Analytical methods for possible WFD 1st watch list substances

Directive 2013/39/EU amending the Environmental Quality Standards Directive 2008/105/EC under the European Water Framework Directive (WFD) has introduced the new “Watch List” monitoring mechanism in order to collect high-quality Union-wide monitoring data for the purpose of supporting future prioritisation exercises. Diclofenac, 17-beta-estradiol, and 17-alpha-ethinylestradiol were identified in Directive 2013/39/EU for inclusion in the 1st Watch List. The Joint Research Centre (JRC) has been tasked with proposing seven substances as candidates for the completion of the 1st Watch List and identifying analytical methods for their monitoring. The procedure and criteria used to identify a short-list of substances for possible inclusion in the Watch List is described in the JRC Science and Policy Report “Development of the 1st Watch List under the Environmental Quality Standards Directive" (Carvalho et al., 2015). EU Member States and stakeholder groups had the opportunity to comment on the proposed substances and on the analytical methods, whose availability was a criterion for the selection of the compounds. The finally proposed 10 (groups of) substances for inclusion in the 1st Watch List are diclofenac, 17-beta-estradiol (E2) and estrone (E1), 17-alpha-ethinylestradiol (EE2), oxadiazon, methiocarb, 2,6-ditert-butyl-4-methylphenol, tri-allate, neonicotinoid insecticides as a group (imidacloprid, thiacloprid, thiamethoxam, clothianidin, acetamiprid), macrolide antibiotics (erythromycin, clarithromycin, azithromycin), and 2-ethylhexyl-4-methoxycinnamate. Analytical methods for additional substances were searched and investigated because they were among those considered for inclusion in the list, but either did not fulfil all selection criteria, in some cases because enough monitoring data were found to exist already, or were not ranked highly enough. These substances were trichlorfon, cyclododecane, aminotriazole (amitrole), dimethenamid-P, diflufenican, dichlofluanid, formaldehyde, triphenyl phosphate, tolylfluanid, ciprofloxacin, and free cyanide. Little or no information on analytical methods was found for trichlorfon, aminotriazole, cyclododecane, and tolylfluanid. For the other compounds analytical methods are available and published. Some of them have already been analysed in the aquatic environment. The analysis of free cyanide in water is difficult. The available analytical methods do not reach the proposed PNEC value of 0.26 µg/l.JRC.H.1-Water Resource

Analytical methods relevant to the European Commission's 2012 proposal on Priority Substances under the Water Framework Directive

