Interpreting the fate of wastewater contaminants in streams is difficult because their inputs vary in time and several processes synchronously affect reactive transport. We present a method to disentangle the various influences by performing a conservative-tracer test while sampling a stream section at various locations for chemical analysis of micropollutants. By comparing the outflow concentrations of contaminants with the tracer signal convoluted by the inflow time series, we estimated reaction rate coefficients and calculated the contaminant removal along a river section. The method was tested at River Steinlach, Germany, where 38 contaminants were monitored. Comparing day-time and night-time experiments allowed distinguishing photo-dependent degradation from other elimination processes. While photo-dependent degradation showed to be highly efficient for the removal of metroprolol, bisoprolol, and venlafaxine, its impact on contaminant removal was on a similar scale to the photo-independent processes when averaged over 24 h. For a selection of compounds analyzed in the present study, bio- and photodegradation were higher than in previous field studies. In the Steinlach study, we observed extraordinarily effective removal processes that may be due to the higher proportion of treated wastewater, temperature, DOC and nitrate concentrations, but also a higher surface to volume ratio from low flow conditions that favorizes photodegradation through the shallow water column and a larger transient storage than observed in comparable studies.

Increasing numbers of organic micropollutants are emitted into rivers via municipal wastewaters. Due to their persistence many pollutants pass wastewater treatment plants without substantial removal. Transport and fate of pollutants in receiving waters and export to downstream ecosystems is not well understood. In particular, a better knowledge of processes governing their environmental behavior is needed. Although a lot of data are available concerning the ubiquitous presence of micropollutants in rivers, accurate data on transport and removal rates are lacking. In this paper, a mass balance approach is presented, which is based on the Lagrangian sampling scheme, but extended to account for precise transport velocities and mixing along river stretches. The calculated mass balances allow accurate quantification of pollutants' reactivity along river segments. This is demonstrated for representative members of important groups of micropollutants, e.g. pharmaceuticals, musk fragrances, flame retardants, and pesticides. A model-aided analysis of the measured data series gives insight into the temporal dynamics of removal processes. The occurrence of different removal mechanisms such as photooxidation, microbial degradation, and volatilization is discussed. The results demonstrate, that removal processes are highly variable in time and space and this has to be considered for future studies. The high precision sampling scheme presented could be a powerful tool for quantifying removal processes under different boundary conditions and in river segments with contrasting properties.

Rivers 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. Both 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. This study showed that the indicator chemical/indicator bioassay approach is suitable for identifying input sources of a mixture of organic micropollutants and to trace changes in the water quality along small rivers. This method forms the necessary basis for evaluating the natural attenuation processes of organic micropollutants on a catchment scale, especially when combined with enhanced sampling strategies in future studies.

Urban areas are a leading source of polycyclic aromatic hydrocarbons (PAHs) that result from combustion processes and are emitted into rivers, especially during rain events and with particle wash-off from urban surfaces. In-stream transport of suspended particles and attached PAHs is linked strongly to sediment turnover processes. This study aimed to identify particle exchange processes that contribute to the transport of suspended particles during flood events. An urban high-flow signal was tracked in high temporal resolution at two sampling sites in the Ammer River (South-western Germany). Samples were analyzed for turbidity, total suspended solids concentrations (TSS), particle-size distribution, organic carbon, and PAH. Maximum discharge and the highest TSS occurred nearly simultaneously at the upstream sampling site, whereas a temporally shifted course was observed for downstream. The total load of particles was similar, yet a decrease of PAH mass (~28%) and an increase of the particulate organic carbon (POC) content (~3.5%-points) occurred. Coarser particles (≥26 µm) dominated at the beginning of the event at both sampling sites. The signal of remobilized riverbed sediment increases downstream and leads to well-established, robust linear correlations between TSS and PAHs. This study highlights that riverbed sediment acts as intermediate storage for contaminated particles from upstream sources that shape, together with the fresh urban input, the “particle signature” of suspensions moving through catchments during high discharge conditions.