The certification of fipronil sulfone and the sum of fipronil and fipronil sulfone expressed as fipronil in egg powder ERM-BB125

This report describes the production of the ERM-BB125, which is an egg material certified for the mass fraction of fipronil sulfone and the sum of fipronil and fipronil sulfone expressed as fipronil. This material was produced following ISO 17034 and is certified in accordance with ISO Guide 35. Eggs from a farm embargoed by the Belgian food safety authorities were freeze-dried, cryo-milled and homogenised. Between-unit homogeneity was quantified and stability during dispatch and storage were assessed in accordance with ISO Guide 35. The material was characterised by an interlaboratory comparison of laboratories of demonstrated competence and adhering to ISO/IEC 17025. Technically invalid results were removed but no outlier was eliminated on statistical grounds only. Uncertainties of the certified values were calculated in accordance with the Guide to the Expression of Uncertainty in Measurement (GUM)and include uncertainties related to possible inhomogeneity, instability and characterisation. The material is intended for the quality control and assessment of method performance. As with any reference material, it can be used for establishing control charts or during validation studies. The CRM is available in sealed glass vials containing at least 5 g of dried egg powder. The minimum amount of sample to be used is 1 g of the dry material.JRC.F.6-Reference Material

CERTIFICATION REPORT The certification of the mass fraction of pesticides in cucumber: ERM-BC403

This report describes the production of ERM®-BC403, which is a cucumber material certified for the mass fraction of selected pesticides. This material was produced following ISO Guide 34:2009 and is certified in accordance with ISO Guide 35:2006. Cucumbers from a biodynamic farm were used as base material. The cucumbers were transformed into slurry, freeze-dried and cryogenically milled. The obtained product was partially reconstituted with water and a separate portion was spiked with a pesticide mixture. The contaminated portion was then mixed with the rest of the material, homogenised and accurately dispensed into 100-ml vials. A second freeze-drying cycle was applied with the vials placed directly in the freeze-dryer. Prior to analysis the resulting sponge of dry cucumber must be reconstituted with a specific volume of water. Between-unit homogeneity was quantified and stability during dispatch and storage were assessed in accordance with ISO Guide 35:2006 [ ]. The material was characterised by an interlaboratory comparison of laboratories of demonstrated competence and adhering to ISO/IEC 17025. Technically invalid results were removed but no outliers were eliminated on statistical grounds only. Uncertainties of the certified values were calculated in accordance with the Guide to the Expression of Uncertainty in Measurement (GUM) [ ] and include uncertainties related to possible inhomogeneity, instability and characterisation. The material is intended for the quality control / assessment of method performance. As with any reference material, it can be used for establishing control charts or used for validation of analytical methods. The CRM is available in sets of two glass vials containing each approximately 3.2 g of dried material. The vials were sealed under an atmosphere of argon. The minimum amount of sample to be used is 2.5 g of the reconstituted material.JRC.F.6-Reference Material

CERTIFICATION REPORT: The certification of the mass fraction of pesticides in soya: ERM®-BC700

This report describes the production of ERM-BC700, which is a soya material certified for the mass fraction of selected pesticides. This material was produced following ISO Guide 34:2009 [ ] and is certified in accordance with ISO Guide 35:2006. Soya beans (Glycine max) originating from Uruguay were sprayed with 11 pesticides in solution. The beans were air dried, cryo-milled and homogenised. Between unit-homogeneity was quantified and stability during dispatch and storage were assessed in accordance with ISO Guide 35:2006. The material was characterised by an interlaboratory comparison of laboratories of demonstrated competence and adhering to ISO/IEC 17025. Technically invalid results were removed but no outlier was eliminated on statistical grounds only. Uncertainties of the certified values were calculated in accordance with the Guide to the Expression of Uncertainty in Measurement (GUM) and include uncertainties related to possible inhomogeneity, instability and characterisation. The material is intended for the quality control / assessment of method performance. As with any reference material, it can be used for establishing control charts or validation studies. The CRM is available in glass vials containing 32 g of cryo-milled soya powder which were sealed under an atmosphere of nitrogen. The minimum amount of sample to be used is 2 gJRC.F.6-Reference Material

