Geo-referenced simulations of E. coli in a sub-catchment of the Vecht River using a probabilistic approach.

The proportion of wild swimmers at non-official bathing sites has increased during the Covid-19 pandemic. Bathing water quality at designated sites is monitored through analysis of the concentration of fecal indicator bacteria such as E. coli. However, non-official sites are generally not monitored. In a previous work, steady state modelling of E. coli was achieved at catchment scale, enabling a comparison of expected concentrations along an entire catchment for longtime average. However, E. coli concentrations can vary over several orders of magnitude at the same monitoring site throughout the year. To capture the temporal variability of E. coli concentrations on the catchment scale, we extended the existing deterministic E. coli sub-module of the GREAT-ER (Geo-referenced Exposure Assessment tool for European Rivers) model for probabilistic Monte-Carlo simulations. Here, selected model parameters are represented by probability distributions instead of fixed values. Wastewater treatment plant (WWTP) emissions and diffuse emissions were parameterized using selected data from a previous monitoring campaign (calibration data set) and in-stream processes were modeled using literature data. Comparison of simulation results with monitoring data (evaluation data set) indicates that predicted E. coli concentrations well-represent median measured concentrations, although the range of predicted concentrations is slightly larger than the observed concentration variability. The parameters with the largest influence on the range of predicted concentrations are flow rate and E. coli removal efficiency in WWTPs. A comparison of predicted 90th percentiles with the threshold for sufficient bathing water quality (according to the EU Bathing Water Directive) indicates that year-round swimming at sites influenced by WWTP effluents is advisable almost nowhere in the study area. A refinement of the model can be achieved if quantitative relationships between the WWTP removal efficiency and both, the treatment technologies as well as the operating parameters are further established.

(Antibiotic-Resistant) E. coli in the Dutch-German Vecht Catchment─Monitoring and Modeling.

Fecally contaminated waters can be a source for human infections. We investigated the occurrence of fecal indicator bacteria (E. coli) and antibiotic-resistant E. coli, namely, extended spectrum beta-lactamase (ESBL)-producing E. coli (ESBL-EC) and carbapenemase-producing E. coli (CP-EC) in the Dutch-German transboundary catchment of the Vecht River. Over the course of one year, bacterial concentrations were monitored in wastewater treatment plant (WWTP) influents and effluents and in surface waters with and without WWTP influence. Subsequently, the GREAT-ER model was adopted for the prediction of (antibiotic-resistant) E. coli concentrations. The model was parametrized and evaluated for two distinct scenarios (average flow scenario, dry summer scenario). Statistical analysis of WWTP monitoring data revealed a significantly higher (factor 2) proportion of ESBL-EC among E. coli in German compared to Dutch WWTPs. CP-EC were present in 43% of influent samples. The modeling approach yielded spatially accurate descriptions of microbial concentrations for the average flow scenario. Predicted E. coli concentrations exceed the threshold value of the Bathing Water Directive for a good bathing water quality at less than 10% of potential swimming sites in both scenarios. During a single swimming event up to 61 CFU of ESBL-EC and less than 1 CFU of CP-EC could be taken up by ingestion.

Ecological Risk Assessment of Pharmaceuticals in the Transboundary Vecht River (Germany and The Netherlands).

Millions of people rely on active pharmaceutical ingredients (APIs) to prevent and cure a wide variety of illnesses in humans and animals, which has led to a steadily increasing consumption of APIs across the globe and concurrent releases of APIs into the environment. In the environment, APIs can have a detrimental impact on wildlife, particularly aquatic wildlife. Therefore, it is essential to assess their potential adverse effects to aquatic ecosystems. The European Water Framework Directive sets out that risk assessment should be performed at the catchment level, crossing borders where needed. The present study defines ecological risk profiles for surface water concentrations of 8 APIs (carbamazepine, ciprofloxacin, cyclophosphamide, diclofenac, erythromycin, 17α-ethinylestradiol, metformin, and metoprolol) in the Vecht River, a transboundary river that crosses several German and Dutch regions. Ultimately, 3 main goals were achieved: 1) the geo-referenced estimation of API concentrations in surface water using the geography-referenced regional exposure assessment tool for European rivers; 2) the derivation of new predicted-no-effect concentrations for 7 of the studied APIs, of which 3 were lower than previously derived values; and 3) the creation of detailed spatially explicit ecological risk profiles of APIs under 2 distinct water flow scenarios. Under average flow conditions, carbamazepine, diclofenac, and 17α-ethinylestradiol were systematically estimated to surpass safe ecological concentration thresholds in at least 68% of the catchment's water volume. This increases to 98% under dry summer conditions. Environ Toxicol Chem 2022;41:648-662. © 2021 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Geo-referenced simulation of pharmaceuticals in whole watersheds: application of GREAT-ER 4.1 in Germany.

