Dioxins and PCBs in solid matter from the river Elbe, its tributaries and the North Sea (longitudinal profile, 2008)

The most recent longitudinal sampling profile, taken in 2008 from the river Elbe and its tributaries Vltava (Moldau), Mulde, Spittelwasser, Saale, Bode the Stör and the North Sea near Helgoland, shows contaminations of solid matter with polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans (dioxins, PCDD/Fs) and polychlorinated biphenyls (PCBs). While the dioxin contamination is mainly located along the German part of the catchment, PCBs are more abundant in the Czech section. In some of the 43 solid samples investigated high levels of contamination were detected. Selected orientation benchmarks for dioxins and PCBs in sediments and fish are exceeded, suggesting potential hazards for organisms in the contaminated rivers and for human consumption. Elevated dioxin concentrations in the Spittelwasser-Mulde system and the Saale catchment, together with consistent dioxin congener patterns Elbe downstream of the confluence, indicate that the region of Bitterfeld-Wolfen is the predominant source of the dioxin pollution, which can be traced until far off shore in the sediments of the North Sea near Helgoland. Thermal metal, presumably Magnesium production via fused salt electrolysis during the 2nd world war is the most probable primary, historic source of the dioxin contamination. The spatial distribution of dioxins as seen in 2008 matched well with earlier campaigns in 2002, both for aquatic solids and alluvial soils, suggesting minor change of the situation since then. Also the samples from the North Sea revealed elevated levels of dioxins that display the congener pattern from the Bitterfeld-Wolfen Region. In contrast to the PCDD/Fs, PCBs are mainly present in the in the Upper Elbe in the Czech Republic. After the German border PCBs display an overall decrease. Other than PCDD/Fs, PCB emissions into the Elbe cannot be attributed to a dominant source or region. Indicator PCBs did rise more or less constantly in concentration until the German border, suggesting a variety of cumulative emission sources along the whole Czech stretch. Thus, no specific recommendation on how to decrease the PCB pressure on the River Elbe can be given on the basis of the data acquired in this study. Detailed regional scale monitoring in the Czech stretch, together with the evaluation of production statistics regarding potential PCB sources are needed here. After all the PCB toxicity in eel is exceeding that of PCDD/F up to an order of magnitude (investigations of eels taken after the flood event in August 2002). As an amendment to the chemical analyses, two Ah-receptor based bioassays (DR CALUXR and EROD), which display the dioxin–like activity of all pollutants present, were performed on a subset of the samples (blind study). For The DR CALUXR the comparison revealed a good agreement between the HRGC/HRMS results along the German stretch and the bioassay. However, along the Czech section of the Elbe the DR CALUXR displayed a 10 times higher dioxin-like activity than the chemical analyses. This suggests that the solid material in the Czech section contains additional persistent dioxin-like acting pollutants. In comparison to the DR CALUXR test, the EROD assay displayed even higher dioxin-like activities. The differences can be explained by the fact that the clean up procedure for the DR CALUXR eliminated the less persistent organic pollutants in the extract, while the EROD procedure remained sensitive to those. Regarding the risk for the aquatic food chain and the human diet, the reduction of PCBs in the River Elbe ecosystem appears crucial as indicated by the dominance of the PCB over the PCDD/Fs in toxicity equivalents detected in eel samples.JRC.H.1-Water Resource

Polychlorinated Biphenyls (PCBs) at the JRC Ispra Site: Air Concentrations, Congener Patterns and Seasonal Variation-Results from the 1st Year of Atmospheric Monitoring of Persistent Organic Pollutants (POPs) at the Ispra EMEP Station

