Thomas L. ter Laak

Relating environmental concentrations of pharmaceuticals to consumption: A mass balance approach for the river Rhine

In this study, pharmaceuticals were frequently monitored in the Rhine delta between the year 2002 and 2008. Average concentrations of several X-ray contrast mediums were above 0.1 microg/L, the average concentration of carbamazepine was about 0.1 microg/L, while average concentrations of the other pharmaceuticals generally fell between 0.1 and 0.01 microg/L. Concentrations were used to calculate annual loads transported by the Rhine at Lobith. These loads were compared to the annual sales upstream of Lobith. This mass balance approach shows that substantial fractions (1.1% to 70.4%) of the 20 most frequently observed pharmaceuticals sold in the Rhine catchment area are recovered in the Rhine at Lobith. The observed annual loads were compared to loads predicted from annual sales in the catchment area, excreted fractions by humans and removal by waste water treatment. Observed and predicted annual loads were rather similar. The difference of the loads obtained from monitoring data and estimated from consumption was smaller than a factor of seven and did not exceed a factor of two for 15 out of the 20 pharmaceuticals. This illustrates the potential of using sales data for the prediction of concentrations in the aqueous environment.

Removal of charged micropollutants from water by ion-exchange polymers - effects of competing electrolytes

A wide variety of environmental compounds of concern, e.g. pharmaceuticals or illicit drugs, are acids or bases that may predominantly be present as charged species in drinking water sources. These charged micropollutants may prove difficult to remove by currently used water treatment steps (e.g. UV/H(2)O(2), activated carbon (AC) or membranes). We studied the sorption affinity of some ionic organic compounds to both AC and different charged polymeric materials. Ion-exchange polymers may be effective as additional extraction phases in water treatment, because sorption of all charged compounds to oppositely charged polymers was stronger than to AC, especially for the double-charged cation metformin. Tested below 1% of the polymer ion-exchange capacity, the sorption affinity of charged micropollutants is nonlinear and depends on the composition of the aqueous medium. Whereas oppositely charged electrolytes do not impact sorption of organic ions, equally charged electrolytes do influence sorption indicating ion-exchange (IE) to be the main sorption mechanism. For the tested polymers, a tenfold increased salt concentration lowered the IE-sorption affinity by a factor two. Different electrolytes affect IE with organic ions in a similar way as inorganic ions on IE-resins, and no clear differences in this trend were observed between the sulphonated and the carboxylated cation-exchanger. Sorption of organic cations is five fold less in Ca(2+) solutions compared to similar concentrations of Na(+), while that of anionic compounds is three fold weaker in SO(4)(2-) solutions compared to equal concentrations of Cl(-).

Quantifying summed fullerene nC60 and related transformation products in water using LC LTQ Orbitrap MS and application to environmental samples

The application of engineered nanomaterials increases strongly. Development of analytical techniques and their application to environmental samples is essential for human and environmental risk assessment of the nanoparticles. The objective of this study was to develop a sensitive analytical method to quantify nC(60) in water, using accurate mass screening liquid chromatography-hybrid linear ion trap Orbitrap mass spectrometry. nC(60) can be transformed by oxidation, reduction and photochemical reaction. Therefore, the formation of some transformation products of nC(60) was studied as well. Finally, the developed analytical method was applied to surface water samples from several locations in the Netherlands. The developed method enabled to detect and quantify aqueous concentrations of the summed nC(60) and its transformation products as low as 5 ng/L. It was observed that nC(60) transformation products exceed quantities of the parent C(60). Despite the high sensitivity of the developed method, no nC(60) or transformation products were detected in an array of Dutch surface waters. This might be due to low emissions, losses in the aqueous phase by sedimentation, sorption or further transformation processes.

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 37.8xa0μg/L. Metformin and its transformation product guanylurea contributed with 53 to 80xa0% 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 (16.0u2009±u20092.3 and 15.7u2009±u20092.1xa0mg/inhabitant/day, respectively) than the Dutch catchment (8.7u2009±u20091.8xa0mg/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.

Broad target chemical screening approach used as tool for rapid assessment of groundwater quality

The chemical water quality is often assessed by screening for a limited set of target chemicals. This conventional target analysis approach inevitably misses chemicals present in the samples. In this study a broad target screening approach for water quality assessment using high resolution and accurate mass spectrometry (HR MS) was applied to detect a wide variety of organic chemicals in 42 groundwater samples. In this approach, both known and unidentified chemicals observed in previous samples define the training set for the analysis of future samples and, additionally, new samples can be used to extend the training set. Nearly 400 chemicals were observed in the samples, of which 82 were known and more than 313 are of unknown identity. The obtained results were interpreted in relation to the source characteristics and land use. Groundwater that was affected by landfills showed the highest total MS response (ion counts) and most individual chemicals and was therefore considered most contaminated. Furthermore, river bank filtrated water was generally more contaminated than phreatic groundwater and groundwater from (semi)confined aquifers was most pristine. Additionally, industrial chemicals were more frequently observed in river bank filtrated water and pesticides were more frequently observed in water originating from rural areas. The broad target screening approach for both known and unidentified chemicals does provide more information on the over-all water quality than conventional target analysis.

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.

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 80u202fh, 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 80u202fh, 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.

Decision support for water quality management of contaminants of emerging concern

Water authorities and drinking water companies are challenged with the question if, where and how to abate contaminants of emerging concern in the urban water cycle. The most effective strategy under given conditions is often unclear to these stakeholders as it requires insight into several aspects of the contaminants such as sources, properties, and mitigation options. Furthermore the various parties in the urban water cycle are not always aware of each others requirements and priorities. Processes to set priorities and come to agreements are lacking, hampering the articulation and implementation of possible solutions. To support decision makers with this task, a decision support system was developed to serve as a point of departure for getting the relevant stakeholders together and finding common ground. The decision support system was iteratively developed in stages. Stakeholders were interviewed and a decision support system prototype developed. Subsequently, this prototype was evaluated by the stakeholders and adjusted accordingly. The iterative process lead to a final system focused on the management of contaminants of emerging concern within the urban water cycle, from wastewater, surface water and groundwater to drinking water, that suggests mitigation methods beyond technical solutions. Possible wastewater and drinking water treatment techniques in combination with decentralised and non-technical methods were taken into account in an integrated way. The system contains background information on contaminants of emerging concern such as physical/chemical characteristics, toxicity and legislative frameworks, water cycle entrance pathways and a database with associated possible mitigation methods. Monitoring data can be uploaded to assess environmental and human health risks in a specific water system. The developed system was received with great interest by potential users, and implemented in an international water cycle network.