Impact of reduced sampling frequency of illicit drug wastewater monitoring in the Netherlands.

Drug consumption estimates are traditionally based on surveys or information from police seizures. Alternatively, residues of illicit drugs in untreated wastewater (influent) can be used to calculate mass loads and subsequently estimate drug consumption in the community throughout the week. For this purpose, wastewater is commonly sampled for seven consecutive days within the Sewage analysis CORe group Europe (SCORE), while other sampling schemes may be implemented in long-term studies outside this consortium. The current study demonstrates how sampling frequency of illicit drug residues in the influent of wastewater treatment plants (WWTPs) affects the derived weekly average. Thirty WWTPs were sampled over the course of 12 years and influents were analyzed for five drugs (metabolites): 3,4-methylenedioxymethamphetamine (MDMA), methamphetamine, amphetamine, benzoylecgonine (a metabolite of cocaine), and 11-nor-9-Carboxy tetrahydrocannabinol (THC-COOH). Subsequently, small and large WWTPs were grouped with a threshold of 100,000 inhabitants. After data curation, standardized loads were calculated (mg/d per 1000 inhabitants). Weekly averages of loads of the drug residues were calculated based on six scenarios (sampling one to six weekdays) and compared to the weekly average in the control situation (sampling seven weekdays) in a Monte Carlo simulation. Results indicate that drug residues with more dynamic loads over a week require more frequent sampling. The analysis illustrates that a decreased sampling frequency (4 or 5 days per week) still leads to a representative weekly average for all drugs tested when a deviation up to a factor of 1.25 is deemed acceptable. However, knowledge on typical levels is necessary to define outliers. We therefore recommend to study dynamics in drug residue loads for WWTPs before reducing sampling frequency in long term monitoring programs.

Surface water monitoring of chemicals associated with animal husbandry in an agricultural region in the Netherlands using passive sampling.

Compounds originating from animal husbandry can pollute surface water through the application of manure to soil. Typically, grab sampling is employed to detect these residues, which only provides information on the concentration at the time of sampling. To better understand the emission patterns of these compounds, we utilized passive samplers in surface water to collect data at eight locations in a Dutch agricultural region, during different time intervals. As a passive sampler, we chose the integrative-based Speedisk® hydrophilic DVB. In total, we targeted 46 compounds, among which 25 antibiotics, three hormones, nine antiparasitics, and nine disinfectants. From these 46 compounds, 22 compounds accumulated in passive samplers in amounts above the limit of quantification in at least one sampling location. Over the 12-week deployment period, a time integrative uptake pattern was identified in 53% of the examined cases, with the remaining 47% not displaying this behavior. The occurrences without this behavior were primarily associated with specific location, particularly the most upstream location, or specific compounds. Our findings suggest that the proposed use of passive samplers, when compared in this limited context to traditional grab sampling, may provide enhanced efficiency and potentially enable the detection of a wider array of compounds. In fact, a number of compounds originating from animal husbandry activities were quantified for the first time in Dutch surface waters, such as flubendazole, florfenicol, and tilmicosine. The set-up of the sampling campaign also allowed to distinguish between different pollution levels during sampling intervals on the same location. This aspect gains particular significance when considering the utilization of different compounds on various occasions, hence, it has the potential to strengthen ongoing monitoring and mitigation efforts.

Assessing city-wide pharmaceutical emissions to wastewater via modelling and passive sampling.

With increasing numbers of chemicals used in modern society, assessing human and environmental exposure to them is becoming increasingly difficult. Recent advances in wastewater-based epidemiology enable valuable insights into public exposure to data-poor compounds. However, measuring all >26,000 chemicals registered under REACH is not just technically unfeasible but would also be incredibly expensive. In this paper, we argue that estimating emissions of chemicals based on usage data could offer a more comprehensive, systematic and efficient approach than repeated monitoring. Emissions of 29 active pharmaceutical ingredients (APIs) to wastewater were estimated for a medium-sized city in the Netherlands. Usage data was collected both on national and local scale and included prescription data, usage in health-care institutions and over-the-counter sales. Different routes of administration were considered as well as the excretion and subsequent in-sewer back-transformation of conjugates into respective parent compounds. Results suggest model-based emission estimation on a city-level is feasible and in good agreement with wastewater measurements obtained via passive sampling. Results highlight the need to include excretion fractions in the conceptual framework of emission estimation but suggest that the choice of an appropriate excretion fraction has a substantial impact on the resulting model performance.

