Combining Passive Sampling and Dosing to Unravel the Contribution of Hydrophobic Organic Contaminants to Sediment Ecotoxicity.

Contaminated sediments are ubiquitous repositories of pollutants and cause substantial environmental risks. Results of sediment bioassays remain difficult to interpret, however, as observed effects may be caused by a variety of (un)known stressors. This study aimed therefore to isolate the effects of hydrophobic organic contaminants from other (non)chemical stressors present in contaminated sediments, by employing a newly developed passive sampling-passive dosing (PSPD) test. The results showed that equilibrium partitioning between pesticides or polyaromatic hydrocarbons (PAHs) in contaminated sediments and a silicone rubber (SR) passive sampler was achieved after 1-3 days. Chlorpyrifos concentrations in pore water of spiked sediment matched very well with concentrations released from the SR into an aqueous test medium, showing that SR can serve as a passive dosing device. Subjecting the 96 h PSPD laboratory bioassay with nonbiting midge (Chironomus riparius) larvae to field-collected sediments showed that at two locations, concentrations of the hydrophobic organic contaminant mixtures were high enough to affect the test organisms. In conclusion, the developed PSPD test was able to isolate the effects of hydrophobic organic contaminants and provides a promising simplified building block for a suite of PSPD tests that after further validation could be used to unravel the contribution of hydrophobic organic chemicals to sediment ecotoxicity.

Research Priorities for the Environmental Risk Assessment of Per- and Polyfluorinated Substances.

Per- and polyfluorinated substances (PFAS) are a group of thousands of ubiquitously applied persistent industrial chemicals. The field of PFAS environmental research is developing rapidly, but suffers from substantial biases toward specific compounds, environmental compartments, and organisms. The aim of our study was therefore to highlight current developments and to identify knowledge gaps and subsequent research needs that would contribute to a comprehensive environmental risk assessment for PFAS. To this end, we consulted the open literature and databases and found that knowledge of the environmental fate of PFAS is based on the analysis of <1% of the compounds categorized as PFAS. Moreover, soils and suspended particulate matter remain largely understudied. The bioavailability, bioaccumulation, and food web transfer studies of PFAS also focus on a very limited number of compounds and are biased toward aquatic biota, predominantly fish, and less frequently aquatic invertebrates and macrophytes. The available ecotoxicity data revealed that only a few PFAS have been well studied for their environmental hazards, and that PFAS ecotoxicity data are also strongly biased toward aquatic organisms. Ecotoxicity studies in the terrestrial environment are needed, as well as chronic, multigenerational, and community ecotoxicity research, in light of the persistency and bioaccumulation of PFAS. Finally, we identified an urgent need to unravel the relationships among sorption, bioaccumulation, and ecotoxicity on the one hand and molecular descriptors of PFAS chemical structures and physicochemical properties on the other, to allow predictions of exposure, bioaccumulation, and toxicity. Environ Toxicol Chem 2023;42:2302-2316. © 2023 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Occurrence, Fate, and Related Health Risks of PFAS in Raw and Produced Drinking Water.

This study investigates human exposure to per- and polyfluoroalkyl substances (PFAS) via drinking water and evaluates human health risks. An analytical method for 56 target PFAS, including ultrashort-chain (C2-C3) and branched isomers, was developed. The limit of detection (LOD) ranged from 0.009 to 0.1 ng/L, except for trifluoroacetic-acid and perfluoropropanoic-acid with higher LODs of 35 and 0.24 ng/L, respectively. The method was applied to raw and produced drinking water from 18 Dutch locations, including groundwater or surface water as source, and applied various treatment processes. Ultrashort-chain (300 to 1100 ng/L) followed by the group of perfluoroalkyl-carboxylic-acids (PFCA, ≥C4) (0.4 to 95.1 ng/L) were dominant. PFCA and perfluoroalkyl-sulfonic-acid (≥C4), including precursors, showed significantly higher levels in drinking water produced from surface water. However, no significant difference was found for ultrashort PFAS, indicating the need for groundwater protection. Negative removal of PFAS occasionally observed for advanced treatment indicates desorption and/or degradation of precursors. The proportion of branched isomers was higher in raw and produced drinking water as compared to industrial production. Drinking water produced from surface water, except for a few locations, exceed non-binding provisional guideline values proposed; however, all produced drinking waters met the recent soon-to-be binding drinking-water-directive requirements.

