled annual SPM samples from 2006-2021 and monthly samples from 2018-2021 collected by the German Environmental Specimen Bank, 31 QACs were quantified by high performance liquid chromatography–mass spectrometry.∑QAC concentrations in annual samples differed by more than tenfold between rivers in the order Saar (average 6.7µg/g) > Rhine (0.9µg/g) > Mulde (0.3µg/g). The strongest potential pandemic imprint was however observed in the Mulde (+67%) and Rhine (+22%). Besides pandemic dynamics, also seasonal variation and mineral content of SPM tentatively affected QAC concentrations. Exceedance of predicted no-effect concentrations for sediment suggest ecotoxicological risks for long-chained QACs already before the pandemic. Our study thus highlights the importance of monitoring the environmental effects of antimicrobial use during pandemics and calls for an urgent minimization of non-essential applications. Environmental implicationThe SARS-CoV-2 pandemic caused a global surge in disinfectant use, including quaternary ammonium compounds (QACs). This raises concerns about their environmental residues, aquatic toxicity and contribution to the (co)selection of antimicrobial resistance in pathogens. To assess these ecotoxicological risks, we investigated spatiotemporal QAC concentration trends in suspended particulate matter of German rivers. While seasonal and spatial fluctuations exceed a potential pandemic “imprint” by a factor of 10, concentrations of some QACs reach ecotoxicological effect levels. This highlights the need to consider particle-associated QAC concentrations, the widespread use of QAC, as well as the environmental implications of chemical public health interventions.

Investigation of the Effect of Oxide Additives on the Band Gap and Photocatalytic Efficiency of TiO2 as a Fixed Film.

The effects of various additives (Y2O3, Ga2O3, and WO3) on photocatalytic degradation efficiency under UV light-emitting diodes (LEDs) and the optical properties of TiO2 Degussa P25 were investigated using ketoprofen and diclofenac, two non-steroidal anti-inflammatory drugs commonly detected in German rivers. Experimental results demonstrated that thin films containing these additives exhibited similar photocatalytic degradation efficiencies as pure TiO2, achieving a 30% degradation of ketoprofen over 150 min. In contrast, the Y2O3/TiO2 thin film showed significantly improved performance, achieving a 46% degradation of ketoprofen in 180 min. Notably, the Y2O3/TiO2 system was three times more effective in degrading diclofenac compared to pure TiO2. Additionally, the Y2O3/TiO2 photocatalyst retained its activity over three successive cycles with only a slight decrease in efficiency. The photocatalytic degradation of both organic pollutants followed first-order kinetics with all photocatalysts. The investigation included SEM imaging to assess the surface homogeneity of the thin films and UV-vis solid-state spectroscopy to evaluate the impact of the additives on the energy band gap of TiO2.

First indication of platinum input into the southern North Sea via German Rivers

Platinum (Pt) is an emerging critical metal, but the long-term environmental impacts of anthropogenic Pt remain largely unknown. We report, for the first time, Pt input from three major German rivers (Ems, Weser and Elbe) into the southern North Sea. All three rivers were a major source of Pt, with a maximum of 6.3 pmol L−1 in the Elbe endmember, compared to generally <1.0 pmol L−1 in the North Sea samples. All samples measured in the North Sea were elevated in Pt (mean of ∼0.9 pmol L−1) relative to typical open-ocean values (∼0.2–0.3 pmol L−1 in the Atlantic and Pacific). Across the Weser and Elbe estuarine transect, an initial sharp drawdown of Pt concentrations at low salinity (S < 1.5) was observed, which correlated well with Fe and Mn concentrations, indicating adsorption and co-precipitation at low salinity. At higher salinities (S ≥ 3) Pt concentrations followed a more conservative distribution relative to salinity. In addition, we followed a 12 h tidal cycle in each of the rivers, which generally reflected an inverse correlation of Pt concentrations against salinity. This study indicates that Pt might be an emerging contaminant in the North Sea, requiring further study to define specific sources.

