CERTIFICATION REPORT The certification of 202Hg enriched methyl mercury amount content and isotopic composition Hg as methyl mercury in ethanol/water solution: ERM®-AE671

This report describes the production of ERM®-AE671, a 2 % ethanol/water material certified for the amount content of isotopically enriched methyl mercury (CH3(202Hg)) and certified for the isotopic composition of Hg present as methyl mercury (CH3Hg+). The material was produced following ISO Guide 34:2009 [[i]]. Twenty two ampoules of ERM-AE670 containing isotopically enriched methyl mercury chloride (CH3(202Hg)Cl) in 2 % ethanol/water solution were used as starting material. Each ampoule contained approximately 5 g of solution. The content of ERM-AE670 ampoules was gravimetrically diluted with 2 % ethanol/water solution to create enough material for 220 new units. The diluted CH3(202Hg)Cl solution was filled into quartz ampoules which were flame sealed. Between-unit homogeneity was quantified and stability during dispatch and storage were assessed in accordance with ISO Guide 35:2006 [[ii]]. The certified value was obtained from the gravimetric preparations, taking into account the amount of content and isotopic composition of the base material. The certified values were confirmed by isotope dilution mass spectrometry as independent verification method measurements within the scope of accreditation to ISO/IEC 17025:2005 [[iii]]. Uncertainties of the certified values were calculated in compliance with the Guide to the Expression of Uncertainty in Measurement (GUM) [[iv]] and include uncertainties related to possible inhomogeneity, instability and characterisation. The main purpose of the material is to be used as spike isotopic reference material for determination of CH3Hg content in an unknown samples by species-specific isotope dilution through a measurement of the mercury isotope amount ratio R(B) = n(200Hg)/n(202Hg) of CH3Hg, in a blend. The CRM is available in quartz glass ampoules containing 5 g of liquid species solution flame sealed under nitrogen atmosphere. The CRM was accepted as European Reference Material (ERM®) after peer evaluation by the partners of the European Reference Materials consortium.JRC.F.6-Reference Material

Combined uncertainty estimation for the determination of the dissolved iron amount content in seawater using flow injection with chemiluminescence detection

This work assesses the components contributing to the combined uncertainty budget associated with the measurement of the Fe amount content by flow injection chemiluminescence (FI-CL) in <0.2 μm filtered and acidified seawater samples. Amounts of loaded standard solutions and samples were determined gravimetrically by differential weighing. Up to 5% variations in the loaded masses were observed during measurements, in contradiction to the usual assumptions made when operating under constant loading time conditions. Hence signal intensities (V) were normalised to the loaded mass and plots of average normalized intensities (in V kg-1) versus values of the Fe amount content (in nmol kg-1) added to a ‘low level’ iron seawater matrix were used to produce the calibration graphs. The measurement procedure implemented and the uncertainty estimation process developed were validated from the agreement obtained with consensus values for three SAFe and GEOTRACES reference materials (D2, GS and GD). Relative expanded uncertainties for peak height and peak area based results were estimated to be around 12% and 10% (k=2) respectively. The most important contributory factors were the uncertainty on the sensitivity coefficient (i.e. calibration slope) and within-sequence-stability (i.e. the signal stability measured over several hours of operation; in this case 32 h). Therefore, an uncertainty estimation based on the intensity repeatability alone, as is often done in FI-CL studies, is not a realistic estimation of the overall uncertainty of the procedure.JRC.D.2-Standards for Innovation and sustainable Developmen

Report of the Eighth Interlaboratory Comparison organised by the Community Reference Laboratory for Heavy Metals in Feed and Food - Total Cd, Pb, As, Hg and Sn and extractable Cd and Pb in Feed of Plant Origin

The Institute for Reference Materials and Measurements (IRMM)of the Joint Research Centre, a Directorate General of the European Commission, operates the Community Reference Laboratory for Heavy Metals in Feed and Food (CRL-HM). One of its core tasks is to organise interlaboratory comparisons (ILCs) among appointed National Reference Laboratories (NRLs). This report presents the results of the eighth ILC of the CRL-HM which focused on the determination of total Cd, Pb, As, Hg and Sn and extractable amounts of Cd and Pb in feed of plant origin following Directive 2002/32/EC of the European Parliament and of the Council on undesirable substances in animal feed. The test material used in this exercise was a candidate reference material, the matrix being rye grass. The material was relabelled and dispatched to the participants on the second half of October 2009. Each participant received approximately 10 g of test material. Thirty participants from 25 member states registered to the exercise of which 27 reported results for total Cd, Pb and Hg, 23 for extractable Pb, 22 for extractable Cd and for total As and 16 for total Sn. One laboratory did not report results due to a breakdown of the instrumentation, and one laboratory reported results only for Hg for the same reason. The assigned values (Xref) for total Cd, Pb, As, Hg and Sn were the candidate certified values as obtained during the certification. The assigned values for extractable Cd and Pb were provided by IRMM using isotope dilution-inductively coupled plass-mass spectrometry (ID-ICP-MS). Participants were invited to report the uncertainty of their measurements, which was provided by the majority of them. The laboratory performance was evaluated using z- end zeta-scores in accordance with ISO 13528. The standard deviation for proficiency assessment (also called target standard deviation), was fixed to 15% of the assigned values for all measurands on the basis of the outcome of previous ILCs organis.JRC.DDG.D.6-Food Safety and Qualit

IMEP-29: Total Arsenic, Cadmium, Lead, Mercury and Tin, and Extractable Cadmium and Lead in Feed of Plant Origin - Interlaboratory Comparison Report