The geo-referenced regional exposure assessment tool for European rivers (GREAT-ER) is designed to support river basin management or the implementation process within the EU Water Framework Directive by predicting spatially resolved exposure concentrations in whole watersheds. The usefulness of the complimentary application of targeted monitoring and GREAT-ER simulations is demonstrated with case studies for three pharmaceuticals in selected German watersheds. Comparison with monitoring data corroborates the capability of the probabilistic model approach to predict the expected range of spatial surface water concentrations. Explicit consideration of local pharmaceutical emissions from hospitals or private doctor's offices (e.g., for X-ray contrast agents) can improve predictions on the local scale without compromising regional exposure assessment. Pharmaceuticals exhibiting low concentrations hardly detectable with established analytical methods (e.g., EE2) can be evaluated with model simulations. Management scenarios allow for a priori assessment of risk reduction measures. In combination with targeted monitoring approaches, the GREAT-ER model can serve as valuable support tool for exposure and risk assessment of pharmaceuticals in whole watersheds.

Occurrence and spatial distribution of microplastics in sediments from Norderney.

The spatial distribution of small potential microplastics (SPM) (<1 mm) in beach sediments was studied on a 500 m stretch of the North Sea island of Norderney. Their correlation with visible plastic debris (VPD) (>1 mm) was also examined. Small microparticles were extracted from 36 one kg sediment samples and analysed by visual microscopic inspection and partly by thermal desorption pyrolysis gas chromatography/mass spectrometry. The smallest particle size that could be analysed with this method was estimated to be 100 µm. The mean number of SPM at the three sampling sites (n = 12) was 1.7, 1.3 and 2.3 particles per kg dry sediment, respectively. SPM were identified as polypropylene, polyethylene, polyethylene terephthalate, polyvinylchloride, polystyrene and polyamide. The organic plastic additives found were benzophenone, 1,2-benzenedicarboxylic acid, dimethyl phthalate, diethylhexyl phthalate, dibutyl phthalate, diethyl phthalate, phenol and 2,4-di-tert-butylphenol. Particles were distributed rather homogenously and the occurrence of SPM did not correlate with that of VPD.

Microplastics in freshwater ecosystems: what we know and what we need to know.

BACKGROUND: While the use of plastic materials has generated huge societal benefits, the 'plastic age' comes with downsides: One issue of emerging concern is the accumulation of plastics in the aquatic environment. Here, so-called microplastics (MP), fragments smaller than 5 mm, are of special concern because they can be ingested throughout the food web more readily than larger particles. Focusing on freshwater MP, we briefly review the state of the science to identify gaps of knowledge and deduce research needs. STATE OF THE SCIENCE: Environmental scientists started investigating marine (micro)plastics in the early 2000s. Today, a wealth of studies demonstrates that MP have ubiquitously permeated the marine ecosystem, including the polar regions and the deep sea. MP ingestion has been documented for an increasing number of marine species. However, to date, only few studies investigate their biological effects. The majority of marine plastics are considered to originate from land-based sources, including surface waters. Although they may be important transport pathways of MP, data from freshwater ecosystems is scarce. So far, only few studies provide evidence for the presence of MP in rivers and lakes. Data on MP uptake by freshwater invertebrates and fish is very limited. KNOWLEDGE GAPS: While the research on marine MP is more advanced, there are immense gaps of knowledge regarding freshwater MP. Data on their abundance is fragmentary for large and absent for small surface waters. Likewise, relevant sources and the environmental fate remain to be investigated. Data on the biological effects of MP in freshwater species is completely lacking. The accumulation of other freshwater contaminants on MP is of special interest because ingestion might increase the chemical exposure. Again, data is unavailable on this important issue. CONCLUSIONS: MP represent freshwater contaminants of emerging concern. However, to assess the environmental risk associated with MP, comprehensive data on their abundance, fate, sources, and biological effects in freshwater ecosystems are needed. Establishing such data critically depends on a collaborative effort by environmental scientists from diverse disciplines (chemistry, hydrology, ecotoxicology, etc.) and, unsurprisingly, on the allocation of sufficient public funding.