Turbidity effects on prey consumption and survival of larval European smelt (Osmerus eperlanus)

The anadromous European smelt (Osmerus eperlanus) plays a key role in food webs of many riverine ecosystems in Europe. However, population sizes in several German rivers (e.g. Elbe or Weser rivers) have diminished drastically over the past decade. Turbidity has been considered one of the stressors affecting the successful recruitment of European smelt, as their early life stages may be particularly sensitive to changes in the abiotic environment. In this study, we investigated whether prey consumption and survival of European smelt larvae would be negatively affected by an acute exposure to elevated turbidity. We reared the larvae in the laboratory and exposed them in four separate trials (18 to 26 days post hatch, 9.5 ± 0.8 mm standard length, mean ± SD) to six turbidity levels (0–500 NTU, nephelometric turbidity units). We found that prey uptake increased at low turbidity levels and decreased at high turbidity levels, with an optimum between 100 and 200 NTU. Survival started to decrease at turbidity levels above 300 NTU. In addition, we conducted a systematic literature analysis in which we found that prey consumption of larval and juvenile fishes had been tested across a wide range of turbidity levels, mostly using pelagic (e.g. planktonic) prey items, with more studies focusing on perciform fishes and juvenile rather than larval life stages. Our empirical findings contribute to establishing thresholds for optimal larval European smelt performance under increased turbidity and provide valuable information for developing mechanistic models that assess potential consequences for European smelt recruitment dynamics.

A novel additive regression model for streamflow forecasting in German rivers

Forecasting streamflows, essential for flood mitigation and the efficient management of water resources for drinking, agriculture and hydroelectric power generation, presents a formidable challenge in most real-world scenarios. In this study, two models, the first based on the Additive Regression of Radial Basis Function Neural Networks (AR-RBF) and the second based on the stacking with the Pace Regression of the Multilayer Perceptron and Random Forest (MLP-RF-PR), were compared for the prediction of short-term (1–3 days ahead) and medium-term (7 days ahead) daily streamflow rates of three different rivers in Germany: the Elbe River at Wittenberge, the Leine River at Herrenhausen, and the Saale River at Hof. The lagged values of streamflow rate, precipitation and temperature were considered for the modeling. Moreover, the Bayesian Optimization (BO) algorithm was used to assess the optimal number of lagged values and hyperparameters. Both models showed accurate predictions for short-term forecasting, with R2 for 1-day ahead predictions ranging from 0.939 to 0.998 for AR-RBF and from 0.930 to 0.996 for MLP-RF-PR, while MAPE ranged from 2.02 % to 8.99 % for AR-RBF and from 2.14 % to 9.68 % for MLP-RF-PR, when exogeneous variables were included. As the forecast horizon increased, a reduction in forecasting accuracy was observed. However, both models could still predict the overall flow pattern, even for 7-day-ahead predictions, with R2 ranging from 0.772 to 0.871 for AR-RBF and from 0.703 to 0.840 for MLP-RF-PR, while MAPE ranged from 10.60 % to 20.45 % for AR-RBF and from 10.44 % to 19.65 % for MLP-RF-PR. Overall, the outcomes of this study suggest that both AR-RBF and MLP-RF-PR can be reliable tools for the short- and medium-term streamflow rate prediction, requiring a short number of parameters to be optimized, making them easy to implement while reducing the calculation time required.

Winter post-droughts amplify extreme nitrate concentrations in German rivers

Hydrological extremes can affect nutrient export from catchments to streams, posing a threat to aquatic ecosystems. In this study, we investigated the effects of hydrological drought on nitrate concentrations in the streamflow of 182 German catchments from 1980 to 2020. We found that across all seasons, 40% and 25% of the catchments showed significantly lower nitrate concentrations during drought and post-droughts, respectively, when compared to non-drought conditions. However, we observed pronounced spatial variability in the responses, particularly during winter droughts and post-droughts, with more catchments exhibiting higher nitrate concentrations. Specifically, nitrate concentrations were significantly higher in 25% of the study catchments during winter droughts, particularly in wetter catchments with low nitrogen retention. During winter post-droughts, nitrate concentrations are significantly higher in 19% of the catchments, especially in wetter catchments with more nitrogen surplus. Moreover, the likelihood of nitrate seasonal extremes increased by 6% during winter post-drought in our study catchments. Considering the projected increase in the frequency of droughts in Germany, the increase in nitrate concentrations during the corresponding post-drought periods poses a potential threat to aquatic ecosystem health.