Characterization of urban sources of antibiotics and antibiotic-resistance genes in a Dutch sewer catchment.

A one year study was conducted in the city of Nijmegen, The Netherlands, to characterize various urban sources of antibiotics and antibiotic resistant genes (ARGs) in wastewater within a single sewer catchment. Prevalence of ermB, tet(W), sul1, sul2, intl1, and 16S rRNA gene was determined at 10 locations within the city. Sampling locations included a nursing home, a student residence, a hospital and an industrial area, among others. Wastewater concentrations of 23 antibiotics were measured using passive sampling. Additionally, excreted loads of 22 antibiotics were estimated based on ambulatory prescription and clinical usage data. Genes sul1 and intl1 were most abundant across most locations. Ciprofloxacin and amoxicillin together contributed over 92 % of the total estimated antibiotic selective pressure at all sampling points. The present study highlights the prominent role that hospitals can have in the prevalence and proliferation of ARGs in urban wastewater. Furthermore, results suggest that even short-term changes in the therapeutic regimen prescribed in hospitals may translate into shifting ARG abundance patterns in hospital wastewater. The methods applied present an opportunity to identify emission hotspots and prioritize intervention options to limit ARG spread from urban wastewater to the environment.

An analytical framework on the leaching potential of veterinary pharmaceuticals: A case study for the Netherlands.

Veterinary pharmaceuticals (VPs) residues may end up on the soil via manure, and from there can be transported to groundwater due to leaching. In this study an analytical framework to estimate the leaching potential of VPs at the national scale is presented. This approach takes soil-applied VPs concentrations, soil-hydraulic and soil-chemical properties, groundwater levels, sorption and degradation of VPs into account. For six commonly soil-applied VPs in the Netherlands, we assess quantities leached to groundwater and their spatial distribution, as well as the relative importance of processes that drive leaching. Our results for VPs Oxytetracycline, Doxycycline, and Ivermectin indicate that maximum quantities that may leach to groundwater are very low, i.e. ≪1 µg/ha, hence spatial differences are not investigated. For VPs Sulfadiazine and Flubendazole we identify a few regions that are potentially prone to leaching, with leached quantities higher than 1 µg/ha. Leaching patterns of these two VPs are dominated by soil properties and groundwater levels rather than soil-applied quantities. For Dexamethasone, even though applied on the soil in much lower concentrations compared to other investigated VPs, spatially widespread leaching to groundwater is found, with leached quantities higher than 1 µg/ha. Due to the leaching affinity of Dexamethasone, variations in the soil-applied amounts have significant influence on the quantities leached to groundwater. Dexamethasone is highlighted as important for the future environmental risk assessment efforts. This study has shown that the leaching potential of VPs is not determined by one single parameter, but by a combination of parameters. This combination also depends on the compound investigated.

The role of the sewer system in estimating urban emissions of chemicals of emerging concern.

The use of chemicals by society has resulted in calls for more effective control of their emissions. Many of these chemicals are poorly characterized because of lacking data on their use, environmental fate and toxicity, as well as lacking detection techniques. These compounds are sometimes referred to as contaminants of emerging concern (CECs). Urban areas are an important source of CECs, where these are typically first collected in sewer systems and then discharged into the environment after being treated in a wastewater treatment plant. A combination of emission estimation techniques and environmental fate models can support the early identification and management of CEC-related environmental problems. However, scientific insight in the processes driving the fate of CECs in sewer systems is limited and scattered. Biotransformation, sorption and ion-trapping can decrease CEC loads, whereas enzymatic deconjugation of conjugated metabolites can increase CEC loads as metabolites are back-transformed into their parent respective compounds. These fate processes need to be considered when estimating CEC emissions. This literature review collates the fragmented knowledge and data on in-sewer fate of CECs to develop practical guidelines for water managers on how to deal with in-sewer fate of CECs and highlights future research needs. It was assessed to what extent empirical data is in-line with text-book knowledge and integrated sewer modelling approaches. Experimental half-lives (n = 277) of 96 organic CECs were collected from literature. The findings of this literature review can be used to support environmental modelling efforts and to optimize monitoring campaigns, including field studies in the context of wastewater-based epidemiology. Supplementary Information: The online version contains supplementary material available at 10.1007/s11157-022-09638-9.