Short-term extractability of sulfadiazine after application to soils.

The long-term environmental fate of the veterinary antibiotic sulfadiazine (SDZ) in soils is determined by a reversible sequestration into a residual fraction and an irreversible formation of non-extractable residues (NER), which can be described as first-order rate processes. However, the concentration dynamics of the resulting fractions of SDZ in soil show an unexplained rapid reduction of extractability during the first 24 h. We therefore investigated the short-term extractability of SDZ in two different soils under different SDZ application procedures over 24 h: with and without manure, for air-dried and for moist soils. In all batches, we observed an instantaneous loss of extractability on a time scale of minutes as well as kinetically determined sequestration and NER formation over 24 h. Data evaluation with a simple kinetic model led to the conclusion that application with manure accelerated the short-term formation of NER, whereas sequestration was very similar for all batches.

Occurrence and distribution of benzothiazole in the Schwarzbach watershed (Germany).

This study quantifies the regional distribution of the micropollutant benzothiazole (BT) in river water by sampling 15 river sites in the Schwarzbach watershed (about 400 km(2)) from November 2008 to February 2010. Additionally, wastewater samples from three municipal wastewater treatment plants (WWTPs) in Germany were analyzed. BT was detected in all wastewater influent and effluent samples as well as in all river water samples collected downstream of wastewater discharge. This corroborates the ubiquitous occurrence of BT in the aqueous environment. Concentrations were between 58 and 856 ng L(-1) in the river water. The observed mean concentration at the outlet of the investigated catchment was 109 ng L(-1). With only a few exceptions, temporal and spatial variations of BT concentrations in river water were low. Rather similar BT concentrations over a wide range of river discharge indicate that dilution along the mainstream is negligible and, thus, supports the hypothesis that paved surface runoff during rain events is an important BT source not only for wastewater influent but also for river water. This was supported by detecting the highest BT concentrations at sampling locations close to the dense highway network around the city of Frankfurt. Since BT was also detected in river water collected from locations that were clearly unaffected by wastewater effluent discharge, surface runoff must be considered as a diffuse source of BT in river water.

Mechanistic link between uptake of sulfonamides and bacteriostatic effect: model development and application to experimental data from two soil microorganisms.

Sulfonamides (SA) are antibiotic compounds that are widely used as human and veterinary pharmaceuticals. They are not rapidly biodegradable and have been detected in various environmental compartments. Effects of sulfonamides on microbial endpoints in soil have been reported from laboratory incubation studies. Sulfonamides inhibit the growth of sensitive microorganisms by competitive binding to the dihydropteroate-synthase (DHPS) enzyme of folic acid production. A mathematical model was developed that relates the extracellular SA concentration to the inhibition of the relative bacterial growth rate. Two factors--the anionic accumulation factor (AAF) and the cellular affinity factor (CAF)--determine the effective concentration of an SA. The AAF describes the SA uptake into bacterial cells and varies with both the extra- and intracellular pH values and with the acidic pKa value of an SA. The CAF subsumes relevant cellular and enzyme properties, and is directly proportional to the DHPS affinity constant for an SA. Based on the model, a mechanistic dose-response relationship is developed and evaluated against previously published data, where differences in the responses of Pseudomonas aeruginosa and Panthoea agglomerans toward changing medium pH values were found, most likely as a result of their diverse pH regulation. The derived dose-response relationship explains the pH and pKa dependency of mean effective concentration values (EC50) of eight SA and two soil bacteria based on AAF and CAF values. The mathematical model can be used to extrapolate sulfonamide effects to other pH values and to calculate the CAF as a pH-independent measure for the SA effects on microbial growth.