Triangulating Amsterdam's illicit stimulant use trends by wastewater analysis and recreational drug use monitoring.

Drug consumption estimates are of relevance because of public health effects as well as associated criminal activities. Wastewater analysis of drug residues enables the estimation of drug consumption and drug markets. Short-term and long-term trends of cocaine, MDMA (ecstasy), amphetamine (speed) and methamphetamine (crystal meth), were studied for the city of Amsterdam. MDMA (+41%) and cocaine (+26%) showed significantly higher weekend vs. week consumption, while no differences were observed for the other drugs. The consumption of MDMA, cocaine, amphetamine and methamphetamine significantly increased between 2011 and 2019. Weekly trends emerging from wastewater analyses were supported by qualitative and quantitative data from a recreational drug use monitoring scheme. However, information collected in panel interviews within nightlife networks and surveys among visitors of pubs, clubs and festivals only partially reflected the long term increase in consumption as registered from wastewater analysis. Furthermore, methamphetamine use was not well presented in survey data, panel studies and test service samples, but could be monitored trough wastewater analysis. This illustrates that wastewater analysis can function as an early warning if use and user groups are small or difficult to reach trough other forms of research. All in all, this study illustrates that wastewater-based epidemiology is complementary to research among user groups, and vice versa. These different types of information enable to connect observed trends in total drug consumption to behaviour of users and the social context in which the use takes place as well as validate qualitative signals about (increased) consumption of psychoactive substances. Such a multi angular approach to map the illicit drug situation on local or regional scale can provide valuable information for public health.

Occurrence, hazard, and risk of psychopharmaceuticals and illicit drugs in European surface waters.

This study aimed to provide insights into the risk posed by psychopharmaceuticals and illicit drugs in European surface waters, and to identify current knowledge gaps hampering this risk assessment. First, the availability and quality of data on the concentrations of psychopharmaceuticals and illicit drugs in surface waters (occurrence) and on the toxicity to aquatic organisms (hazard) were reviewed. If both occurrence and ecotoxicity data were available, risk quotients (risk) were calculated. Where abundant ecotoxicity data were available, a species sensitivity distribution (SSD) was constructed, from which the hazardous concentration for 5% of the species (HC5) was derived, allowing to derive integrated multi-species risks. A total of 702 compounds were categorised as psychopharmaceuticals and illicit drugs based on a combination of all 502 anatomical therapeutic class (ATC) 'N' pharmaceuticals and a list of illicit drugs according to the Dutch Opium Act. Of these, 343 (49%) returned occurrence data, while only 105 (15%) returned ecotoxicity data. Moreover, many ecotoxicity tests used irrelevant endpoints for neurologically active compounds, such as mortality, which may underestimate the hazard of psychopharmaceuticals. Due to data limitations, risks could only be assessed for 87 (12%) compounds, with 23 (3.3%) compounds indicating a potential risk, and several highly prescribed drugs returned neither occurrence nor ecotoxicity data. Primary bottlenecks in risk calculation included the lack of ecotoxicity data, a lack of diversity of test species and ecotoxicological end points, and large disparities between well studied and understudied compounds for both occurrence and toxicity data. This study identified which compounds merit concern, as well as the many compounds that lack the data for any calculation of risk, driving research priorities. Despite the large knowledge gaps, we concluded that the presence of a substantial part (26%) of data-rich psychopharmaceuticals in surface waters present an ecological risk for aquatic non-target organisms.

Fate of microplastics in the drinking water production.