Water quality deterioration remains a major stressor for macroinvertebrate, diatom and fish communities in German rivers

About 60 % of Europe's rivers fail to meet ecological quality standards derived from biological criteria. The causes are manifold, but recent reports suggest a dominant role of hydro-morphological and water quality-related stressors. Yet, in particular micropollutants and hydrological stressors often tend to be underrepresented in multiple-stressor studies. Using monitoring data from four Federal States in Germany, this study investigated the effects of 19 stressor variables from six stressor groups (nutrients, salt ions, dissolved oxygen/water temperature, mixture toxicity of 51 micropollutants, hydrological alteration and morphological habitat quality) on three biological assemblages (fishes, macroinvertebrates, benthic diatoms). Biological effects were analyzed for 35 community metrics and quantified using Random Forest (RF) analyses to put the stressor groups into a hierarchical context. To compare metric responses, metrics were grouped into categories reflecting important characteristics of biological communities, such as sensitivity, functional traits, diversity and community composition as well as composite indices that integrate several metrics into one single index (e.g., ecological quality class).Water quality-related stressors – but not micropollutants – turned out to dominate the responses of all assemblages. In contrast, the effects of hydro-morphological stressors were less pronounced and stronger for hydrological stressors than for morphological stressors. Explained variances of RF models ranged 23–64 % for macroinvertebrates, 16–40 % for benthic diatoms and 18–48 % for fishes. Despite a high variability of responses across assemblages and stressor groups, sensitivity metrics tended to reveal stronger responses to individual stressors and a higher explained variance in RF models than composite indices. The results of this study suggest that (physico-chemical) water quality deterioration continues to impact biological assemblages in many German rivers, despite the extensive progress in wastewater treatment during the past decades. To detect water quality deterioration, monitoring schemes need to target relevant physico-chemical stressors and micropollutants. Furthermore, monitoring needs to integrate measures of hydrological alteration (e.g., flow magnitude and dynamics). At present, hydro-morphological surveys rarely address the degree of hydrological alteration. In order to achieve a good ecological status, river restoration and management needs to address both water quality-related and hydro-morphological stressors. Restricting analyses to just one single organism group (e.g., macroinvertebrates) or only selected metrics (e.g., ecological quality class) may hamper stressor identification and its hierarchical classification and, thus may mislead river management.

Further Insight into Extractable (Organo)fluorine Mass Balance Analysis of Tap Water from Shanghai, China.

The ubiquitous occurrence of per- and polyfluoroalkyl substances (PFAS) and the detection of unexplained extractable organofluorine (EOF) in drinking water have raised growing concerns. A recent study reported the detection of inorganic fluorinated anions in German river systems, and therefore, in some samples, EOF may include some inorganic fluorinated anions. Thus, it might be more appropriate to use the term "extractable fluorine (EF) analysis" instead of the term EOF analysis. In this study, tap water samples (n = 39) from Shanghai were collected to assess the levels of EF/EOF, 35 target PFAS, two inorganic fluorinated anions (tetrafluoroborate (BF4-) and hexafluorophosphate (PF6-)), and novel PFAS through suspect screening and potential oxidizable precursors through oxidative conversion. The results showed that ultra-short PFAS were the largest contributors to target PFAS, accounting for up to 97% of ΣPFAS. To the best of our knowledge, this was the first time that bis(trifluoromethanesulfonyl)imide (NTf2) was reported in drinking water from China, and p-perfluorous nonenoxybenzenesulfonate (OBS) was also identified through suspect screening. Small amounts of precursors that can be oxidatively converted to PFCAs were noted after oxidative conversion. EF mass balance analysis revealed that target PFAS could only explain less than 36% of EF. However, the amounts of unexplained extractable fluorine were greatly reduced when BF4- and PF6- were included. These compounds further explained more than 44% of the EF, indicating the role of inorganic fluorinated anions in the mass balance analysis.