IMEP-23: The Eight WFD PAHs in Water in Presence of Humic Acid

IMEP-23 is linked to the Water Framework Directive (WFD). It studied the capability of control laboratories to measure the eight WFD PAHs in the presence of humic acid in a water matrix. Humic acid simulates natural colloidal organic matter and is known to adsorb PAHs. This gives rise to various issues that are of large importance for the control laboratories. Participants' results were benchmarked against the IMEP certified reference values. On average 80 % of the z scores was satisfactory. Zeta scores were calculated for those laboratories who provided an uncertainty estimate. These were less satisfactory and this shows that many laboratories encounter difficulties to provide a reasonable uncertainty estimate.JRC.D.4-Isotope measurement

Schwermetalle und prioritäre organische Schadstoffe in Böden Bulgariens

0\. Title 1\. Introduction and goals 1 2\. Pollution in the environment 4 2.1. Sources 5 2.1.1. Sources of heavy metals 5 2.1.2. Sources of organic pollutants 6 2.2. Transport and deposition 9 2.3. Persistence in environment and ecotoxicology 11 2.4. Bulgaria 14 2.4.1 Soil types 14 2.4.2 Soil pollution 15 3\. Investigation area 18 3.1 Geographical position and geology of investigated territories 19 3.1.1 Pirdop - Zlatitza valley 19 3.1.2 Plovdiv region 22 3.1.3 National park "Rogen" 25 4\. Analytical and statistical methods 29 4.1 Pedological analysis 29 4.2 Analytical methods for determination of heavy metals 30 4.3 Analytical methods for determination of organic compounds 31 4.4 Statistical methods 33 5\. Results and discussion 35 5.1 Distribution of heavy metals in soil horizons 35 5.1.1 Distribution of heavy metals in arable soils, damaged by metal pollution 35 5.1.1 Distribution of heavy metals in forest soils, situated in background areas 40 5.2 Distribution of Cd, Cu, Ni, Pb, and Zn in particle - size fraction extracted from polluted and unpolluted soil profiles 44 5.3 Determination of priority organic compounds in investigated soils 54 5.3.1 Polyaromatic hydrocarbons (PAH) 55 5.3.2 Organochlorine pesticides 59 5.4 Statistical analysis 62 6\. Calculation of critical loads 63 6.1 Introduction 63 6.2 Definition of critical limits 64 6.3 Model 67 6.4 Calculation of critical load for Pb and Cd 69 6.4.1 Input data 69 6.4.2 Calculation of Critical loads 73 7\. Summary 78 8\. Zusammenfassung 86 9\. References 90 Appendix AcknowledgemensThe soils are considered as a main and most important natural resource for Bulgaria, which are used in agriculture, forestry and many other branches of national economy. But the quality of the soils in same locations and their multifunctionality are threaten with the impact of a great number of point and diffuse sources of inorganic and organic pollutants. These sources of pollutants are connected with industrial activities during last 40 years. This investigation was carried out as an attempt to find out a method for determination the background contents of some inorganic substances, which is not influenced by the degree of pollution in soils. For this purpose the total content of Cd, Cu, Ni, Pb, and Zn had been determined in whole soil samples and in particle-size fractions extracted from main soil horizons of five representative soil profiles, situated in polluted and unpolluted sites in South Bulgaria. The investigated soils are distinguished in two groups: polluted P1, P2, P3 (arable lands) and non-polluted P4, P5 (forest soils). Determined concentrations of studied elements in soil surface of P1, P2 and P3, which are in the impact zone of point sources of heavy metals, are for Cd: 2- 32 mg/kg; Cu: 136-180 mg/kg; Ni: 34-54 mg/kg; Pb: 33-1370 mg/kg; Zn: 65-1890 mg/kg. The determined values varying in wide ranges and for elements (Cu, Pb and Zn) prevail the maximum permissible concentrations (MPC) according Bulgarian state standards, showing significant level of pollution from near Cu-Pb-Zn plants. The determined concentrations of investigated elements in forest soils are for Cd: <1mg/kg; Cu: 10-34 mg/kg; Ni: 15-80 mg/kg; Pb: 41-42 mg/kg; Zn: 70-153 mg/kg and they are near to background values for Bulgarian soils. In studied soils was observed clear trend for concentration of the analysed elements in clay fraction (particles <0.002 mm) in comparison to the whole soil. The content of investigated elements in sand fraction (particles 2.0 - 0.2 mm) separated from soil horizons is close to the mean background content of these elements in Bulgarian soils and in terrigenous soil forming rocks. The result show that with level of significance of 90%, sand fraction extracted from A- horizon brings information about geogenic/background content of investigated metals in soils, independently whether the soils are polluted or not polluted. Determined total