Emission estimation and prioritization of veterinary pharmaceuticals in manure slurries applied to soil.

Veterinary pharmaceuticals (VPs) are emitted into the environment and transfer to groundwater and surface water is diffuse and complex, whereas actual information on the fate is frequently limited. For 17 VPs of potential concern in the Netherlands, we assessed sources and emission due to animal slurry applications to soil. Hence, we examined the use of VPs in four livestock sectors in the Netherlands for 2015-2018, and quantified animal excretion rates and dissipation during slurry storage. For almost all VPs, administrated quantities to the animals during the period 2015-2018 decreased. VP concentrations during a storage period of six months could decrease between 10 and 98% depending on the compound. Predicted concentrations of VPs in slurries after storage compared well with measured concentrations in the literature. Based on the storage model outcomes, we developed a residue indicator, that quantifies the potential for residues in applied slurry. This indicator agrees well with the most frequently detected VPs in the Dutch slurries, and is therefore useful to prioritize measures aiming at reducing VP emissions into the environment.

Risk-management tool for environmental prioritization of pharmaceuticals based on emissions from hospitals.

Over the past decade, the health care sector has become increasingly aware of the impact of pharmaceutical emissions to the environment. Yet, it remains unclear which compounds are the most relevant to address and at what point emission control is most effective. This study presents a modelling framework to prioritize pharmaceuticals based on their relative risks for aquatic organisms, using purchase and prescription data from hospitals. The framework consists of an emission prediction module and a risk prioritization module. The emission prediction module accounts for three different routes of intake (oral, intravenous, rectal), for non-patient consumption, and for delayed athome excretion due to relatively long half-lives or prescription durations of selected pharmaceuticals. We showcase the modelling framework with 16 pharmaceuticals administered at two Dutch academic hospitals. Predictions were validated with experimental data from passive sampling in the sewer system. With the exception of metformin, all predictions were within a factor of 10 from measurements. The risk prioritization module ranks each pharmaceutical based on its predicted relative risk for aquatic organisms. The resulting prioritization suggests that emission mitigation strategies should mainly focus on antibiotics and non-steroidal anti-inflammatory drugs (NSAIDs).

Impact of industrial waste water treatment plants on Dutch surface waters and drinking water sources.

Direct industrial discharges of Chemicals of Emerging Concern (CEC) to surface water via industrial wastewater treatment plants (IWTP) gained relatively little attention compared to discharges via municipal sewage water treatment plants. IWTP effluents may however seriously affect surface water quality. Here we modelled direct industrial emissions of all 182 Dutch IWTP from 19 different industrial classes, and derived their impact on Dutch surface water quality and drinking water production. We selected industrial chemicals relevant for drinking water production, however a lack of systematic information on concentrations in IWTP effluents for many chemicals of interest was found. Therefore, we used data from the European Pollutant Release and Transfer Register and data on Dutch IWTP as surrogate. We coupled these to a detailed hydrological model under two extreme river discharge conditions, and compared the predicted and measured concentrations. We derived relative impact factors for the IWTP based on their contribution to concentrations at surface water locations with a drinking water function. In total, a third of the abstracted water for drinking water production is influenced by the IWTP. From all Dutch 182 IWTP, only a limited number has - based on the model approach using surrogate parameters - a high impact on surface waters with a drinking water function. Mitigation measures can be taken cost-efficiently, by placing extra treatment technologies at the IWTP with high impact. Finally, we propose recommendations for licensing and controlling industrial aqueous emissions and give suggestions to fill the currently existing knowledge gaps and diminish uncertainties in the approach.

Modelling the Release, Transport and Fate of Engineered Nanoparticles in the Aquatic Environment - A Review.

Engineered nanoparticles, that is, particles of up to 100 nm in at least one dimension, are used in many consumer products. Their release into the environment as a consequence of their production and use has raised concern about the possible consequences. While they are made of ordinary substances, their size gives them properties that are not manifest in larger particles. It is precisely these properties that make them useful. For instance titanium dioxide nanoparticles are used in transparent sunscreens, because they are large enough to scatter ultraviolet light but too small to scatter visible light.To investigate the occurrence of nanoparticles in the environment we require practical methods to detect their presence and to measure the concentrations as well as adequate modelling techniques. Modelling provides both a complement to the available detection and measurement methods and the means to understand and predict the release, transport and fate of nanoparticles. Many different modelling approaches have been developed, but it is not always clear for what questions regarding nanoparticles in the environment these approaches can be applied. No modelling technique can be used for every possible aspect of the release of nanoparticles into the environment. Hence it is important to understand which technique to apply in what situation. This article provides an overview of the techniques involved with their strengths and weaknesses. Two points need to be stressed here: the modelling of processes like dissolution and the surface activity of nanoparticles, possibly under influence of ultraviolet light, or chemical transformation has so far received relatively little attention. But also the uncertainties surrounding nanoparticles in general-the amount of nanoparticles used in consumer products, what constitutes the appropriate measure of concentration (mass or numbers) and what processes are relevant-should be explicitly considered as part of the modelling.