Seasonal variations of microplastic pollution in the German River Weser

Rivers play a major role in the distribution of microplastics (MPs) in the environment, however, research on temporal variations in these highly dynamic systems is still in its infancy. To date, most studies dealing with the seasonality of MP contamination in rivers focus on bi-yearly analysis, while temporal fluctuations over the course of the year are rarely studied. To shed more light on seasonal variability of MP abundance and potential driving factors, we have thus sampled the water surface of one location in the Weser River in Germany monthly over one entire year. In our study, we targeted MP in the size range 10–5000 μm, using two different state-of-the-art sampling methods (manta net for large MP (l-MP; 500–5000 μm) and a filtration system for small MP (s-MP; 10–500 μm)) and analysis techniques (ATR-FTIR and FPA-μFTIR) for chemical identification. Our findings show a strong size-dependent positive correlation of the MP concentration with discharge rates (specifically direct runoff) and suspended particulate matter (SPM) for s-MPs, specifically in the size range 10–149 μm. L-MPs, however, show a different environmental behaviour and do not follow these patterns. With our study, we were able to deliver a much higher temporal resolution, covering a broader size range of MPs compared to most studies. Our findings point towards an interplay of two possible mechanisms: a) the riverbeds play an important role in large-scale MP and SPM release via resuspension during high discharge events, and b) precipitation-driven soil erosion and runoff from urban surfaces (e.g. rain sewers) introduce MP and SPM. Hence, our study serves as a basis for more detailed investigations of MP transport in and between ecosystems.

Overestimating management progress—modelled vs. monitored silver eel escapement in a North Sea draining river

Abstract The success of European efforts towards the recovery of the European eel (Anguilla anguilla) population will rely on accurate assessments of local stock status for the implementation of conservation measures. Yet, direct and continuous monitoring of the escapement of potential spawners (“silver eels”) is unfeasible in most habitats. Therefore, population models are widely used to estimate local silver eel escapement, but require input information on recruitment, demographic characteristics, and mortalities that are often estimated with great uncertainties. We conducted a combined mark–recapture and acoustic telemetry study across two migration seasons to quantify the actual silver eel escapement in a sub-catchment of the German river Ems. Results were compared with predictions from the demographic model used to provide stock parameters in Germany according to the EU eel-regulation. Mark–recapture results suggested an annual female silver eel escapement of ∼15–17 tons, while the demographic model predicted 90–98 tons, indicating a considerable overestimation. Our results suggest that realistic prediction of silver eel escapement is hardly feasible without high-quality input information and highlight the need for site-specific model calibrations against monitoring data. Overestimations of local stock sizes are problematic if they obscure the necessity for adequate conservation measures, hindering their implementation.

The temporal abundance-distribution relationship in a global invader sheds light on species distribution mechanisms

The geographic expansion and abundance fluctuations of invasive species offer unprecedented insights to investigate potential mechanisms underlying the distribution-abundance relationship, one of the most universal patterns in community ecology. However, the abundance of invasive species is rarely documented in the needed detail. Data from historical records, scientific and popular literature, citizen science and expert interviews were synthesized to obtain insights into the long-term expansion and abundance cycles of the Chinese mitten crab, one of the world’s 100 worst invasive species. Thus for the first time, global long-term data on population size fluctuations have been correlated with the global spatiotemporal invasion history of a non-native species. Geographic expansions and increases in abundance co-occurred in the 1930s and again since the 1990s in agreement with the distribution-abundance relationship. Furthermore, a regional case study for the German river Elbe indicates that increases in abundance may be driven by improved riverine water quality and rising sea surface temperatures. Environmental restoration and climate change therefore benefit this invasive species, and could lead to further geographic expansion and increases in abundance.

Quantification and characterization of PFASs in suspended particulate matter (SPM) of German rivers using EOF, dTOPA, (non-)target HRMS

In this study, we compare analytical methods for PFAS determination–target analysis, non-target screening (NTS), direct total oxidizable precursor assay (dTOPA) and extractable organically bound fluorine (EOF). Therefore, suspended particulate matter (SPM) samples from German rivers at different locations in time series from 2005 to 2020 were analyzed to investigate temporal and spatially resolved trends. In this study 3 PFAS mass balances approaches were utilized: (i) PFAA target vs. PFAS dTOPA, (ii) PFAS target vs. EOF and (iii) PFAS target vs. PFAS dTOPA vs. organofluorines NTS vs. EOF. Mass balance approach (i) revealed high proportions of precursor substances in SPM samples. For the time resolved analysis an increase from 94% (2005) to 97% in 2019 was observable. Also for the spatial resolved analysis precursor proportions were high with >84% at all sampling sites. Mass balance approach (ii) showed that the unidentified EOF (uEOF) fraction increased over time from 82% (2005) to 99% (2019). Furthermore, along the river courses the uEOF increased. In the combined mass balance approach (iii) using 4 different analytical approaches EOF fractions were further unraveled. The EOF pattern was fully explainable at the sampling sites at Saar and Elbe rivers. For the time resolved analysis, an increased proportion of the EOF was now explainable. However, still 27% of the EOF for the time resolved analysis and 25% of the EOF for the spatial resolved analysis remained unknown. Therefore, in a complementary approach, both the EOF and dTOPA reveal unknown gaps in the PFAS mass balance and are valuable contributions to PFAS risk assessment. Further research is needed to identify organofluorines summarized in the EOF parameter.