Microplastics are ubiquitous and consequently enter drinking water treatment plants. Knowledge of the microplastic fate in drinking water production is still very limited, although explorative studies have shown tap water contains low contents of microplastics. In this study, we measure microplastic concentrations in drinking water sources and assess the effectiveness of various drinking water treatment facilities to reduce the microplastic concentrations in water to gain insight into the fate of microplastics. Two analytical techniques, laser direct infrared spectroscopy (LDIR) and optical microscopy, have been applied to cover the particle size range from 20 µm to 5 mm. In total five different drinking water sites were investigated using four different types of raw water (groundwater, surface water, dune filtrate and riverbank filtrate) for drinking water production. This research shows that drinking water treatment removes the majority of microplastics and that concentration of microplastics larger than 20 µm in tap water is less than 2 microplastics particles per litre. Between the different raw water sources it is found that groundwater had by far the lowest microplastics concentrations (< 1.000 microplastics per m3) and the highest concentration was found in riverine water, up to 460.000 particles per m3, specifically in the Lek Canal () (a canal connected to the river Rhine). On average the most abundant plastics found are polyamide (PA, 33%), polyethylene terephthalate (PET, 15%), rubbers (10%), polyethylene (PE, 10%) and chlorinated polyethylene (CPE, 7%). This study also showed that natural treatment steps, such as dune infiltration and sedimentation, remove microplastics effectively. However, this may introduce an adverse effect where microplastics potentially accumulate in the sediment and environment.

Wastewater-based epidemiology for illicit drugs: A critical review on global data.

Illicit drug use is complex, hidden and often highly stigmatized behaviour, which brings a vast challenge for drug surveillance systems. Drug consumption can be estimated by measuring human excretion products in untreated wastewater, known as wastewater-based epidemiology (WBE). Over the last decade, the application of wastewater-based epidemiology to monitor illicit drug loads increased and WBE is currently applied on a global scale. Studies from over the globe are evaluated with regard to their sampling method, analytical accuracy and consumption calculation, aiming to further reduce relevant uncertainties in order to make reliable comparisons on a global level. Only a limited number is identified as high-quality studies, so further standardization of the WBE approach for illicit drugs is desired especially with regard to the sampling methodology. Only a fraction of the reviewed papers explicitly reports uncertainty ranges for their consumption data. Studies which had the highest reliability are recently published, indicating an improvement in reporting WBE data. Until now, WBE has not been used in large parts of Africa, nor in the Middle East and Russia. An overview of consumption data across the continents on commonly studied drugs (cocaine, MDMA, amphetamine and methamphetamine) is provided. Overall, high consumption rates are confirmed in the US, especially for cocaine and methamphetamine, while relatively low illicit drug consumption is reported in Asia.

patRoon: open source software platform for environmental mass spectrometry based non-target screening.

Mass spectrometry based non-target analysis is increasingly adopted in environmental sciences to screen and identify numerous chemicals simultaneously in highly complex samples. However, current data processing software either lack functionality for environmental sciences, solve only part of the workflow, are not openly available and/or are restricted in input data formats. In this paper we present patRoon, a new R based open-source software platform, which provides comprehensive, fully tailored and straightforward non-target analysis workflows. This platform makes the use, evaluation and mixing of well-tested algorithms seamless by harmonizing various common (primarily open) software tools under a consistent interface. In addition, patRoon offers various functionality and strategies to simplify and perform automated processing of complex (environmental) data effectively. patRoon implements several effective optimization strategies to significantly reduce computational times. The ability of patRoon to perform time-efficient and automated non-target data annotation of environmental samples is demonstrated with a simple and reproducible workflow using open-access data of spiked samples from a drinking water treatment plant study. In addition, the ability to easily use, combine and evaluate different algorithms was demonstrated for three commonly used feature finding algorithms. This article, combined with already published works, demonstrate that patRoon helps make comprehensive (environmental) non-target analysis readily accessible to a wider community of researchers.

Shifting the imbalance: Intentional reuse of Dutch sewage effluent in sub-surface irrigation.