This report collects information on chemical analytical methods for the analysis of the new proposed priority substances (PS) of the European Water Framework Directive (WFD) and some existing PS for which the Environmental Quality Standards (EQS) have been changed under the first review of the PS list. First, analytical “standard” methods (ISO, CEN, US EPA) were searched. Then, the EU Member States (MS) were asked via the Chemical Monitoring and Emerging Pollutants (CMEP) expert group to provide validated “in-house methods” used as a national reference and to report their limits of detection (LODs) or quantification (LOQs). Finally, published literature articles were searched to get an overview of today’s analytical performance. Compliance monitoring for the WFD requires the achievement of a LOQ equal or below a value of 30% of the relevant EQS. The achieved method limits of quantification (LOQs) are therefore compared with 30% of the EQS, which is 0.3 × EQS. Very low annual average AA-EQS values in the picogram-per-liter (pg/l) concentration range have been set for several of the new proposed PS: For Cypermethrin 80 pg/l (8 pg/l for coastal salt waters), for Dichlorvos 60 pg/l in coastal waters, for Dicofol 32 pg/l in coastal waters, for 17-alpha-ethinylestradiol 35 pg/l (7 pg/l in coastal waters), for 17-beta-estradiol 80 pg/l in coastal waters, and for Heptachlor/-Heptachlorepoxide 0.2 pg/l (10 fg/l in coastal waters). Dicofol and Heptachlor/-Heptachlorepoxide, for which biota EQS have been set (biota EQS: 33 µg/kg, and 6.7 ng/kg, respectively), however, are intended to be analysed in biota. Moreover, a very challenging water EQS has been set for the already existing PS Brominated Diphenylethers (BDEs) (49 femtogram-per-liter (fg/l), and 2.4 fg/l in coastal waters). However, it is intended that BDEs be analysed in biota (EQS: 8.5 ng/kg). In addition, the water EQS for Polyaromatic Hydrocarbons (PAHs) has been lowered to 0.17 ng/l, and a biota EQS of 2-10 µg/kg added, which is more easy to reach. In general, it is very difficult to reach with currently available analytical instruments LOQs in the low pg/l concentration range. A possibility could be the use of gas chromatography (GC) with high resolution mass spectrometry (HRMS). This technique, however, is not generally available in normal water monitoring laboratories. Also in the field of liquid chromatography mass spectrometry (LC-MS), instruments with improved sensitivity have become available in the last years. Moreover, lower LOQs can be achieved by extracting higher volumes of water (10-1000 liters). These large-volume techniques, however, are very work and time intensive, and very costly, and are therefore not useful for routine WFD compliance monitoring (analysis of one sample per month). The most challenging substances proposed as new PS are: Cypermethrin (EQS: 80 pg/l, and 8 pg/l for coastal salt waters), Dichlorvos (EQS: 60 pg/l in coastal waters), 17-alpha-ethinylestradiol (EQS: 35 pg/l, and 7 pg/l in coastal waters), and 17-beta-estradiol (EQS: 0.4 ng/l, and 80 pg/l in coastal waters). Dicofol, Dioxins and dioxin-like compounds, Heptachlor/Heptachlorepoxide, Hexabromo-cyclododecane (HBCDD), Perfluorooctane sulfonic acid (PFOS), and the BDEs are intended to be analysed in biota. Minor analytical problems could be encountered for the following substances: Aclonifen (EQS: 0.12 µg/l, and 12 ng/l for coastal salt waters), Bifenox (EQS: 12 ng/l, and 1.2 ng/l for coastal waters), Cybutryne (=Irgarol) (EQS: 2.5 ng/l), Diclofenac (EQS: 0.10 µg/l, and 10 ng/l for coastal waters), Quinoxyfen (EQS: 0.15 µg/l, and 15 ng/l for coastal waters), and Terbutryn (EQS: 65 ng/l, and 6.5 ng/l for coastal waters).JRC.H.1-Water Resource

Olfaction scaffolds the developing human from neonate to adolescent and beyond

The impact of the olfactory sense is regularly apparent across development. The foetus is bathed in amniotic fluid that conveys the mother’s chemical ecology. Transnatal olfactory continuity between the odours of amniotic fluid and milk assists in the transition to nursing. At the same time, odours emanating from the mammary areas provoke appetitive responses in newborns. Odours experienced from the mother’s diet during breastfeeding, and from practices such as pre-mastication, may assist in the dietary transition at weaning. In parallel, infants are attracted to and recognise their mother’s odours; later, children are able to recognise other kin and peers based on their odours. Familiar odours, such as those of the mother, regulate the child’s emotions, and scaffold perception and learning through non-olfactory senses. During adolescence, individuals become more sensitive to some bodily odours, while the timing of adolescence itself has been speculated to draw from the chemical ecology of the family unit. Odours learnt early in life and within the family niche continue to influence preferences as mate choice becomes relevant. Olfaction thus appears significant in turning on, sustaining and, in cases when mother odour is altered, disturbing adaptive reciprocity between offspring and caregiver during the multiple transitions of development between birth and adolescence

An Assessment of Three Priority Hazardous Substances at the European Scale

In this report we present a survey of existing information for the assessment of loads of hazardous substances to the European coastal waters. Based on the information available, we select three example substances (PFOS, trifluralin and lindane) for which we perform an assessment of the baseline conditions and (limited) retrospective analysis using direct and inverse modeling. We also suggest criteria and methods to assess future scenarios of chemical loads in response to legislative provisions and accounting for the physico-chemical properties of the substances, based on the use of lumped models but accounting for the spatial variability of environmental processes and emissions.JRC.DDG.H.5-Rural, water and ecosystem resource

