Summary recommendations on "Analytical methods for substances in the Watch List under the Water Framework Directive".

The Watch List (WL) is a monitoring program under the European Water Framework Directive (WFD) to obtain high-quality Union-wide monitoring data on potential water pollutants for which scarce monitoring data or data of insufficient quality are available. The main purpose of the WL data collection is to determine if the substances pose a risk to the aquatic environment at EU level and subsequently to decide whether a threshold, the Environmental Quality Standards (EQS) should be set for them and, potentially to be listed as priority substance in the WFD. The first WL was established in 2015 and contained 10 individual or groups of substances while the 4th WL was launched in 2022. The results of monitoring the substances of the first WL showed that some countries had difficulties to reach an analytical Limit of Quantification (LOQ) below or equal to the Predicted No-Effect Concentrations (PNEC) or EQS. The Joint Research Centre (JRC) of the European Commission (EC) organised a series of workshops to support the EU Member States (MS) and their activities under the WFD. Sharing the knowledge among the Member States on the analytical methods is important to deliver good data quality. The outcome and the discussion engaged with the experts are described in this paper, and in addition a literature review of the most important publications on the analysis of 17-alpha-ethinylestradiol (EE2), amoxicillin, ciprofloxacin, metaflumizone, fipronil, metformin, and guanylurea from the last years is presented.

Dynamics of active pharmaceutical ingredients loads in a Swiss university hospital wastewaters and prediction of the related environmental risk for the aquatic ecosystems.

The wastewater contamination of a Swiss university hospital by active pharmaceutical ingredient (API) residues was evaluated with a three months monitoring campaign at the outlet of the main building. Flow-proportional samples were collected with an automatic refrigerated sampler and analyzed for 15 API, including antibiotics, analgesics, antiepileptic and anti-inflammatory drugs, by using a validated LC-MS/MS method. The metals Gd and Pt were also analyzed using ICP-MS. Measured concentrations were compared to the predicted ones calculated after the drug average consumption data obtained from the hospital pharmacy. The hospital contribution to the total urban load was calculated according to the consumption data obtained from city pharmacies. Lastly, the environmental hazard and risk quotients (RQ) related to the hospital fraction and the total urban consumption were calculated. Median concentrations of the 15 selected compounds were ranging from 0.04 to 675 µg/L, with a mean detection frequency of 84%. The ratio between predicted and measured environmental concentrations (PEC/MEC) has shown a good accuracy for 5 out of 15 compounds, revealing over- and under-estimations of the PEC model. Mean daily loads were ranging between 0.01 and 14.2g/d, with the exception of paracetamol (109.7 g/d). The hospital contribution to the total urban loads varied from 2.1 to 100% according to the compound. While taking into account dilution and removal efficiencies in wastewater treatment plant, only the hospital fraction of the antibiotics ciprofloxacin and sulfamethoxazole showed, respectively, a high (RQ>1) and moderate (RQ>0.1) risk for the aquatic ecosystems. Nevertheless, when considering the total urban consumption, 7 compounds showed potential deleterious effects on aquatic organisms (RQ>1): gabapentin, sulfamethoxazole, ciprofloxacin, piperacillin, ibuprofen, diclofenac and mefenamic acid. In order to reduce inputs of API residues originating from hospitals various solutions can be envisioned. With results of the present study, hospital managers can start handling this important issue.

Development of an LC-MS/MS Method for the Assessment of Selected Active Pharmaceuticals and Metabolites in Wastewaters of a Swiss University Hospital.

