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 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

Residues of antimicrobial agents and related compounds of emerging concern in manure, water and soil

In order to prepare a larger and EU-wide monitoring exercise aiming at the characterisation of processed manure as well as on the waters exposed directly or indirectly to the (processed) manure a first pilot exercise was organised to develop an appropriate protocol. While the first related report compiled a series of background information collected, the results on the analytical characterization of pilot sites operated by the Slovak University of Agriculture in Nitra are presented and discussed. Manure samples (processed and untreated), runoff, groundwater and surface water samples, were analysed for 488 compounds covering typical representatives of herbicides, fungicides, insecticides, pharmaceuticals, ingredients of personal care products and other industrially used chemicals. For 60 of these compounds (corresponding to 12 %), concentration above the established limits of quantification of these novel multi-compound technique were obtained. The study demonstrates the applicability of the hybrid target / non-target analytical approach called "Compound Fishing" and the reports presents the design for a related EU-wide exercise. Although this study does characterize the respective test sites, it delivers an understanding of environmental pressures created on sites and under real-field scenarios. The experimental work conducted allows also to establish a link between the evaluation of scientific literature, the biogeochemical modelling and the field conditions scenarios of when processed manure is applied.JRC.D.2-Water and Marine Resource

EU Wide Monitoring Survey on Waste Water Treatment Plant Effluents

In the year 2010, effluents from 90 European waste water treatment plants (WWTPs) were collected and analysed in total for 160 organic chemicals and 20 inorganic trace elements. The analyses were complemented by applying also effect-based monitoring approaches aiming at estrogenicity and dioxin-like toxicity analysed by in vitro reporter gene bioassays, and yeast and diatom culture acute toxicity optical bioassays. The analytical work was performed in six European expert laboratories. This European-wide monitoring study on the occurrence of micropollutants in WWTP effluents represents the largest EU wide monitoring survey on WWTP effluents ever performed. It produced a comprehensive data set on many so far only locally investigated “emerging” compound classes including pharmaceuticals and personal care products (PPCPs), veterinary (antibiotic) drugs, perfluoroalkyl substances (PFASs), organophosphate ester flame retardants, pesticides (and some metabolites) or industrial chemicals such as benzotriazoles (corrosion inhibitors), polycyclic musk fragrances, x-ray contrast agents, Gadolinium compounds, and siloxanes. The obtained results show the presence of 131 target organic compounds in European wastewater effluents, in concentrations ranging from low nanograms to milligrams per liter. These results obtained from 90 different European WWTPs allow the calculation of a European median level for the chemicals investigated. The most relevant compounds identified in the effluent water samples in terms of frecquency of detection, maximum, average and median concentration levels were Sucralose, Acesulfame K (artificial sweeteners), PFOA, PFHxA, PFHpA, PFOS (perfluoroalkyl substances), N,N’-Diethyltoluamide (DEET; insect repellent), Benzotriazoles (corrosion inhibitors), the pharmaceuticals Bisoprolol, Carbamazepine, Ciprofloxacine, Citaprolam, Clindamycine, Codeine, Diltiazem, Diphenhydramin, Eprosartan, Fexofenadine, Flecainide, Gemfibrozil, Fluconazole, Haloperidol, Ibersartan, Ibuprofen, Ketoprofen, Oxazepam, Risperidone, Sulfamethoxazole, Telmisartan, Tramadol, Trimethoprim, Venlafaxin, the organo-phosphate ester flame retardants Tri-iso-butylphosphate (TIBP), Tributylphosphate (TBP), Tris(2-chloroethyl)phosphate (TCEP), Tris(2-chloroisopropyl)phosphate (TCPP), Tris(2-butoxyethyl)phosphate (TDCP), Tris(2-butoxyethyl)phosphate (TBEP), Triphenyl-phosphate (TPP), 2-Ethylhexyldiphenyl-phosphate (EHDPP), the x-ray contrast media Amidotrizoic acid, Iohexol, Iopromid, Iomeprol, Iopamidol, the pesticides Terbutylazine, Terbutylazine-desethyl (metabolite), MCPA, Mecoprop, Diuron, Triclosan (antibacterial), and Gadolinium (from magnetic resonance imaging contrast media used in hospitals).JRC.H.1-Water Resource