Nucleophile Reaktivität von Wittig-Yliden, phosphorylstabilisierten Carbanionen und anorganischen Anionen

Die Disseratation umfasst im 1. Teil die Erweiterung und Ergänzung der von Prof. Dr. Herbert Mayr und Dr. Matthias Patz 1994 erstmals aufgestellten Reaktivitätsskala zur Beschreibung der Reaktivität von Elektrophilen und Nucleophilen. Dies ermöglichte im 2. Teil der Arbeit, die Nucleophilie von Wittg-Yliden, Wadsworth-Horner-Emmons- und Horner-Wittig-Reagenzien zu bestimmen und Aussagen zu Vorhersagbarkeit der Geschwindigkeit ihrer Olefinierungsreaktionen zu treffen. Im dritten Teil werden die Reaktivitäten einfacher anorganischer Anionen betrachtet und gezeigt, dass sich die Reaktionen des ambidenten Thiocyanat-Ions nicht mit Pearsons Hart-und-Weich-Theorie beschreiben lassen

Cyanotoxins: methods and approaches for their analysis and detection

Cyanotoxins are secondary metabolites produced by cyanobacteria, a group of photosynthetic prokaryota especially found in freshwater. In favourable conditions (i.e. high nutrient levels, light intensity, water temperature), cyanobacteria can form blooms, a natural phenomenon characterised by an algal biomass accumulation and the possible release of cyanotoxins in water ecosystems. Toxins represent an emerging threats for the aquatic organisms which can bioaccumulate these compounds and transfer them throughout the food chain to wildlife and humans. Other ways of exposure for humans include the oral, dermal and inhalation route. The consumption of contaminated drinking water, skin contact and swallowing water during recreational activities are among the most frequently reasons for human poisonings caused by cyanotoxins. The associated symptoms usually range from severe headache to fever, respiratory paralysis and in rare case, death. The World Health Organization (WHO) has issued a provisional guideline value of 1 µg/L in drinking water for Microcystin-LR (MC-LR), the most toxic, widespread and common toxin in water supplies. Due to the lack of complete toxicological data for a range of cyanotoxins, their concentration in drinking water is not yet well regulated even in countries belonging to the European Union (EU). In this report, attention is focused on the methodologies commonly used to detect cyanotoxins in water environments. These applications can be grouped in: I) microscopy analysis II) physicochemical methods III) molecular-based methods IV) biochemical-based methods V) chemical methods. Each technique shows specific limitations in terms of sensitivity, reliability and limit of detection. The choice of the best one to use is determined in accordance with the information they provide, the availability of facilities and the technical expertise of the operators. Most of the research about cyanotoxins has been mainly focused on microcystins (MCs). The other cyanotoxins have been much less investigated and more tools need to be developed to overcome this problem. Notwithstanding there is no a single analytical application able to detect all cyanotoxin variants in an environmental sample. Some current methods described in this report show great promise in terms of being simple, cost-effective, specific and sensitive for the analysis of a defined toxin.JRC.D.2-Water and Marine Resource

Review of the 1st Watch List under the Water Framework Directive and recommendations for the 2nd Watch List

The surface water Watch List (WL) under the Water Framework Directive (WFD) is a mechanism for obtaining high-quality Union-wide monitoring data on potential water pollutants for the purpose of determining the risk they pose and thus whether Environmental Quality Standards (EQS) should be set for them at EU level. According to the EQS Directive (article 8b) , this list should be updated every 2 years. The main objectives of this report are: • To present an overview of the data gathered during the 1st year of monitoring of the 1st WL (also called WL dataset in this report), • To assess whether this WL dataset is sufficient to determine the risk posed by the WL substances, and consequently to determine whether any of these substances can be taken out of the WL, • To propose new substance(s) to be included in the second WL, using the information and results from the latest review of the list of priority substances, as well as any other relevant information available at the time of this report. The executive summary first explains the context for the assessment. Then, mirroring the report itself, it presents an overview of the WL dataset for the different WL substances, it specifies the criteria for taking substances out of the WL and the substances proposed on the basis of these criteria, and finally it presents the criteria for including new substances in the WL and the new proposed WL candidates.JRC.D.2-Water and Marine Resource