A multi-residue analytical method was developed and validated for the quantification of 11 selected active pharmaceutical ingredients (API) and 2 human metabolites in hospital effluents using solid-phase extraction followed by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS). Targeted analytes belong to different therapeutic classes: non steroidal anti-inflammatory drugs (NSAID), analgesics, antibiotics and psychiatric drugs. Solid-phase extraction recoveries ranged between 21 and 101% for the selected API. Calibration curves were built with 6 standard samples prepared in ultrapure water ranging from 0.05 to 10 µg/L and showed regression coefficients above 0.994. The instrumental detection limits (IDL) varied between 0.05 and 5 µg/L, and the method detection limits (MDL) between 0.1 and 100 ng/L. Precision of the method, evaluated with spiked water samples at four different concentrations, varied between 84 and 117% for all compounds and an overall variability below 20%, with the exception of carbamazepine (71-123%). Except for two compounds, recoveries of spiked hospital wastewaters at four different concentrations (0.1, 1, 10 and 100 µg/L) varied between 44 and 133%, with relative standard deviation (RSD) between 0.6 and 28.5%. The evaluation of the matrix effects showed that diluted samples exhibit lower signal suppression. Analysis of effluent samples from a Swiss university hospital resulted in a mean detection frequency of 92% for the selected compounds, with concentrations up to 1535 µg/L for the analgesic paracetamol.

Prioritization methodology for the monitoring of active pharmaceutical ingredients in hospital effluents.

The important number of active pharmaceutical ingredients (API) available on the market along with their potential adverse effects in the aquatic ecosystems, lead to the development of prioritization methods, which allow choosing priority molecules to monitor based on a set of selected criteria. Due to the large volumes of API used in hospitals, an increasing attention has been recently paid to their effluents as a source of environmental pollution. Based on the consumption data of a Swiss university hospital, about hundred of API has been prioritized following an OPBT approach (Occurrence, Persistence, Bioaccumulation and Toxicity). In addition, an Environmental Risk Assessment (ERA) allowed prioritizing API based on predicted concentrations and environmental toxicity data found in the literature for 71 compounds. Both prioritization approaches were compared. OPBT prioritization results highlight the high concern of some non steroidal anti-inflammatory drugs and antiviral drugs, whereas antibiotics are revealed by ERA as potentially problematic to the aquatic ecosystems. Nevertheless, according to the predicted risk quotient, only the hospital fraction of ciprofloxacin represents a risk to the aquatic organisms. Some compounds were highlighted as high-priority with both methods: ibuprofen, trimethoprim, sulfamethoxazole, ritonavir, gabapentin, amoxicillin, ciprofloxacin, raltegravir, propofol, etc. Analyzing consumption data and building prioritization lists helped choosing about 15 API to be monitored in hospital wastewaters. The API ranking approach adopted in this study can be easily transposed to any other hospitals, which have the will to look at the contamination of their effluents.

Fluorescence spectroscopy to study dissolved organic matter interactions with agrochemicals applied in Swiss vineyards.

UV/Vis fluorescence spectroscopy was used to study the possible interactions of dissolved organic matter (DOM) with the herbicide glyphosate and copper-based fungicide used in vineyards. The study focused on the role of DOM in the transport of these micropollutants from parcels to surface waters (river, lake). Soil solution and river water samples were collected in the Lavaux vineyard area, western Switzerland. Their fluorescence excitation emission matrices (EEM) were decomposed using parallel factor (PARAFAC) analysis, and compared to their content in glyphosate and copper. PARAFAC analysis of EEM of both types of samples showed the contribution of protein-like and humic-like fluorophores. In soil water samples, complexes between fulvic-like and humic-like fluorophores of DOM, copper, and glyphosate were likely formed. In surface water, DOM-copper and glyphosate-copper interactions were observed, but not between glyphosate and DOM.

Dynamics and environmental risk assessment of the herbicide glyphosate and its metabolite AMPA in a small vineyard river of the Lake Geneva catchment.