concentration of investigated element in studied soils were used as a base for calculation of the critical load for lead and cadmium (metals from first priority) according to Protocol of heavy metals signed in 1998. The critical load is the acceptable total load of anthropogenic heavy metal inputs (deposition, fertilizers, other anthropogenic sources). It corresponds to the sum of tolerable outputs from the system (harvest, leaching) minus the natural inputs (weathering release). Calculated critical loads for lead and cadmium on a regional scale for both types of land use vary as follows: Cadmium: 1.0 - 3.12 mg.m-2.yr-1 for arable lands and 4.89 - 5.80 mg.m-2.yr-1 for forest soils. Lead: 7.0 - 10.39 mg.m-2.yr-1 for arable lands and 15.7 - 18.4 mg.m-2.yr-1 for forest soils. The other aim of this study was to determine the concentrations of priority organic pollutants in investigated soils and to obtain the basic data for content of this component as well in arable as in forest soils. The concentrations of SUM-PAH ranges from 31.01 µg/kg to 56.44 µg/kg d. w. for arable lands, and for forest soil these concentrations are between 22.09 µg/kg and 28.66 µg/kg d.w. Unlike PAHs, the determined concentration of DDX-compound vary in a wide ranges from 11.24 µg/kg to 950.43 µg/kg d.w. The SUM-DDX concentration in the most contaminated soil (P2 = 950.43 ng/g d.w.) was at least a factor of 30 higher than other samples.Der Boden wird als wichtigste Naturresource fuer die Landwirtschaft, Forstwirtschaft und andere Zweige der Volkswirtschaft Bulgariens betrachtet. Die Qualitaet des Bodens ist an vielen Standorten durch punktuelle und diffuse anorganische und organische Schadstoffquellen gefaehrdet, die innerhalb der letzten 40 Jahre eingetragen wurden. Die vorliegende Arbeit beschaeftigt sich mit Methoden der Differenzierung anorganischer Schadstoffe in Gesamtgehalte an Cd, Cu, Ni, Pb und Zn in einzelnen Bodenhorizonten kontaminierter und unkontaminierter Boeden aus Suedbulgarien, differenziert nach Konrgroessenfraktionen. Die untersuchten Boeden wurden in 2 Gruppen unterteilt: kontaminierte Profile P1, P2, P3 (landwirtschaftliche Nutzung) und P4, P5 (Waldnutzung). In den kontaminierten Oberflaechenproben der Bodenprofile P1, P2 und P3 wurden fuer Cd: 2-32 mg/kg; Cu: 136-180 mg/kg; Ni: 34-54 mg/kg; Pb: 33-1370 mg/kg und Zn: 65-1890 mg/kg ermittelt. Die bestimmten Gehalte variieren ueber einen breiten Konzentrationsbereich, fuer die Elemente Cu, Pb und Zn wurden die maximal zulaessigen Konzentrationen (MPC) der bulgarischen Standards ueberschritten, einen signifikanten Level der Kontamination durch nahegelegene Cu-Pb-Zn- Fabriken illustrierend. Die Gehalte in den Waldbodenprofilen betragen Cd: <1mg/kg; Cu: 10-34 mg/kg; Ni: 15-80 mg/kg; Pb: 41-42 mg/kg; Zn: 70-153 mg/kg, sie liegen im Bereich der Backgroundlevel fuer bulgarische Boeden. Die Untersuchungen zeigen eine klare Anreicherung in der Tonfraktion (Partikelkorngroesse (0,002 mm), relativ zum Gesamtgehalt betrachtet. Die Gehalte in der Sandfraktion (Partikelkorngroesse 2,0 - 0,2 mm) lagen nahe den Backgroundwerten fuer bulgarische Boeden und denen im Anstehenden. Statistische Analysen ermittelten signifikante (90%) Übereinstimmungen zwischen den bestimmten Gehalten in der Sandfraktion der A- und C-Horizonte, unabhaengig von Kontaminationsgrad. Auf der Basis der bestimmten Gehalte wurden Critical Loads fuer die prioritaeren Schwermetalle Blei und Cadmium nach dem 1998 unterzeichneten Protokoll kalkuliert, die einen Indikator fuer die oekologische Sensibilitaet einer Region gegenueber diesem Schwermetall anzeigen und bei Überschreiten eine staatliche Reduktionsmassnahme indizieren, auch wenn sie entfernt von der Quelle via atmosphaerische Deposition auftreten. Die Werte korrespondieren mit den Austraegen durch Ernte und Leaching sowie die natuerlichen Eintraege durch Verwitterung. Die berechneten Critical Loads fuer Cadmium und Blei betragen: 1,0 - 3,12 mg.Cd m-2.yr-1 und 7,0-10,39 mg.Pb m-2.yr-1 fuer landwirtschaftliche Boeden und 4,89 - 5,80 mg.Cd m-2.yr-1 und 15,7-18,4 mg.Pb m- 2.yr-1 fuer Waldboeden. Weiterhin wurden in den Oberflaechenproben prioritaere organische Umweltchemikalien bestimmt, um Hintergrundwerte fuer diese Klasse von Kontaminanten zu bestimmen. Die PAH- Konzentrationen rangierten von 31,01 µg SUM-PAH kg-1 bis 56,44 µg SUM-PAH kg-1 TS fuer landwirtschaftliche Boeden und zwischen 22.09 µg SUM-PAH kg-1 und 28,66 µg SUM-PAH kg-1 TS fuer Waldboeden. Diese Konzentrationen repraesentieren sehr gerineg Hintergrundgehalte, die keine Kontamination durch diese Verbindungen darstellen. Im Gegensatz zu den PAHs wurden DDX- Kongenere in z.T. deutlich erhoehten Konzentrationen von 11,24 bis zu 950,43 µg SUM-DDX kg-1 TS nachgewiesen. Die hoechsten Gehalte im Boden P2 waren um den Faktor 30 hoeher als in anderen Proben