Fate of beta-blocker human pharmaceuticals in surface water: comparison of measured and simulated concentrations in the Glatt Valley Watershed, Switzerland.

This study focused on the occurrence and fate of four beta-blockers (atenolol, sotalol, metoprolol, propranolol) in wastewater and surface water. Measured concentrations were compared with predicted concentrations using an implementation of the geo-referenced model GREAT-ER for the Glatt Valley Watershed (Switzerland). Particularly, the question was addressed how measured and simulated data could complement each other for the exposure assessment of human pharmaceuticals and other micropollutants entering surface water through wastewater treatment plants (WWTP). Concentrations in the Glatt River ranged from

Assessing persistence and long-range transport potential of current-use pesticides.

Despite the fact that current-use pesticides (CUP) have different chemical properties to first-generation organochlorine products, the long-term and long-range environmental behavior of these chemicals is still unclear. Data for 45 active ingredients of CUPs were collected, most of which originate from the results of simulation tests submitted for authorization. According to the Stockholm Convention on persistent organic pollutants (POPs), two of the 45 CUPs exceed both screening level criteria for persistence and long-range transport potential (LRTP). Thirteen CUPs meet the persistence criterion and just one for LRTP. This classification is compared to the reference chemicals approach using overall persistence (P(ov)) and characteristic travel distance (CTD) calculated with a multimedia model. Although none of the 45 CUP have a CTD above the LRTP boundary line, three of them exceed the overall persistence criterion derived from legacy POPs for classification. Nineteen CUPs are transported over longer distances in water than in air. For such polar substances a LRTP boundary has yet to be defined. We recommend the multimedia model modeling approach to calculate P(ov) and LRTP as a second tier in persistence and LRTP assessment.

A conceptual model describing the fate of sulfadiazine and its metabolites observed in manure-amended soils.

Sulfadiazine (SDZ) belongs to the chemical class of sulfonamides, one of the most important groups of antibiotics applied in animal husbandry in Europe. These antibiotics end up in the soil after manure from treated animals is applied as fertilizer. They can inhibit soil microbial functions and enhance the spread of resistance genes among soil microorganisms. In order to assess the exposure of soil microorganisms to SDZ, a conceptual kinetic model for the prediction of temporally resolved antibiotic concentrations in soil was developed. The model includes transformation reactions, reversible sequestration and the formation of non-extractable residues (NER) from SDZ and its main metabolites N(4)-acetyl-sulfadiazine (N-ac-SDZ) and 4-hydroxy-sulfadiazine (OH-SDZ). The optimum model structure and rate constants of SDZ kinetics and its metabolites were determined by fitting different model alternatives to sequential extraction data of a manure-amended Cambisol soil. N-ac-SDZ is degraded to SDZ with a half-life of 4d, whereas OH-SDZ is not. Though, based on the available data, the hydroxylation of SDZ seems to be negligible, it is still included in the model structure since this process has been observed in recent studies. Sequestration into a residual fraction has similar kinetics for SDZ, N-ac-SDZ and OH-SDZ and is one order of magnitude faster than the reverse translocation. The irreversible formation of NER is restricted to SDZ and OH-SDZ. The model shows good agreement when applied to extraction data measured independently for a Luvisol soil. The combination of sequential extraction data and the conceptual kinetic model enables us to gain further insight into the long-term fate and exposure of sulfonamides in soil.

Geo-referenced modeling of zinc concentrations in the Ruhr river basin (Germany) using the model GREAT-ER.