A simulation study on effects of exposure to a combination of pesticides used in an orchard and tuber crop on the recovery time of a vulnerable aquatic invertebrate.

The aim of the present study was to assess whether population effects and recovery times increase when a population of a vulnerable aquatic invertebrate is exposed to concentrations of 1 or multiple pesticides. The 2 sets of pesticide combinations tested are typical for orchard and tuber crops in The Netherlands. Exposure concentrations were predicted using the FOCUS step 3 modeling framework and the Dutch drainage ditch scenario. Recovery times were assessed using the MASTEP population model. We simulated the population dynamics and pesticide effects in a Monte Carlo style by using median effective concentration values drawn from an arthropod species sensitivity distribution. In the tuber scenario, exposure to λ-cyhalothrin resulted in long-term effects, whereas exposure to the co-occurring compound fluazinam hardly resulted in (additional) effects. In the orchard scenario, 3 pesticides resulted in large effects just after exposure, but pulse exposures to these compounds did not coincide. The probabilities of effects for the single compounds added up for the combination; in contrast, the recovery times were not higher for the combination compared to those associated with exposure to the individual compounds. The conclusion from the present study's simulations is that exposure to the evaluated pesticide packages may lead to increased mortality probabilities and effect sizes of the combination, but does not lead to longer recovery times for populations with synchronized reproduction than when exposed to the individual compounds.

Acetylcholinesterase inhibition and increased food consumption rate in the zebrafish, Danio rerio, after chronic exposure to parathion.

Acetylcholinesterase (AChE) inhibition is widely regarded as a good biomarker of exposure to organophosphorus pesticides (OP). However, less is known about the relationship between AChE inhibition and consequences for growth, reproduction and survival on organisms. Acute toxicity tests with fish have shown that high percentages of AChE inhibition are needed to cause detrimental effects, but not much is known about the consequences of chronic exposure to this group of chemicals for both AChE activity and higher levels of biological organisation. In this study, zebrafish (Danio rerio) were exposed to sublethal concentrations of the OP parathion for 250 days in a flow-through system. Besides AChE activity, a variety of other parameters were measured: whole-body protein and lactate content, consumption rate, survival, growth and reproduction. AChE inhibition was correlated with exposure concentration, but not with exposure time, and was significant above 0.9 microg/l after 144 days and above 4.3 microg/l after 250 days of exposure. Both parathion and the cosolvent dimethylsulfoxide (DMSO) significantly increased food consumption rate of the fish. Survival, growth, reproduction and lactate content were not affected, while protein concentrations showed only minor effects. These findings support the hypothesis that AChE is a very sensitive biomarker for exposure, but not accurately predict higher level adverse effects following long-term exposure to OPs.

Sensitivity of the zebrafish (Danio rerio) early life stage test for compounds with different modes of action.

The sensitivity of the early life stage (ELS) toxicity test for two compounds with different modes of action was determined, and related to other toxicity tests with the same compounds. The zebrafish. Danio rerio, was used as a test organism, and the two model compounds were 1,2,3-trichlorobenzene (123TCB), a non-polar narcotic, and parathion, an acetylcholinesterase (AChE) inhibitor. Hatching and survival after 28 days were significantly reduced in the highest 123TCB treatment (263 microg/l), but not in any of the parathion treatments. Growth of the larvae was negatively affected at parathion concentrations above 20 microg/l, while AChE was only significantly inhibited at the highest concentration, 93 microg/l. No effects on growth were found in the 123TCB treatments. In comparison with acute and chronic studies with both compounds, the ELS test turned out to be less sensitive than chronic studies and more sensitive than acute studies. The difference in sensitivity between the tests systems seems however, to depend on the mode of action of the compound.