Occurrence and levels of selected compounds in European compost and digestate samples

This report describes work conducted by the European Commission’s Joint Research Centre (JRC) in the context of an Administrative Arrangement between DG Environment and the JRC. This work aimed at the generation, within a limited timeframe, of a large amount of analytical data, with high scientific and statistical value, for a number of compost and digestate types (afterwards referred to as COMDIG samples), to help provide a general overview and estimation of that possible variability within and between different COMDIG materials. The report includes the results of a targeted and independent screening of typical European situations of COMDIG materials with regard to the occurrence and levels of compounds of concern, many of which have never been assessed at a pan-European level. In total, 139 samples, mostly taken as grab samples and originating from 15 countries, were assessed for 22 minor and trace elements and 92 organic compounds including ingredients of personal care products and pharmaceuticals. The underlying analytical methods are carefully documented with regard to their performance characteristics. Where available, the so-called “horizontal” standards were followed. The results obtained are assessed statistically. Although the analysed single samples are insufficient to make any statement on the performance of the treatment processes leading to COMDIG samples, this collective of data provide a glimpse of the pan-European situation as regards the studied compounds.JRC.H.1-Water Resource

Feasibility of a Monitoring Mechanism Supporting a Watch List under the Water Framework Directive

This report describes work conducted by the European Commission’s Joint Research Centre in the context of its support to the implementation of the Water Framework Directive 2000/60/EC. The work aimed at the feasibility assessment of an experimental monitoring exercise in support to a so-called Watch List Mechanism in a collaborative design involving EU Member States laboratories and some 200 official monitoring station operated by the Member States. The report includes all details on sampling stations, performance of analytical methods as well as the results of the analyses of all samples with regard to the occurrence and levels of 20 compounds of concern. In total, 219 whole water samples originating from 25 EU Member States and 2 other European countries, were assessed for contents of acesulfame, glyphosate and its metabolite AMPA, 1H-Benzotriazole and tolyltriazoles, bisphenol A, triclosan and triclocarban, carbamazepine and its metabolite 10,11-dihydro-10,11-dihydroxycarbamazepine, sulfamethoxazole, perfluoropropionic acid, tris-2-chloropropyl phosphate, methyl tert-butyl ether, silver, boron and chloride (Cl-) in water. Furthermore, 23 sediment samples were analysed for decabromodiphenylethane and decabromodiphenyl ether. The underlying analytical methods are carefully documented with regards to their performance characteristics. Obtained results are assessed statistically and where possible compared to other findings. Although the analysed single samples are insufficient to make any statement on the performance of the treatment processes leading to the compost, the collective of data allows having a glance at the pan-European situation as regards the studies compounds. Background information from literature describing the situation before the survey is included, too. The report is divided into a core part and two annexes. For practical reasons, the report is split into two volumes: Volume 1 contains the report and the single analytical results; volume 2 contains the documentation of the sampling stations.JRC.H.1-Water Resource

Characterization of the Danube River sediments using the PMF multivariate approach

Chemical composition data for the Danube River and its tributaries sediments were analyzed using positive matrix factorization (PMF). The objective was to identify both natural and anthropogenic sources affecting the catchment area of the river. During the Joint Danube Survey 2 (JDS2) campaign 148 bottom sediments samples were collected. The following elements were analyzed by means of the X-Ray fluorescence (XRF) technique: Al, As, Ca, Cd, Cl, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, P, Pb, S, Si, Ti, V and Zn. Mercury was determined by cold vapour atomic absorption spectrometry (CV-AAS). Three factors were obtained considering the whole data set (Danube and tributaries), identified as: (1) a carbonate component characterized by Ca and Mg; (2) an alumino-silicate component dominated by Si and Al content and the presence of some metals attributed to natural processes; (3) an anthropogenic source identified by Hg, S, P and some heavy metals load. To better characterize the role of tributaries, the Danube and tributaries data sets, were also analyzed separately. The same three source factors were identified in the Danube data set. For the tributaries, a four-factor source model gave one further factor dominated by S and P, which could be attributed to the use of fertilizers in agriculture.JRC.H.1-Water Resource