Worldwide, agricultural irrigation currently accounts for 69% of freshwater withdrawal. Countries with a temperate climate, such as the Netherlands, experience periodic freshwater shortages in agriculture. The pressure on available freshwater will increase due to climate change and a growing demand for freshwater by e.g. industrial activities. Possible alternative water resources are considered in order to meet the current and future water demand. In this study we explore where, and how much, sewage treatment plant (STP) effluent can directly be reused in agricultural sub-surface irrigation (SSI) during an average and a dry season scenario, for all active (335) Dutch STPs. SSI systems may have a higher water demand as part of the STP effluent is transported with groundwater flow, although aboveground irrigation has a loss of water due to interception. Furthermore, such aboveground irrigation systems provide direct contact of crops with irrigation water. SSI systems provide a soil barrier which may function as a filter and buffer zone. In the Dutch situation, direct intentional reuse of STP effluent can fulfill up to 25% of croplands SSI water demand present within a five-kilometer transport buffer from the STPs during an average season and 17% during a dry season. Hereto, respectively, 78% and 84% of the total available Dutch STP effluent would be used. Thus, the intentional direct STP effluent reuse in agricultural SSI has the potential to satisfy a significant amount of the agricultural water demand at a national scale, presuming responsible reuse: safe applications for humans and environment and no limiting effects on water availability for other actors.

Retention soil filters for the treatment of sewage treatment plant effluent and combined sewer overflow.

Retention soil filters (RSFs) are vertical flow constructed wetlands. They are mainly used for the treatment of combined sewer overflow or stormwater, and not operated during dry weather conditions. However, RSFs have been successfully tested as continuous post treatment for sewage treatment plant effluents. In this paper we present a new approach, namely dual usage of the retention soil filter. During dry weather the RSF is used for the polishing treatment of sewage treatment plant effluent and during overflow events, the retention soil filter treats the combined sewer overflow. This study was conducted at two pilot RSFs that were fed with sewage treatment effluent for four years. Removal of TOC, DOC, nutrients and 21 organic micropollutants was determined during six months at different sequences of regular effluent and overflow treatment conditions. TOC, DOC and nutrients, appearing in high concentration in combined sewer overflow, were effectively removed, and metformin and caffeine micropollutants showed >99% removal. Residues from this combined sewer treatment that were sorbed on filter material or stored in pore water were washed out directly after treatment when STP effluent infiltration was initiated. This effect declined within 20 h after combined sewer overflow treatment. Dry periods of 18 h between combined sewer and sewage treatment plant effluent feeding counteracted the wash out effects. The highest removal efficiency was found in the beginning of the feeding time of 28 h, indicating that shorter feeding cycles enhance the overall efficiency of the RSF. Finally, the results show that a single RSF system can successfully reduce emissions of TOC, DOC, nutrients and micropollutants to surface waters from two different emission pathways, i.e. from regular treated effluents and storm related sewer overflows. In conclusion, the dual usage of RSF is a promising approach and ready for upscaling and implementation.

Integration of target analyses, non-target screening and effect-based monitoring to assess OMP related water quality changes in drinking water treatment.

The ever-increasing production and use of chemicals lead to the occurrence of organic micro-pollutants (OMPs) in drinking water sources, and consequently the need for their removal during drinking water treatment. Due to the sheer number of OMPs, monitoring using targeted chemical analyses alone is not sufficient to assess drinking water quality as well as changes thereof during treatment. High-resolution mass spectrometry (HRMS) based non-target screening (NTS) as well as effect-based monitoring using bioassays are promising monitoring tools for a more complete assessment of water quality and treatment performance. Here, we developed a strategy that integrates data from chemical target analyses, NTS and bioassays. We applied it to the assessment of OMP related water quality changes at three drinking water treatment pilot installations. These installations included advanced oxidation processes, ultrafiltration in combination with reverse osmosis, and granular activated carbon filtration. OMPs relevant for the drinking water sector were spiked into the water treated in these installations. Target analyses, NTS and bioassays were performed on samples from all three installations. The NTS data was screened for predicted and known transformation products of the spike-in compounds. In parallel, trend profiles of NTS features were evaluated using multivariate analysis methods. Through integration of the chemical data with the biological effect-based results potential toxicity was accounted for during prioritization. Together, the synergy of the three analytical methods allowed the monitoring of OMPs and transformation products, as well as the integrative biological effects of the mixture of chemicals. Through efficient analysis, visualization and interpretation of complex data, the developed strategy enabled to assess water quality and the impact of water treatment from multiple perspectives. Such information could not be obtained by any of the three methods alone. The developed strategy thereby provides drinking water companies with an integrative tool for comprehensive water quality assessment.

