Benzotriazole UV stabilizers (BUVSs) are widely applied in plastics to prevent discoloration and to enhance product stability. This study describes for the first time the occurrence of nine different lipophilic BUVSs (UV-326, UV-320, UV-329, UV-350, UV-328, UV-327, UV-928, UV-234 and UV-360) in sediment, suspended particulate matter (SPM) and bream liver samples of German rivers. All investigated BUVSs were detected in sediments and SPM at concentrations in the low ng/g dry weight (dw) range. The so far rarely analyzed compound UV-360 as well as UV-326 were the predominant BUVSs in sediments and SPM from the river Rhine reaching maximum concentrations of 62 and 44 ng/g dw, respectively. Five BUVSs were also confirmed to bioaccumulate in bream liver, but neither UV-360 nor UV-326 was detected above the limit of quantification (LOQ). In contrast, highest concentrations in bream liver were determined for UV-327 (65 ng/g dw) and UV-328 (40 ng/g dw).A retrospective time trend analysis of BUVSs in SPM from two sites (river Rhine, 2005 to 2013; river Saar, 2006 to 2013) revealed increasing contamination levels of UV-329 and decreasing levels of UV-320 and UV-350. At one site (river Rhine) time trends of BUVS concentrations were also investigated in bream liver (1995–2013) and supported a considerably reduced exposure to UV-350.A first assessment of the environmental fate of BUVSs by sediment-water batch systems revealed a rapid partitioning into the sediment and no considerable degradation within 100 d.

Rivers play a crucial role in collecting and transporting microplastics. Nonetheless, the degree to which microplastic pollution of freshwaters affects its biota remains understudied. Sampling of wild fishes has so far demonstrated that microplastic ingestion occurs commonly across species with alternate feeding modes, as well as in different environmental compartments. Due to the exploratory nature of many preceding studies, drawing insight about factors driving microplastic ingestion has remained difficult. It continues unknown for instance, what the importance of varying environmental microplastic concentrations is to predict ingestion rates in fish from those areas. Here we show that ingestion rates of microplastic particles (>300 μm) in the benthic round goby from the Rhine river were negligible (1 particle in 417 fish). Among the 535 visually selected putative microplastic fragments, stringent data processing steps to reduce the number of false positives during reference library searches, revealed the importance of taking such steps into account in comparison with other data processing routines. Our observations remained consistent, despite having collected fish from a strongly polluted site of the lower Rhine, which served as contrast to a significantly cleaner site upstream. These results demonstrate that higher environmental microplastic concentrations are not necessarily mirrored by higher ingestion rates in a given fish species.

Microplastics are emerging pollutants in water bodies worldwide. The environmental entry areas must be studied to localise their sources and develop preventative and remedial solutions. Rivers are major contributors to the marine microplastics load. Here, we focus on a specific type of plastic microbead (diameter 286–954 μm, predominantly opaque, white–beige) that was repeatedly identified in substantial numbers between kilometres 677 and 944 of the Rhine River, one of Europe's main waterways. Specifically, we aimed (i) to confirm the reported abrupt increase in microbead concentrations between the cities of Leverkusen and Duisburg and (ii) to assess the concentration gradient of these particles along this stretch at higher resolution. Furthermore, we set out (iii) to narrow down the putative entry stretch from 81.3 km, as reported in an earlier study, to less than 20 km according to our research design, and (iv) to identify the chemical composition of the particles and possibly reveal their original purpose. Surface water filtration (mesh: 300 μm, n = 9) at regular intervals along the focal river stretch indicated the concentration of these spherules increased from 0.05 to 8.3 particles m−3 over 20 km. This spot sampling approach was supported by nine suspended solid samples taken between 2014 and 2017, encompassing the river stretch between Leverkusen and Duisburg. Ninety-five percent of microbeads analysed (202/212) were chemically identified as crosslinked polystyrene-divinylbenzene (PS-DVB, 146/212) or polystyrene (PS, 56/212) via Raman or Fourier-transform infrared spectroscopy. Based on interpretation of polymer composition, surface structure, shape, size and colour, the PS(-DVB) microbeads are likely to be used ion-exchange resins, which are commonly applied in water softening and various industrial purification processes. The reported beads contribute considerably to the surface microplastic load of the Rhine River and their potential riverine entry area was geographically narrowed down.

Numerous studies on microplastics (MPs; Ø < 5 mm) in the aquatic environment have been published, but knowledge about the occurrence and ecological risks of MPs is limited. This is in part because current data on the distribution of MPs are comparable only to a limited extent, due to the many different methods of investigation. In addition, sample preparation is often difficult such that standard procedures are lacking. The aim of this work was to simplify the preparation of different kinds of MP samples. Our method makes use of the electrostatic behavior of plastic particles to facilitate their separation from sample matter, with up to 99% of the original sample mass removed without any loss of MPs. To determine the efficacy of this approach, four different materials (quartz sand, freshwater suspended particulate matter, freshwater sediment, and beach sand) were spiked with MPs (size: 0.063–5 mm from the seven most common types of plastics, one bioplastic type, polyethylene fibers, and tire wear. A modified electrostatic metal/plastic separator was used to reduce the sample mass and concentrate the plastics based on their physical separation. The recovery achieved with this method was as high as nearly 100% for each type of material. The method was then tested on plastic particles of different shapes and types isolated from the Rhine River. These were successfully electroseparated from the four materials, which demonstrated the utility of this method. Its advantages include the simplified handling and preparation of different field samples as well as a much shorter processing time, because after the last separation step there is hardly any biological material remaining in the sample fraction.