The use of pesticides may lead to environmental problems, such as surface water pollution, with a risk for aquatic organisms. In the present study, a typical vineyard river of western Switzerland was first monitored to measure discharged loads, identify sources, and assess the dynamic of the herbicide glyphosate and its metabolite aminomethylphosphonic acid (AMPA). Second, based on river concentrations, an associated environmental risk was calculated using laboratory tests and ecotoxicity data from the literature. Measured concentrations confirmed the mobility of these molecules with elevated peaks during flood events, up to 4970 ng/L. From April 2011 to September 2011, a total load of 7.1 kg was calculated, with 85% coming from vineyards and minor urban sources and 15% from arable crops. Compared with the existing literature, this load represents an important fraction (6-12%) of the estimated amount applied because of the steep vineyard slopes (∼10%). The associated risk of these compounds toward aquatic species was found to be negligible in the present study, as well as for other rivers in Switzerland. A growth stimulation was nevertheless observed for the algae Scenedesmus vacuolatus with low concentrations of glyphosate, which could indicate a risk of perturbation in aquatic ecosystems, such as eutrophication. The combination of field and ecotoxicity data allowed the performance of a realistic risk assessment for glyphosate and AMPA, which should be applied to other pesticide molecules.

The herbicide glyphosate and its metabolite AMPA in the Lavaux vineyard area, Western Switzerland: proof of widespread export to surface waters. Part I: method validation in different water matrices.

An analytical method for the quantification of the widely used herbicide, glyphosate, its main by-product, aminomethylphosphonic acid (AMPA) and the herbicide glufosinate at trace level was developed and tested in different aqueous matrices. Their derivatization with 9-fluorenylmethyl chloroformate (FMOC-Cl) was done prior to their concentration and purification by solid phase extraction. The concentrated derivates were then analyzed by liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS). Spiking tests at three different concentrations were realized in several water matrices: ultrapure water, Evian(©) mineral water, river water, soil solution and runoff water of a vineyard. Except for AMPA in runoff water, obtained regression curves for all matrices of interest showed no statistical differences of their slopes and intercepts, validating the method for the matrix effect correction in relevant environmental samples. The limits of detection and quantification of the method were as low as 5 and 10 ng/l respectively for the three compounds. Spiked Evian(©) and river water samples at two different concentrations (30 and 130 ng/l) showed mean recoveries between 86 and 109%, and between 90 and 133% respectively. Calibration curves established in spiked Evian(©) water samples between 10 and 1000 ng/l showed r(2) values above 0.989. Monitoring of a typical vineyard river showed peaks of pollution by glyphosate and AMPA during main rain events, sometimes above the legal threshold of 100 ng/l, suggesting the diffuse export of these compounds by surface runoff. The depth profile sampled in the adjacent lake near a waste water treatment plant outlet showed a concentration peak of AMPA at 25m depth, indicating its release with treated urban wastewater.

The herbicide glyphosate and its metabolite AMPA in the Lavaux vineyard area, western Switzerland: proof of widespread export to surface waters. Part II: the role of infiltration and surface runoff.

Two parcels of the Lavaux vineyard area, western Switzerland, were studied to assess to which extent the widely used herbicide, glyphosate, and its metabolite aminomethylphosphonic acid (AMPA) were retained in the soil or exported to surface waters. They were equipped at their bottom with porous ceramic cups and runoff collectors, which allowed retrieving water samples for the growing seasons 2010 and 2011. The role of slope, soil properties and rainfall regime in their export was examined and the surface runoff/throughflows ratio was determined with a mass balance. Our results revealed elevated glyphosate and AMPA concentrations at 60 and 80 cm depth at parcel bottoms, suggesting their infiltration in the upper parts of the parcels and the presence of preferential flows in the studied parcels. Indeed, the succession of rainy days induced the gradual saturation of the soil porosity, leading to rapid infiltration through macropores, as well as surface runoff formation. Furthermore, the presence of more impervious weathered marls at 100 cm depth induced throughflows, the importance of which in the lateral transport of the herbicide molecules was determined by the slope steepness. Mobility of glyphosate and AMPA into the unsaturated zone was thus likely driven by precipitation regime and soil characteristics, such as slope, porosity structure and layer permeability discrepancy. Important rainfall events (>10 mm/day) were clearly exporting molecules from the soil top layer, as indicated by important concentrations in runoff samples. The mass balance showed that total loss (10-20%) mainly occurred through surface runoff (96%) and, to a minor extent, by throughflows in soils (4%), with subsequent exfiltration to surface waters.