EU Wide Monitoring Survey of Polar Persistent Pollutants in European River Waters

This study provides the first EU-wide reconnaissance of the occurrence of polar organic persistent pollutants in European river waters. 122 individual water samples from over 100 European rivers, streams or similar water bodies from 27 European Countries were analysed for 35 selected compounds, comprising pharmaceuticals (e.g. carbamazepine, diclofenac), antibiotics (sulfamethoxazole), pesticides (e.g. 2,4-D, mecoprop, bentazone, terbutylazine), perfluorinated compounds PFCs (PFOS, PFOA), benzotriazoles (corrosion inhibitors), hormones (estrone, estradiol), and alkylphenolics (bisphenol A, nonylphenol). Only the dissolved (liquid) water phase, and not the suspend material was investigated. Around 40 laboratories actively participated in this sampling and monitoring exercise organised by the Joint Research Centre¿s Institute for Environment and Sustainability (JRC-IES) of the European Commission (EC) in autumn 2007. The selection of sampling sites was done by the participating EU Member States. The most frequently and at the highest concentration levels detected compounds were benzotriazole, caffeine, carbamazepine, tolyltriazole, and nonylphenoxy acetic acid (NPE1C). Other important substances identified were naproxen, bezafibrate, ibuprofen, gemfibrozil, PFOS, PFOA, sulfamethoxazole, isoproturon, diuron, and nonylphenol. The highest median concentrations of all samples were measured for benzotriazole (226 ng/L), caffeine (72 ng/L), carbamazepine (75 ng/L), tolyltriazole (140 ng/L), and NPE1C (233 ng/L). Relatively high perfluorooctanoate (PFOA) levels were detected in the Rivers Danube, Scheldt, Rhone, and Wyre, and ¿elevated¿ perfluorooctansulfonate (PFOS) concentrations in the Rivers Scheldt, Seine, Krka, Severn, Rhine, and Llobregat. A higher median concentration for all river samples was found for PFOS (6 ng/L), compared to PFOA (3 ng/L). Only about 10 % of the river water samples analysed could be classified as ¿very clean¿ in terms of chemical pollution, since they contained only a few compounds in very low concentrations. The most pristine water samples came from Estonia, Lithuania, and Sweden. For the target compounds chosen, we are proposing limit values in surface waters which are not based on eco-toxicological considerations; these warning levels are (for most compounds) close to the 90th percentile of all water samples analysed. A first EU-wide data set has been created on the occurrence of polar persistent pollutants in river surface waters to be used for continental scale risk assessment and related decision support.JRC.H.5-Rural, water and ecosystem resource

Validation of analytical methods for the WFD “watch list” pilot exercise

Validation of an analytical method is a necessary step in controlling the quality of quantitative analysis. Method validation is an established process which is the provision of documentary evidence that a system fulfills its pre-defined specification or the process of providing that an analytical method is acceptable for its intended purpose. The objectives of the present study were: • to validate a SPE-LC-MS/MS method for the determination of carbamazepine (CBZ), 10,11-dihydro-10,11-dihydroxy-carbamazepine (CBZ-DiOH), sulfamethoxazole (SMZ) and pentafluoropropionic acid (PFPrA) in surface water samples; • to validate a SPE-GC-MS method for the determination of tris (1-chloro-2-propyl) phosphate (TCPP) content in surface water samples. Method validations were performed according to the ISO 17025 requirement and the BT/TF151 WI CSS 99026 document. The calibration curves, working ranges, recoveries, detection and quantification limits, trueness as well as repeatability were determined. The budget uncertainty was also estimated following a top-down approach based on in-house validation data.JRC.H.1-Water Resource