With the aim of gathering information on atmospheric POPs concentrations in one of the ¿monitoring holes¿ in Europe, a monitoring and research atmospheric site was set up at the JRC Ispra Site. Regular monitoring activities started on April 2005 and finished on March 2007 in this first stage. Air and precipitation samples were collected regularly throughout this period. First results obtained on PCBs ambient air concentrations (7 indicator PCBs: 28, 52, 101, 118, 153, 138 and 180) from the first year of monitoring (April 2005-2006) are presented in this report. In addition, congener patterns, air gas/particulate phase partition and seasonal variation are discussed. The range of ¿7 PCB total (gas + particulate phases) monthly averaged concentration during the sampling period varied from 76 ± 17 to 31 ± 5 pg m-3. Concentrations are within the range of those reported for rural, semi-rural or remote areas around the world. A seasonal variation of air concentrations was observed, with higher levels in summer months (higher average temperatures) and lower values in winter (lower average temperatures). In addition, indications of seasonal variation affecting congener patterns and the gas - particulate phase partition for the studied PCB were found. PCBs were in general predominant in the air gas phase, dominating therefore the contribution to the total airborne concentration, although the percentage in the gas phase decreases when increasing level of chlorination and during the low temperature season (winter months). A one year data set of PCB ambient air concentrations has been generated, constituting a useful dataset that now remains available for further use, such as inclusion in the EMEP network or for POPs fate modelling validation and future risk assessment of POPs in sub-alpine locations. More results for other target POPs are under processing and are expected to be reported soon.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

HCHs in solid matter from the River Elbe, its tributaries and the North Sea

The River Elbe (Czech: Labe ) is one of the major rivers of Central Europe. It originates in the Krkonoše Mountains of northwestern Czech Republic before traversing Bohemia (Czech Republic), then Germany and flowing into the North Sea at Cuxhaven, 110 km northwest of Hamburg. Its total length is 1,094 km. The Elbe’s major tributaries are the Vltava (German: Moldau), Saale, Havel, Mulde, SchwarzeElster, and Ohre rivers. The Elbe River basin, comprising the Elbe and its tributaries, has a catchment area of 148,268 km2, the fourth largest in Europe. The basin spans four countries, with its largest parts in Germany (65.5%) and the Czech Republic (33.7%). Much smaller parts lie in Austria (0.6%) and Poland (0.2%). The basin is inhabited by 24.5 million people (1). Organochlorine pesticides are man-made organics chemicals. Hexachlorocyclohexanes (HCHs) have been extensively used and are therefore found widely distributed in the environment. HCHs are listed under the Stockholm Convention on POPs (persistent organic compound) and are included into the priority list of Water Frame Directive. Here we show the results of HCHs in solids matter of 35 different sites along the River Elbe, selected tributaries, and the North SeaJRC.H.1-Water Resource

Residues of antimicrobial agents and related compounds of emerging concern in manure, water and soil Part 1 – Pilot-sampling campaign in Slovakia and first findings

In a thinking of circular economy, the understanding how problematic chemical substances may migrate and travel across the various boundaries of a life-cycle is of pivotal importance to ensure that the philosophy of reuse and recycle is not jeopardized by new risks of contamination. In this framework, veterinary medicinal products (VMP) and there, in particular the anti-microbial agents are a growing source of concern in the context of the reuse of processed manure as a fertilizer. This is mainly due to the lack of understanding of their role in the development of anti-microbial resistances and their propagation. While the mechanistic study how the propagation takes places at molecular genetic level receives much attention, the actual data situation on occurrence of VMPs and AMAs in agricultural land remains opaque and poor. In order to prepare a larger and EU-wide monitoring exercise on the waters exposed directly or indirectly to the (processed) manure a first pilot exercise was organised to develop an appropriate protocol. This first report compiles a series of background information collected, describes the execution of first pilot sampling and presents the first elements in the development of a validated analytical methods.JRC.D.2-Water and Marine Resource

Water Framework Directive. Watch List Method. Analysis of diclofenac in water

Validation of an analytical method is a necessary step in controlling the quality of quantitative analysis. Method validation is an established process which provides documentary evidence that a system fulfills its pre-defined specification, or shows that an analytical method is acceptable for its intended purpose. The purpose of the present study was to validate an SPE-LC-MS/MS method for the determination of diclofenac in surface water samples according to the requirements laid down in ISO 17025. The calibration curves, working ranges, recoveries, detection and quantification limits, trueness as well as repeatability were determined. The uncertainty budget was estimated following a top-down approach based on in-house validation data. The expanded relative uncertainty was estimated as 13 and 8% at low and high concentration levels respectively, based on 15 replicate measurements on 5 days, and as 30 and 18% for a single measurement performed on a single day.JRC.H.1 - Water Resource