Zinc enters surface waters from a variety of different emission sources. The geo-referenced model GREAT-ER (Geo-referenced Regional Exposure Assessment Tool for European Rivers) was applied to simulate spatially resolved zinc concentrations in the Ruhr river basin. The model links geo-referenced emissions (loads) to concentrations at local and regional scales and allows for evaluating the relative importance of emission sources. For each emission from point sources (household, industry, urban runoff) and non-point sources (agriculture, natural background), zinc loads were independently estimated using appropriate reference parameters (number of inhabitants, surface area drained, agricultural area, zinc ore regions). For point emissions from industry and mine drainage loads were taken directly from available data compilations. Simulated total zinc concentrations agree well with monitoring data. The strength of the modeling tool became evident from the unequivocal link that could be established between observed surface water concentrations and the large zinc input from geogenic sources and abandoned mines. These emission sources are regional characteristics of the Ruhr river basin and due to the fact that some regions are relatively rich in zinc ore, which was extracted over a long period of time. Although most of these emissions occur in the upper part of the catchment, they contribute to approximately one-third to the zinc load at the confluence with the Rhine River. Urban emissions from household, traffic (road) and buildings (roof) were shown to be responsible for approximately half of the concentration in the Ruhr at the confluence with the Rhine River.

Analysis of potassium formate in airport storm water runoff by headspace solid-phase microextraction and gas chromatography-mass spectrometry.

Potassium formate was extracted from airport storm water runoff by headspace solid-phase microextraction (HS-SPME) and analyzed by GC-MS. Formate was transformed to formic acid by adding phosphoric acid. Subsequently, formic acid was derivatized to methyl formate by adding methanol. Using sodium [(2)H]formate (formate-d) as an internal standard, the relative standard deviation of the peak area ratio of formate (m/z 60) and formate-d (m/z 61) was 0.6% at a concentration of 208.5 mg L(-1). Calibration was linear in the range of 0.5-208.5 mg L(-1). The detection limit calculated considering the blank value was 0.176 mg L(-1). The mean concentration of potassium formate in airport storm water runoff collected after surface de-icing operations was 86.9 mg L(-1) (n=11) with concentrations ranging from 15.1 mg L(-1) to 228.6 mg L(-1).

Emissions of OTNE (Iso-E-super) - mass flows in sewage treatment plants.

The fate and mass flows of OTNE ([1,2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethylnaphthalen-2yl]ethan-1-one) which is commercialized as Iso-E-Super were studied in three large scale sewage treatment plants (STPs) in detail. The results are compared to 14 smaller ones located in Germany and Switzerland. OTNE inflow concentrations ranged from 4000 to 13,000 ngl(-1) while the effluent concentrations ranged from 500 to 6,900 ngl(-1). It is eliminated from the waste water with 56-64% during waste water treatment. High OTNE concentrations in sewage sludge showed that the elimination was mainly driven by sorption to sludge. This complies with major elimination in the first settling basins (primary settling tanks) while it was removed to a lesser extent in the aeration basin of the activated sludge treatment or in successive biofilters. The mass flows of OTNE in the influent of the German STPs were between 0.9 and 1.9 g per inhabitant and year. In the annual effluents mass flows of OTNE ranged between 0.2 and 0.8 g per inhabitant which complies with data measured in 13 smaller STPs from Switzerland. The similarity of data suggests that the observed mass flow data might be extrapolated to other European regions.

Determination of soil biodegradation half-lives from simulation testing under aerobic laboratory conditions: a kinetic model approach.

A kinetic model approach for determination of biodegradation half-lives from soil simulation testing is presented. The model describes transformation of the parent compound to metabolites and formation of bound (non-extractable) residues as well as mineralization in soil under aerobic laboratory conditions. Experimental data for several pesticide compounds from various soil simulation tests are used for fitting kinetic rate constants. Formation of bound residues, either from parent or metabolites or from both, can be described by first-order kinetics for all examined compounds. Correlation of kinetic rate constants of primary degradation and formation of bound residues from parent compound suggests a common mechanism, presumably co-metabolic microbial activity, for both processes. Inverse modelling allows for estimation of primary degradation half-life DegT50 instead of disappearance time DT50. Application of the DegT50 approach in PBT assessment might result in a different persistent classification for which the developed model delivers an appropriate evaluation tool.