Development of a new Cucumber Reference Material for Pesticide Residue Analysis: Feasibility Study for Material Processing, Homogeneity and Stability Assessment

The feasibility of the production of a reference material for pesticide residue analysis in a cucumber matrix was investigated. Cucumber was spiked at 0.075 mg/kg with 15 pesticides, namely acetamiprid, azoxystrobin, carbendazim, chlorpyrifos, cypermethrin, diazinon, (α+β)-endosulfan, fenitrothion, imazalil, imidacloprid, iprodione, malathion, methomyl, tebuconazole and thiabendazole. Three different strategies were considered for material processing, based on the physicochemical properties of the vegetable and the target pesticides. As a result, a frozen spiked slurry of fresh cucumber, a spiked freeze-dried cucumber powder, and a freeze-dried cucumber powder spiked by spraying of the powder were studied. The effects of processing and aspects related to material reconstitution were evaluated by monitoring the pesticide levels in the three materials. Two analytical methods based on LC-MS/MS and GC-MS/MS respectively were developed and validated in-house. The spiked freeze-dried cucumber powder was selected as the most feasible material and more exhaustive studies of homogeneity and stability of pesticide residues in the matrix were carried out. Homogeneity between units was satisfactory at a sample intake of dried material as low as 0.1 g. A 9-week stability study was undertaken following an isochronous design at -20 ºC, 4 ºC and 18 ºC, with -70 ºC as reference temperature. The pesticides tested showed adequate stability at -20 ºC during the 9 weeks period as well as at -70 ºC for a period of 18 months. These results constitute a good basis for the development of a new candidate reference material for selected pesticides in a cucumber matrix.JRC.D.5-Standards for Food Bioscienc