Water Framework Directive Watch List Method Analytical method for determination of compounds selected for the first Surface Water Watch List

Validation of an analytical method is a necessary step in controlling the quality of quantitative analysis. Method validation is an established process which provides documentary evidence that a system fulfils its pre-defined specification, or shows that an analytical method is acceptable for its intended purpose. The purpose of the present study was to develop and validate analytical procedures for the quantitative determination in surface water of substances selected in the First Watch List. Two different methods were developed and validated: • A multi-residual method based on SPE-LC-MS/MS analysis, using OASIS HLB as sorbent material for the extraction of 1 litre water samples and quantitative determination of EE2, E2, E1, diclofenac, azithromycin, clarythromycin, methiocarb acetamiprid, clothianidin, imidacloprid, thiacloprid, thiametoxam and oxadiazon. • A multi-residual method based on LLE-GC-MS, using hexane as extraction solvent for the extraction of 0.01 litre water samples and quantitative determination of BHT, EHMC and Triallate. The calibration curves, working ranges, recoveries, detection and quantification limits, trueness as well as repeatability were determined. The uncertainty budget was estimated based on in-house validation data. JRC.H.1-Water Resource

Analysis of chemical constitutents and additives in hydraulic fracturing waters 1. Technical review and proposal for a non-target approach

This technical report is a first one of series of reports addressing the issue of chemical constituents and additives occurring in the waters related to hydraulic fracturing in the exploitation of unconventional hydrocarbons. Specific focus is on the types of chemical constituents being addressed so far in flowaback, produced waters and potentially exposed ground and surface water. It gives on overview on typical approaches. With regard to organic constituents it addresses the typically examined compounds and investigates to which extent non-targeted approaches with accurate mass spectrometry can be used to fill existing knowledge gaps. The concept of an envisaged feasibility study for a imoproved baseline assessment is described, too.JRC.D.2-Water and Marine Resource

Water Framework Directive, Watch List Method - Analysis of 17b-estradiol and estrone

Validation of an analytical method is a necessary step in controlling the quality of quantitative analysis. Method validation is an established process which provides documentary evidence that a system fulfils its pre-defined specification, or shows that an analytical method is acceptable for its intended purpose. The purpose of the present study was to validate an SPE-LC-MS/MS method for the determination of 17b-estradiol and estrone in surface water samples according to the requirements laid down in ISO 17025. The calibration curves, working ranges, recoveries, detection and quantification limits, trueness as well as repeatability were determined. The uncertainty budget was estimated following a top-down approach based on in-house validation data. For 17-estradiol, the expanded relative uncertainty was estimated as 16 and 15% at low and high concentration levels respectively, based on 15 replicate measurements on 5 days, and as 50 and 44% for a single measurement performed on a single day. For estrone, the expanded relative uncertainty was estimated as 13 and 12% at low and high concentration levels respectively, based on 15 replicate measurements on 5 days, and as 42 and 38% for a single measurement performed on a single day.JRC.D.2 - Water and Marine Resource

Comparison of Monitoring Approaches for Selected Priority Pollutants in Surface Water CMA On-Site 2

27 Analytical Laboratories from eleven EU Member States and two non-EU countries have participated in a technical on-site event during which sampling and analytical methodologies for chemical monitoring according to proposed WFD provisions have been compared. Coordination of the project was provided by the European Commission Joint Research Centre in collaboration with the Italian Water Research Institute, the Hungarian Ministry of Environment and Water and the Serbian Ministry for Environment and Spatial Planning. The Laboratories had been invited to take samples from a major European river according to their standard protocols and to analyse them for PAHs, PBDE and Nonyl-, Octylphenol. It was shown that even some of the most challenging WFD priority substances, selected on purpose for this exercise, can be measured at WFD relevant concentrations (0.3 x EQS) with methods currently applied in Member States. Depending on the analyte group, the obtained results were not within proposed data quality limits for some participants and therefore further development of methods and harmonisations of efforts is suggested.JRC.H.5 - Rural, water and ecosystem resource