A mechanistical model for the uptake of sulfonamides by bacteria.

The uptake of sulfonamides into bacterial cells was simulated by a dynamic model to estimate bioavailability and steady-state accumulation of sulfonamides in the cells. Uptake of sulfonamides is modeled as diffusion-like transport of the neutral molecule and the ionic species. Speciation outside and inside the cell depends on the extra- and intracellular pH and the pK(a)-value of the antibiotic active SO(2)NH moiety. The ratio between intra- and extracellular sulfonamide concentration is used as a measure for potential sulfonamide accumulation in bacterial cells. Simulated ratios are in good agreement with experimental data for various sulfonamides with pK(a2) values ranging from 5.0 up to 11.8. Sensitivity analyses indicate that intracellular sulfonamide concentration depend significantly on the degree of ionization in the cytoplasm and the surrounding medium. No accumulation in the cell occurs, if the external pH exceeds the intracellular pH. For sulfonamides with large pK(a)-values the internal activity equals the activity in the extracellular solution. Highest accumulation is reached if the pH gradient from inside to outside the cell is large, which depends on the bacterial pH-regulation mechanisms. The pH-dependent intracellular accumulation of various sulfonamides correlates well with their observed antibiotic effect on selected bacteria.

Application of multimedia models for screening assessment of long-range transport potential and overall persistence.

We propose a multimedia model-based methodology to evaluate whether a chemical substance qualifies as POP-like based on overall persistence (Pov) and potential for long-range transport (LRTP). It relies upon screening chemicals against the Pov and LRTP characteristics of selected reference chemicals with well-established environmental fates. Results indicate that chemicals of high and low concern in terms of persistence and long-range transport can be consistently identified by eight contemporary multimedia models using the proposed methodology. Model results for three hypothetical chemicals illustrate that the model-based classification of chemicals according to Pov and LRTP is not always consistent with the single-media half-life approach proposed by the UNEP Stockholm Convention and thatthe models provide additional insight into the likely long-term hazards associated with chemicals in the environment. We suggest this model-based classification method be adopted as a complement to screening against defined half-life criteria at the initial stages of tiered assessments designed to identify POP-like chemicals and to prioritize further environmental fate studies for new and existing chemicals.

Influence of distributional shape of substance parameters on exposure model output.

Uncertainty of environmental concentrations is calculated with the regional multimedia exposure model of EUSES 1.0 by considering probability input distributions for aqueous solubility, vapor pressure, and octanol-water partition coefficient, K(ow). Only reliable experimentally determined data are selected from available literature for eight reference chemicals representing a wide substance property spectrum. Monte Carlo simulations are performed with uniform, triangular, and log-normal input distributions to assess the influence of the choice of input distribution type on the predicted concentration distributions. The impact of input distribution shapes on output variance exceeds the effect on the output mean by one order of magnitude. Both are affected by influence and uncertainty (i.e., variance) of the input variable as well. Distributional shape has no influence when the sensitivity function of the respective parameter is perfectly linear. For nonlinear relationships, overlap of probability mass of input distribution with influential ranges of the parameter space is important. Differences in computed output distribution are greatest when input distributions differ in the most influential parameter range.

Comparing estimates of persistence and long-range transport potential among multimedia models.

Overall persistence (Pov) and long-range transport potential (LRTP) of organic chemicals are environmental hazard metrics calculated with multimedia fate and transport models. Since there are several models of this type, it is important to know whether and how different model designs (model geometry, selection of compartments and processes, process descriptions) affect the results for Pov and LRTP. Using a set of 3175 hypothetical chemicals covering a broad range of partition coefficients and degradation half-lives, we systematically analyze the Pov and LRTP results obtained with nine multimedia models. We have developed several methods that make it possible to visualize the model results efficiently and to relate differences in model results to mechanistic differences between models. Rankings of the hypothetical chemicals according to Pov and LRTP are highly correlated among models and are largely determined by the chemical properties. Domains of chemical properties in which model differences lead to different results are identified, and guidance on model selection is provided for model users.