In situ removal of four organic micropollutants in a small river determined by monitoring and modelling.

Organic micropollutants (OMPs) are widely detected in surface waters. So far, the removal processes of these compounds in situ in river systems are not yet totally revealed. In this study, a combined monitoring and modelling approach was applied to determine the behaviour of 1-H benzotriazole, carbamazepine, diclofenac and galaxolide in a small river system. Sewage treatment plant effluents and the receiving waters of the river Swist were monitored in 9 dry weather sampling campaigns (precipitation < 1 mm on the sampling day itself and <5 mm total precipitation two days before the sampling) during different seasons over a period of 3 years. With the results gained through monitoring, mass balances have been calculated to assess fate in the river. With the DWA Water Quality Model, OMP concentrations in the river were successfully simulated with OMP characteristics gained through literature studies. No removal was determined for 1-H benzotriazole and carbamazepine, whereas diclofenac showed removal that coincided with light intensity. Moreover, modelling based on light sensitivity of diclofenac also suggested relevant degradation at natural light conditions. These two approaches suggest removal by photodegradation. The highest removal in the river was detected for galaxolide, presumably due to volatilisation, sorption and biodegradation. Furthermore, short-term concentration variability in the river was determined, showing that daily concentration patterns are influenced by dynamics of sewage treatment plant effluent volumes and removal processes in the river.

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.

Retention soil filter as post-treatment step to remove micropollutants from sewage treatment plant effluent.

Retention soil filters (RSFs) are a specific form of vertical flow constructed wetlands for the treatment of rain water and/or wastewater. We have tested 3 pilot RSFs to investigate removal of dissolved organic carbon (DOC) and 14 different organic micropollutants (OMPs) from the effluent of a large scale sewage treatment plant (STP). Two of them were operated as conventional RSF with material (sand with CaCO3 and organic matter) from two different full-scale RSFs. The third pilot RSF contained filter material (sand with CaCO3) with additional biochar in the upper layer (0-10 cm) and granulated activated carbon (GAC) in the lower layer (60-90 cm). The filters were planted with Phragmites australis. The RSFs were operated and monitored for 3 years, and water samples were taken regularly at inflow, outflows and in 3 depths within the filters. In total 523 samples were taken. In the conventional RSF, best median removal was detected for galaxolide, diclofenac 4-hydroxy, metoprolol and clarithromycin (75-79%). No removal was seen for sulfamethoxazole and carbamazepine. The DOC and OMP removal in the conventional RSFs was best in the upper layer with highest organic matter content, increased in time over the three years of operation and also with extended contact time. In the effluent of the RSF with GAC, 10 out of the 14 OMPs could not be detected; 4 OMPs were detected, but only metformin with removal < 80%, thus showing a more efficient removal than the conventional RSF. A decrease in DOC removal was detected in the GAC layer (>88% to 60%) over the 2.5 years of operation. Biochar was most effective in OMP removal in the first operational year. It can be concluded that the increasing removal efficiency of the conventional RSF material - also present in the RSF with biochar and GAC - might mitigate the reduced efficiency of the sorbent additives biochar and GAC. This enables to extend the operational lifetime of the filters with acceptable removal rates. Finally, our study demonstrates that an RSF with GAC shows an enhanced removal of OMPs, which is a suitable post-treatment step for STPs.

Pharmaceutical concentration variability at sewage treatment plant outlets dominated by hydrology and other factors.