Fate and occurrence of 4 selective serotonin reuptake inhibitors, one serotonin-noradrenergic reuptake inhibitor and one noradrenergic-dopamineric reuptake inhibitor and their human metabolites were determined in a German municipal wastewater treatment plant as well as in the Rhine River and selected tributaries. The enantiomeric fractions of venlafaxine and its metabolites were not altered during wastewater treatment and were similar in all river samples underlining that no appreciable biodegradation occurs. In the Rhine catchment area highest concentrations were detected for venlafaxine, citalopram and their human metabolites. Projected future climate change would lead to an increased portion of treated wastewater in rivers due to reduced discharges during low flow situations by the end of the 21st century. However, the effect of climate change on the pattern and concentrations of antidepressants is predicted to be of minor importance in comparison to altered consumption quantities caused by demographic developments and changes in life styles.

Using canonical correspondence analysis (CCA), relationships were investigated between plant species composition and flooding characteristics, heavy metal contamination and soil properties in a lowland floodplain of the Rhine River. Floodplain elevation and yearly average flooding duration turned out to be more important for explaining variation in plant species composition than soil heavy metal contamination. Nevertheless, plant species richness and diversity showed a significant decrease with the level of contamination. As single heavy metal concentrations seemed mostly too low for causing phytotoxic effects in plants, this trend is possibly explained by additive effects of multiple contaminants or by the concomitant influences of contamination and non-chemical stressors like flooding. These results suggest that impacts of soil contamination on plants in floodplains could be larger than expected from mere soil concentrations. In general, these findings emphasize the relevance of analyzing effects of toxic substances in concert with the effects of other relevant stressors.

We assessed dietary exposure of the little owl Athene noctua to trace metal contamination in a Dutch Rhine River floodplain area. Diet composition was calculated per month for three habitat types, based on the population densities of six prey types (earthworms, ground beetles and four small mammal species) combined with the little owl’s functional response to these prey types. Exposure levels showed a strong positive relationship with the dietary fraction of earthworms, but also depended on the dietary fraction of common voles, with higher common vole fractions resulting in decreasing exposure levels. Spatio-temporal changes in the availability of earthworms and common voles in particular resulted in considerable variation in exposure, with peaks in exposure exceeding a tentative toxicity threshold. These findings imply that wildlife exposure assessments based on a predefined, average diet composition may considerably underestimate local or intermittent peaks in exposure.

Surface water of rivers like the Rhine is a highly relevant environmental and an important source of the Dutch drinking water. To improve protection of the environment and drinking water supply, it is important to have a continuous overview of the chemical composition of the river. Such an overview may be obtained with contemporary, untargeted analytical platforms like gas chromatography-mass spectrometry. Interpretation of such untargeted data is however challenged by the presence of many chemicals of natural origin. We developed a novel approach to screen for anthropogenic chemicals using non-parametric tests on the time trends of yet unidentified chemicals. The approach uses PARAFAC2 to extract unknown components present in GC–MS data and provides an assessment of whether such components may be anthropogenic. This significantly reduces screening efforts required by human laboratory staff. In total, out of twelve suspect unknown components, eleven were classified as anthropogenic, providing compelling evidence that studying unknown components can be highly valuable for regulatory bodies. This approach filters out many naturally occurring compounds, leaving more resources available for wet-lab identification of suspected anthropogenic chemicals.

Rivers play an irreplaceable role in nature and human society but are the most vulnerable ecosystem in the world to multiple environmental stressors. However, the global-scale research status and the distribution patterns of major stressors in large rivers remain unclear. This study analysed research publications (12,807 documents from 1900 to 2019) related to six large rivers with continental representativeness to tackle these knowledge gaps. The results showed that the total outputs have grown rapidly over the study period, particularly since the 1990s. Consistent with the varied environmental characteristics and problems among the rivers, the research outputs and focuses demonstrated clear differences, which could further be attributed to geographical location, journal preferences and the economic strength of the country in which the river is located. Overall, climate change was the most frequently and widely considered environmental stressor in large rivers. Regardless of climate change, species diversity and hydropower development were widely addressed in the Amazon, Congo and Mekong river basins. Water pollution was the main stressor studied in the Rhine River and Mississippi River, while agricultural irrigation and drought were the most frequently addressed research subjects in the Murray-Darling River. This study provides a comprehensive understanding of the research status and stressor distribution in large global rivers, highlighting the relationship between river research and geographical regions, pointing out future research directions and providing management guidance for large rivers.