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

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

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 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

Comparing measured and modelled PFOS concentrations in a UK freshwater catchment and estimating emission rates

The lifecycle, sources and fate of perfluorooctane sulfonate (PFOS) continue to generate scientific and political interest, particularly since PFOS was listed by the Stockholm Convention and largely restricted in Europe. It continues to be detected in aquatic environments, with only limited studies into the on-going sources. This paper explores PFOS emissions discharged by the general population into a small catchment comprising two rivers in the UK. A sampling campaign was undertaken to improve our understanding of population-derived PFOS sources from sewage treatment plants (STPs) and in rivers. A corresponding modelling exercise allowed an emission estimate of 13 μg/day/per capita to be derived for the Aire and Calder rivers. PFOS emission was linked to STP discharges bylinear regression of measured and modelled concntrations (R2 = 0.49–0.85). The model was able to accurately estimate the spatial trends of PFOS in the rivers, while predicted concentrations were within a factor of three based on per capita emission values taken from the literature. Measured PFOS concentrations in rivers suggested that emissions from STPs are partially dependent on treatment type, where plants with secondary or tertiary treatment such as activated sludge processes emit less PFOS, possibly due to increased partitioning and retention. With refinements based on the type of treatment at each STP, predictions were further improved. The total PFOS mass discharged annually via rivers from the UK has been estimated to be between 215 and 310 kg, based on the per capita emission range derived in this study

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

Technical proposals for the safe use of processed manure above the threshold established for Nitrate Vulnerable Zones by the Nitrates Directive (91/676/EEC)

Potential exists to reconcile on-going technological and market developments for the recycling of nutrients in a circular economy with the objective of protecting water bodies against pollution originating from livestock manure. The objective of this report is to help define those harmonised criteria that could allow nitrogen (N) fertilisers, partially or entirely derived from manure through processing, to be used in areas subject to the ceiling of 170 kg N/ha/yr prescribed in Annex III of the Nitrates Directive following otherwise identical provisions applied to N containing chemical fertilisers in the Nitrates Directive (91/676/EEC), while ensuring the achievement the Directive’s objectives and adequate agronomic benefits. Such materials are referred to as REcovered Nitrogen from manURE (RENURE) in this report. This work combines biogeochemical modelling techniques, analytical measurements and quantitative (meta-analysis) and qualitative literature review techniques to assess use impacts of candidate RENURE materials on environmental pollution, including nitrate leaching. The results indicated that processed manure characterised by a ratio of total organic carbon to total N ≤ 3 or a mineral N to total N ratio ≥ 90% may have a similar N leaching potential and agronomic efficiency to Haber-Bosch derived and equivalent chemical N fertilisers. In particular, nitrogen-rich processed manure materials, such as scrubbing salts, mineral concentrates, and liquid digestates obtained through centrifugation and/or advanced solids removal might be able to meet these requirements. To comply with the objectives of environmental protection, it is, however, necessary to combine the use of RENURE with good management practices, including the use of living plant covers or equivalent measures, low NH3 emission application techniques and good RENURE storage conditions. Altogether, this report proposes a set of material and use requirements to enable the safe use of RENURE in areas with water pollution by nitrogen, in amounts above the threshold established by the Nitrates Directive (91/676/EEC). It is concluded that the possible implementation of RENURE as part of manure management systems enables a progression towards a more circular economy and an avenue for increased resource efficiency in the EU food production system.JRC.B.5-Circular Economy and Industrial Leadershi

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