A study was conducted in which the effluent at four small to medium sized sewage treatment plants (STP) in North Rhine-Westphalia, Germany was monitored for three pharmaceutical compounds (carbamazepine, diclofenac, metoprolol) over a period of four years. Grab sampling and auto sampling campaigns were accomplished with respect to various weather conditions in the catchment area. Flow volumes and hydraulic retention times (HRT) from various sampling dates which provide information on processes causing emission changes were additionally taken into account. Monitoring results showed that concentration scattering in the effluent is related to HRT in the sewage treatment plants. Dilution effects following rain events in the catchment area were analysed for the three investigated substances. Short-term emission changes explained by dilution only could be well determined by the mathematical relation between discharge and concentration, and for carbamazepine to be solely determined by the dilution effects at all HRTs. For metoprolol, a clear decrease in concentrations was observed at HRTs above 80 h, and a significant contribution of biodegradation was supported by independent biodegradation tests. For three out of the four STPs, a decrease in concentrations of diclofenac was observed at hydraulic retention times above 80 h, indicating removal, whereas the relationship between concentration and HRT of the other STP could be explained by dilution only. The study shows that emissions can vary with weather conditions, hampering the assessment of emissions and estimation of concentrations in surface waters from generic removal rates only. Furthermore, it illustrates the importance of HRT of rather stable substances in wastewater treatment.

Projected impact of climate change and chemical emissions on the water quality of the European rivers Rhine and Meuse: A drinking water perspective.

Low river discharges of the rivers Rhine and Meuse are expected to occur more often and more prolonged in a changing climate. During these dry periods the dilution of point sources such as sewage effluents is reduced leading to a decline in chemical water quality. This study projects chemical water quality of the rivers Rhine and Meuse in the year 2050, based on projections of chemical emissions and two climate scenarios: moderate and fast climate change. It focuses on specific compounds known to be relevant to drinking water production, i.e. four pharmaceuticals, a herbicide and its metabolite and an artificial sweetener. Hydrological variability, climate change, and increased emission show a significant influence on the water quality in the Rhine and Meuse. The combined effect of changing future emissions of these compounds and reduced dilution due to climate change has leaded to increasing (peak) concentrations in the river water by a factor of two to four. Current water treatment efficiencies in the Netherlands are not sufficient to reduce these projected concentrations in drinking water produced from surface water below precautionary water target values. If future emissions are not sufficiently reduced or treatment efficiencies are not improved, these compounds will increasingly be found in drinking water, albeit at levels which pose no threat to human health.

Data-driven prioritization of chemicals for various water types using suspect screening LC-HRMS.

For the prioritization of more than 5200 anthropogenic chemicals authorized on the European market, we use a large scale liquid chromatography-high resolution mass spectrometry (LC-HRMS) suspect screening study. The prioritization is based on occurrence in 151 water samples including effluent, surface water, ground water and drinking water. The suspect screening linked over 700 detected compounds with known accurate masses to one or multiple suspects. Using a prioritization threshold and removing false positives reduced this to 113 detected compounds linked to 174 suspects, 24 compounds reflect a confirmed structure by comparison with the pure reference standard. The prioritized compounds and suspects are relevant for detailed risk assessments after confirmation of their identity. Only one of the 174 prioritized compounds and suspects is mentioned in water quality regulations, and only 20% is mentioned on existing lists of potentially relevant chemicals. This shows the complementarity to commonly used target-based methods. The semi-quantitative total concentration, expressed as internal standard equivalents of detected compounds linked to suspects, in effluents is approximately 10 times higher than in surface waters, while ground waters and drinking waters show the lowest response. The average retention time, a measure for hydrophobicity, of the detected compounds per sample decreased from effluent to surface- and groundwater to drinking water, confirming the occurrence of more polar compounds in drinking water. The semi-quantitative total concentrations exceed the conservative and precautionary threshold of toxicological concern. Therefore, adverse effects of mixtures cannot be neglected without a more thorough risk assessment.

Towards spatially smart abatement of human pharmaceuticals in surface waters: Defining impact of sewage treatment plants on susceptible functions.

For human pharmaceuticals, sewage treatment plants (STPs) are a major point of entry to surface waters. The receiving waters provide vital functions. Modeling the impact of STPs on susceptible functions of the surface water system allows for a spatially smart implementation of abatement options at, or in the service area of, STPs. This study was performed on a nation-wide scale for the Netherlands. Point source emissions included were 345 Dutch STPs and nine rivers from neighboring countries. The Dutch surface waters were represented by 2511 surface water units. Modeling was performed for two extreme discharge conditions. Monitoring data of 7 locations along the rivers Rhine and Meuse fall mostly within the range of modeled concentrations. Half of the abstracted volumes of raw water for drinking water production, and a quarter of the Natura 2000 areas (European Union nature protection areas) hosted by the surface waters, are influenced by STPs at low discharge. The vast majority of the total impact of all Dutch STPs during both discharge conditions can be attributed to only 19% of the STPs with regard to the drinking water function, and to 39% of the STPs with regard to the Natura 2000 function. Attributing water treatment technologies to STPs as one of the possible measures to improve water quality and protect susceptible functions can be done in a spatially smart and cost-effective way, using consumption-based detailed hydrological and water quality modeling.