Pristine levels of suspended sediment in large German river channels during the Anthropocene?

Abstract. Suspended sediment is an integral part of riverine transport and functioning that has been strongly altered during the Anthropocene due to the overwhelming human pressure on soils, sediments, and the water cycle. Understanding the controls of changing suspended sediment in rivers is therefore vital for effective management strategies. Here we present results from a trend analysis of suspended sediments covering 62 monitoring stations along the German waterways (catchment sizes range between 2000 and 160 000 km2) with more than 440 000 water samples taken between 1990 and 2010. Based on daily monitoring of suspended sediment concentration (SSC), we found significant declines in mean annual SSC and annual suspended sediment loads (SSLs) at 49 of 62 monitoring stations totaling −0.92 mg L−1 yr−1. At some stations decreases during the 20 years represent up to 50 % of the long-term average SSC. Significant decreases in SSC are associated with declining SSL despite an increase in sheet and rill erosion by almost 150 % derived from modeling due to changes in land use and management as well as rainfall erosivity. The contemporary suspended sediment loads of the Rhine at the German–Dutch border are approaching the natural base level of ∼1 Mt yr−1, which was reached by the Rhine during the mid-Holocene when the suspended sediment load was adjusted to the Holocene climatic conditions and before the onset of increased loads due to human-induced land use changes in the Rhine catchment. At this point we can only speculate regarding potential reasons for a decline in sediment transport in larger rivers despite erosion increase. We argue that increased sediment retention in upstream headwaters is presumably the major reason for declining SSC in the large river channels studied.

Stoichiometry on the edge—humans induce strong imbalances of reactive C:N:P ratios in streams

Anthropogenic nutrient inputs led to severe degradation of surface water resources, affecting aquatic ecosystem health and functioning. Ecosystem functions such as nutrient cycling and ecosystem metabolism are not only affected by the over-abundance of a single macronutrient but also by the stoichiometry of the reactive molecular forms of dissolved organic carbon (rOC), nitrogen (rN), and phosphorus (rP). So far, studies mainly considered only single macronutrients or used stoichiometric ratios such as N:P or C:N independent from each other. We argue that a mutual assessment of reactive nutrient ratios rOC:rN:rP relative to organismic demands enables us to refine the definition of nutrient depletion versus excess and to understand their linkages to catchment-internal biogeochemical and hydrological processes. Here we show that the majority (94%) of the studied 574 German catchments show a depletion or co-depletion in rOC and rP, illustrating the ubiquity of excess N in anthropogenically influenced landscapes. We found an emerging spatial pattern of depletion classes linked to the interplay of agricultural sources and subsurface denitrification for rN and topographic controls of rOC. We classified catchments into stoichio-static and stochio-dynamic catchments based on their degree of intra-annual variability of rOC:rN:rP ratios. Stoichio-static catchments (36% of all catchments) tend to have higher rN median concentrations, lower temporal rN variability and generally low rOC medians. Our results demonstrate the severe extent of imbalances in rOC:rN:rP ratios in German rivers due to human activities. This likely affects the inland-water nutrient retention efficiency, their level of eutrophication, and their role in the global carbon cycle. Thus, it calls for a more holistic catchment and aquatic ecosystem management integrating rOC:rN:rP stoichiometry as a fundamental principle.