Towards Less Manipulated Reference Materials for Food and Environmental Analysis

The need for reliable and comparable analytical data in food and environmental monitoring stipulate the need for "new/alternative" types of reference materials matching more closely real world samples. Matrix certified reference materials are required in the validation of methods of analyses of real environmental samples, because matrix effects may result in bias of the analytical results. The study was designed to assess the equivalence between three different processing options for the production of food/environmental reference materials. Finding an appropriate analyte/matrix combination was the first step. A stable analyte, PCBs (polychlorinated biphenyls) was chosen in this case, in order not to complicate the study too much by choosing analytes that could potentially degrade. A fatty fish such as mackerel was chosen as in such matrices the naturally occurring levels of PCBs are sufficiently high not to create too many difficulties for the quantification. Spiking should be avoided because this would compromise the closeness to a real sample and would complicate the homogeneity of the fresh material. The fatty matrix is also a challenge in the processing, as a homogeneous distribution of the fatty parts has to be ensured. PCBs 28, 52, 101, 118, 138, 153 and 180 have been selected because they are frequently determined. They show a high occurrence in environmental and waste samples and represent both lower and higher chlorinated congeners. This paper summarises the protocol used to determine the homogeneity of the three material presentations. And the results from the analyses carried out to measure the PCB content of batches stored at different conditions. Evaluation of the suitability of the test materials will be performed with respect to its behaviour under different storage conditions.JRC.DG.D.2-Reference material

IMEP-23: The Eight EU-WFD Priority PAHs in Water in the Presence of Humic Acid

Recently, the International Measurement Evaluation Programme (IMEP) organized an interlaboratory comparison on total concentrations of eight polycyclic aromatic hydrocarbons (PAHs) in natural inland waters. It was carried out in support to the European Union Water Framework Directive (EU-WFD) that lists these eight as priority substances. As sample matrix, we used groundwater spiked with humic acid as a model for the colloidal substances that are present in natural inland waters. Humic substances can adsorb PAHs, but we found that some laboratories did not apply analytical procedures that sufficiently accounted for this. One of these laboratories was involved in establishing the reference values. We show how this impacted on the reliability of their measurements. Many participants accepted our invitation to report their measurement uncertainties. We assessed their results against our reference values and uncertainties, and provided z and zeta scores. Although the overall measurement capability appears satisfactory, there is room for improvement of analytical procedures as regards the use of measurement standards.JRC.D.5-Food Safety and Qualit

CCQM-K102 Polybrominated diphenyl ethers in sediment

The key comparison CCQM-K102: Polybrominated diphenyl ethers in sediment was coordinated by the JRC, Directorate F – Health, Consumers & Reference Materials, Geel (Belgium) under the auspices of the Organic Analysis Working Group (OAWG) of the Comité Consultatif pour la Quantité de Matière (CCQM). Thirtheen National Metrology institutes or Designated Institutes and the JRC participated. Participants were requested to report the mass fraction (on a dry mass basis) of BDE 47, 99 and 153 in the freshwater sediment study material. The sediment originated from a river in Belgium and contained PBDEs (and other pollutants) at levels commonly found in environmental samples. The comparison was designed to demonstrate participants' capability of analysing non-polar organic molecules in abiotic dried matrices (approximate range of molecular weights: 100 to 800 g/mol, polarity corresponding to pKow < -2, range of mass fraction: 1-1000 µg/kg). All participants (except one using ultrasonic extraction) applied Pressurised Liquid Extraction or Soxhlet, while the instrumental analysis was performed with GC-MS/MS, GC-MS or GC-HRMS. Isotope Dilution Mass Spectrometry approach was used for quantification (except in one case). The assigned Key Comparison Reference Values (KCRVs) were the medians of thirteen results for BDE 47 and eleven results for BDE 99 and 153, respectively. BDE 47 was assigned a KCRV of 15.60 µg/kg with a combined standard uncertainty of 0.41 µg/kg, BDE 99 was assigned a KCRV of 33.69 µg/kg with a combined standard uncertainty of 0.81 µg/kg and BDE 153 was assigned a KCRV of 6.28 µg/kg with a combined standard uncertainty of 0.28 µg/kg. The k-factor for the estimation of the expanded uncertainty of the KCRVs was chosen as k = 2. The degree of equivalence (with the KCRV) and its uncertainty were calculated for each result. Most of the participants to CCQM-K102 were able to demonstrate or confirm their capabilities in the analysis of non-polar organic molecules in abiotic dried matrices. Throughout the study it became clear that matrix interferences can influence the accurate quantification of the PBDEs, if the analytical methodology applied is not appropriately adapted and optimised. This comparison shows that quantification of PBDEs at the µg/kg low-middle range in a challenging environmental abiotic dried matrix can be achieved with relative expanded uncertainties below 15 % (more than 70 % of participating laboratories), well in line with the best measurement performances in the environmental analysis field.JRC.F.6-Reference Material