Different compositions of pharmaceuticals in Dutch and Belgian rivers explained by consumption patterns and treatment efficiency.

In the current study, 43 pharmaceuticals and 18 transformation products were studied in the river Meuse at the Belgian-Dutch border and four tributaries of the river Meuse in the southern part of the Netherlands. The tributaries originate from Belgian, Dutch and mixed Dutch and Belgian catchments. In total, 23 pharmaceuticals and 13 transformation products were observed in samples of river water collected from these rivers. Observed summed concentrations of pharmaceuticals and transformation products in river water ranged from 3.5 to 37.8 µg/L. Metformin and its transformation product guanylurea contributed with 53 to 80 % to this concentration, illustrating its importance on a mass basis. Data on the flow rate of different rivers and demographics of the catchments enabled us to calculate daily per capita loads of pharmaceuticals and transformation products. These loads were linked to sales data of pharmaceuticals in the catchment. Simple mass balance modelling accounting for human excretion and removal by sewage treatment plants revealed that sales could predict actual loads within a factor of 3 for most pharmaceuticals. Rivers that originated from Belgian and mixed Dutch and Belgian catchments revealed significantly higher per capita loads of pharmaceuticals (16.0 ± 2.3 and 15.7 ± 2.1 mg/inhabitant/day, respectively) than the Dutch catchment (8.7 ± 1.8 mg/inhabitant/day). Furthermore, the guanylurea/metformin ratio was significantly lower in waters originating from Belgium (and France) than in those from the Netherlands, illustrating that sewage treatment in the Belgian catchment is less efficient in transforming metformin into guanylurea. In summary, the current study shows that consumption-based modelling is suitable to predict environmental loads and concentrations. Furthermore, different consumption patterns and wastewater treatment efficiency are clearly reflected in the occurrence and loads of pharmaceuticals in regional rivers.

Hepatic clearance of 6 polycyclic aromatic hydrocarbons by isolated perfused trout livers: prediction from in vitro clearance by liver S9 fractions.

Isolated perfused trout livers were used to evaluate in vitro-in vivo metabolism extrapolation procedures for fish. In vitro depletion rates for 6 polycyclic aromatic hydrocarbons (PAHs) were measured using liver S9 fractions and extrapolated to the intact tissue. Predicted hepatic clearance (CLH) values were then compared with values exhibited by intact livers. Binding in liver perfusates was manipulated using bovine serum albumin (BSA) and was characterized by solid-phase microextraction. Additional studies were conducted to develop binding terms (f U; calculated as the ratio of unbound fractions in liver perfusate [f U,PERF] and the S9 system [f U,S9]) used as inputs to a well-stirred liver model. Hepatic clearance values for pyrene and benzo[a]pyrene, predicted by extrapolating in vitro data to the intact tissue, were in good agreement with measured values (< 2-fold difference). This can be partly attributed to the rapid rate at which both compounds were metabolized by S9 fractions, resulting in perfusion-limited clearance. Predicted levels of CLH for the other PAHs underestimated observed values although these differences were generally small (< 3-fold, except for naphthalene). Setting f U = 1.0 improved clearance predictions at the highest tested BSA concentration (10mg/ml), suggesting that trout S9 fractions exhibit lower levels of intrinsic activity than the intact tissue or that the full binding assumption (ie, f U = f U,PERF/f U,S9) underestimates the availability of hydrophobic substrates to hepatic metabolizing enzymes. These findings provide qualified support for procedures currently being used to predict metabolism impacts on chemical accumulation by fish based on measured rates of in vitro activity.