Legacy Phosphorus in Sediments of Lowland Waterways

Riverbed sediments in agricultural landscapes are loaded with phosphorus (P). They may act as a source or sink for riverine P, possibly causing harmful algae blooms and eutrophication in streams and receiving water bodies, including coastal waters. In this study, we aimed at identifying the labile, moderately labile, and stable P fraction (Hedley fractionation) in sediments of a northeastern German river basin (3000 km2). A non-metrical multidimensional scaling (NMDS) was used to identify the most significant environmental predictors of the P fractionation in sediments. The total P contents of the sediments varied over a wide range (698 ± 701 mg P kg−1 sediment−1), spanning from 98 to 2648 mg P kg−1 sediment−1. Adjacent agricultural reference soils had markedly lower total P contents of 354 ± 132 mg P kg−1 soil−1, ranging from 146 to 483 P kg−1 soil−1. There were almost no differences between the P contents of the top (0–2 cm) and the bottom (2–10 cm) layer. The dominant P fractions were the moderately labile (NaOH-P) and the stable (H2SO4-P) fractions, which accounted for more than 50% of the total P at each sampling point. The NMDS revealed that iron and aluminum contents, as well as land use, are significant predictors for the P fractionation of the sediment. The sediment P-composition reflects the P-status of the agriculturally used mineral soils. However, the size of the contributing catchment as well as the length of the water way have no effects on sediment P. In conclusion, sediment P stocks, though variable, may impede the good ecological status of river waters for decades, especially in lowland basins where hydraulic conditions and a very low stream velocity often create low redox and P dissolution conditions in sediments.

Quantification of 68 elements in river water monitoring samples in single-run measurements

Triple-quadrupole inductively coupled plasma mass spectrometry (ICP-QQQ-MS) is a unique analytical technique which is, next to speciation analyses, applied for the determination of total element concentrations in several matrices. Due to its wide linear range, short analysis times, and the collision-reaction gas technology, it is capable of addressing a high number of analytes in a single run with sufficient low limits of quantification for river water monitoring. Over the last decades, the focus of the environmental monitoring changed from “traditional” and regulated analytes to elements of possibly rising concern from new applications such as the so-called technology-critical elements (TCE). By widening the analytical window of this method for applications in networks of future river water monitoring, a better understanding of natural transport processes and global biogeochemical element cycles will be established and the total number of methods can be reduced. During method development and validation, certified reference materials, calibration check solutions, and spiked river water samples from 12 major German rivers covering different catchment areas were measured and evaluated with the three cell gases He, H2 and O2. The method delivers a best as possible undisturbed simultaneous determination for 68 out of 71 target analytes with recoveries in an accepted range of 80–120% for river water samples (dissolved fraction; <0.45 μm). After comprehensive evaluation, we offer a novel best-practice multi-element method for river water monitoring with the goal of fostering the exchange and discussion between practitioners in long-term river monitoring. It enables the readers to create their own methods based on the scientific needs to monitor elemental “fingerprints” of rivers and their catchments.

Temporal patterns and drivers of CO2 emission from dry sediments in a groyne field of a large river

Abstract. River sediments falling dry at low water levels are sources of CO2 to the atmosphere. While the general relevance of CO2 emissions from dry sediments has been acknowledged and some regulatory mechanisms have been identified, knowledge on mechanisms and temporal dynamics is still sparse. Using a combination of high-frequency measurements and two field campaigns we thus aimed to identify processes responsible for CO2 emissions and to assess temporal dynamics of CO2 emissions from dry sediments at a large German river. CO2 emissions were largely driven by microbial respiration in the sediment. Observed CO2 fluxes could be explained by patterns and responses of sediment respiration rates measured in laboratory incubations. We exclude groundwater as a significant source of CO2 because the CO2 concentration in the groundwater was too low to explain CO2 fluxes. Furthermore, CO2 fluxes were not related to radon fluxes, which we used to trace groundwater-derived degassing of CO2. CO2 emissions were strongly regulated by temperature resulting in large diurnal fluctuations of CO2 emissions with emissions peaking during the day. The diurnal temperature–CO2 flux relation exhibited a hysteresis which highlights the effect of transport processes in the sediment and makes it difficult to identify temperature dependence from simple linear regressions. The temperature response of CO2 flux and sediment respiration rates in laboratory incubations was identical. Also deeper sediment layers apparently contributed to CO2 emissions because the CO2 flux was correlated with the thickness of the unsaturated zone, resulting in CO2 fluxes increasing with distance to the local groundwater level and with distance to the river. Rain events lowered CO2 emissions from dry river sediments probably by blocking CO2 transport from deeper sediment layers to the atmosphere. Terrestrial vegetation growing on exposed sediments greatly increased respiratory sediment CO2 emissions. We conclude that the regulation of CO2 emissions from dry river sediments is complex. Diurnal measurements are mandatory and even CO2 uptake in the dark by phototrophic micro-organisms has to be considered when assessing the impact of dry sediments on CO2 emissions from rivers.

Discharge and Water Quality of the River Moselle from 1990 to 2020 as Related to Climatic Changes and De-Industrialization

Reductions in industrial pollutant loads and the introduction and modernization of wastewater treatment facilities have improved the quality of inland waters in Europe and elsewhere, but climatic change, changes in runoff and the legacy of mine wastes may increase pressures on many aquatic environments. In the present study, data obtained by monitoring the French–German river are collated to visualize long-term trends in the pollution, river discharges and temperatures of Moselle waters. While air temperatures and accumulated heat sums in the catchment area showed an upward trend, precipitation and discharge levels as well as river temperatures were less affected by the ongoing climatic change. At the same time, the electric conductivity, i.e., the total suspended solids, did not show the anticipated reductions, while oxygen levels and pH values have showed upward trends since the 1990s. Despite the improvements in classical water quality parameters, the flooding of abandoned mines, increased water abstraction for cooling and agriculture and untreated old and emerging pollutants may aggravate environmental problems in the future. Climatic change will probably modify the runoff of pollutant loads by increasing the severity of flash floods and by concentrating water pollutants in drought spells.

Identification and trend analysis of organic cationic contaminants via non-target screening in suspended particulate matter of the German rivers Rhine and Saar

Non-target screening of suspended particulate matter (SPM), collected from the German rivers Rhine and Saar, was conducted with the goal of identifying organic, permanent cationic contaminants and of estimating their temporal trends over an extended period. Therefore, annual composite samples of SPM, provided by the German Environmental Specimen Bank, were extracted and analyzed with high resolution LC-QToF-MS/MS. To facilitate the identification of substances belonging to the class “permanent cations”, prioritization methods were applied utilizing the physicochemical properties of these compounds. These methods include both interactions of the analyte molecules with cation exchange resins and analyzing mass deviations when changing from non-deuterated to deuterated mobile phase solvents during LC-MS analysis. By applying both methods in a combined approach, 123 of the initially detected 2695 features were prioritized, corresponding to a 95% data reduction. This led to the identification of 22 permanent cationic species. The organic dyes Basic Yellow 28 and Fluorescent Brightener 363 as well as two quaternary ammonium compounds (QACs) were detected in environmental samples for the first time to best of or knowledge. The other compounds include additional QACs, as well as quaternary tri-phenylphosphonium compounds (QPC/TPP). In addition to identification, we determined temporal trends of all compounds over a period of 13 years and assessed their ecotoxicological relevance based on estimated concentrations. The two QACs oleyltrimethylammonium and eicosyltrimethylammonium show significant increasing trends in the Rhine SPM and maximum concentrations in the Saar SPM of about 900 and 1400 µg/kg, respectively. In the case of the dyes, constant trends have been observed at the end of the studied period, but also maximum concentrations of 400 µg/kg for Basic Yellow 28 in 2006 and 1000 µg/kg for Fluorescent Brightener 363 in 2015, potentially indicating a strong ecotoxicological risk.

Short-term effects of macrophyte removal on aquatic biodiversity in rivers and lakes

Mass development of macrophytes is an increasing problem in many aquatic systems worldwide. Dense mats of macrophytes can negatively affect activities like boating, fishing or hydropower production and one of the management measures often applied is mechanical removal. In this study, we analyzed the effect of mechanical macrophyte removal on phytoplankton, zooplankton, and macroinvertebrate (pelagic and benthic samples) assemblages. Our study covered five sites in four countries in Europe and Africa with highly variable characteristics. In all sites, dense mats of different macrophyte species (Juncus bulbosus in a river in Norway; a mix of native macrophytes in a German river, Elodea nuttallii in a lake in Germany, Ludwigia spp. In a French lake and Pontederia crassipes in a South African lake) are problematic and mechanical removal was applied. In every country, we repeated the same BACI (Before-After-Control-Impact) design, including “before”, “one week after”, and “six weeks after” sampling in a control and an impact section. Repeating the same experimental design at all sites allowed us to disentangle common effects across all sites from site-specific effects. For each taxonomic group, we analyzed three structural and three functional parameters, which we combined in a scoring system. Overall, the removal of macrophytes negatively affected biodiversity, in particular of zooplankton and macroinvertebrate assemblages. In contrast, plant removal had positive effects on the phytoplankton assemblages. Effects were more pronounced one week after removal than six weeks after. Consequently, we suggest a stronger consideration of the effect of plant removal on biodiversity to arrive at more sustainable management practices in the future.