The Institute for Reference Materials and Measurements (IRMM) of the Joint Research Centre (JRC), a Directorate-General of the European Commission, operates the International Measurement Evaluation Programme® IMEP. It organises interlaboratory comparisons (ILC's) in support to EU policies. This report presents the results of an ILC which focussed on the determination of total As, Cd, Pb, Hg and Sn, and extractable Cd and Pb in feed of plant origin following Directive 2002/32/EC of the European Parliament and of the Council on undesirable substances in animal feed. The test material used in this exercise was a candidate reference material, the matrix being rye grass. The material was relabelled and dispatched to the participants in the second half of October 2009. Each participant received one bottle containing approximately 10 g of test material. Sixty-two participants from 23 countries registered to the exercise of which 59 reported results. The assigned values (Xref) for total Cd, Pb, As, Hg and Sn were the reference values as obtained during the certification campaign taking place simultaneously to the ILC. The assigned values for extractable Cd and Pb were provided by IRMM using isotope dilution-inductively coupled plasma-mass spectrometry (ID-ICP-MS). Participants were invited to report the uncertainty of their measurements, which was done by around 90% of them. The laboratory performance was evaluated using z-and zeta-scores in accordance with ISO 13528. The standard deviation for proficiency assessment (also called target standard deviation), was fixed at 15% for all measurands on the basis on the outcome of previous ILCs. The outcome of the exercise was altogether positive, with 68% or more of the participants reaching satisfactory z-scores for all measurands except for total As and Hg, which appeared to be problematic in this exercise, showing a non-normal results distribution and tendency to very high means. The zeta-scores were not as good as the z-scores, which indicates a persisting problem of appropriate uncertainty estimation. Finally, total Sn was included for the first time in an ILC. Results were better than expected, but can certainly be improved.JRC.DG.D.6 - Food Safety and Qualit

IMEP-111: Total Cadmium, Lead, Arsenic, Mercury and Copper and Extractable Cadmium and Lead in Mineral Feed - Report of the Eleventh Interlaboratory Comparison Organised by the European Union Reference Laboratory for Heavy Metals in Feed and Food

The Institute for Reference Materials and Measurements (IRMM) of the Joint Research Centre, a Directorate-General of the European Commission, operates the European Union Reference Laboratory for Heavy Metals in Feed and Food (EU-RL-HM). One of its core tasks is to organize interlaboratory comparisons (ILCs) among appointed National Reference Laboratories. This report presents the results of the eleventh proficiency test (PT) of the EU-RL-HM which focused on the determination of total Cd, Pb, As, Hg and Cu and extractable Cd and Pb in mineral feed according to Directive 2002/32/EC of the European Parliament and of the Council on undesirable substances in animal feed. The test material used in this exercise was the Certified Reference Material (CRM) BCR-032, Moroccan phosphate rock. The material was relabelled to prevent identification by the participants and was dispatched the second half of October 2010. Each participant received one bottle containing approximately 100 g of test material. Thirty-one laboratories from 26 countries registered to the exercise of which 28 reported results for total Cd and total Pb, 25 for total Hg and total Cu, 23 for total As and for extractable Cd and extractable Pb. The assigned values (Xref) for total Cd, As and Cu are the indicative values taken from the BCR-032 certificate. The assigned values (Xref) for total Pb, total Hg and for extractable Cd and Pb were provided by IRMM using isotope dilution-inductively coupled plasma-mass spectrometry (ID-ICP-MS). For total Cd, As, Hg and Cu and for extractable Cd, the uncertainty of the assigned values (uref) was calculated by combining the uncertainty of the characterization (uchar) and a contribution for between-bottle homogeneity (ubb) (which was calculated from the certification report). For total and extractable Pb the number of replicates performed to establish the assigned value was higher (11 replicates) than for the other measurands (6 replicates). Since the aliquots were taken from different bottles, it was assumed that uchar included a contribution for the homogeneity. For total Cd, As and Cu, uchar were taken from the CRM certificate as indicated by the producer. For extractable Cd the same uchar as for total Cd was used. For total Pb and Hg and for extractable Pb, uchar was calculated according to the ISO Guide for the Expression of Uncertainty in Measurement (GUM). Participants were invited to report the uncertainties of their measurements. This was done by the majority of the laboratories taking part in this exercise.JRC.DG.D.6-Food Safety and Qualit

IMEP-31: Total Arsenic, Cadmium, Copper, Lead and Mercury, as well as Extractable Cadmium and Lead in Mineral Feed - Interlaboratory Comparison Report

The Institute for Reference Materials and Measurements (IRMM) of the Joint Research Centre (JRC), a Directorate-General of the European Commission, operates the International Measurement Evaluation Programme® IMEP. It organises interlaboratory comparisons (ILC's) in support to EU policies. This report presents the results of an ILC which focussed on the determination of total As, Cd, Cu, Pb, and Hg, as well as extractable Cd and Pb in mineral feed according to Directive 2002/32/EC of the European Parliament and of the Council on undesirable substances in animal feed. The test material used in this exercise was the Certified Reference Material (CRM) BCR-032 (Moroccan phosphate rock) from the IRMM. The material was relabelled and each participant received one bottle containing approximately 100 g of test material. Fifty-six laboratories from 26 countries registered to the exercise and 51 of them reported results. Total As, Cd, Cu and Hg were certified in BCR-032 in 1979. The material was re-analysed by two expert laboratories and As an Cd values could be confirmed. Copper could not be analysed in time by an expert laboratory, and thus it was decided to use the indicative value from the certificate as assigned value. The assigned values for total Hg and total Pb were determined at IRMM by a primary method. The same method was used to determine extractable Cd and Pb, whose mass fractions appeared to be identical to the respective total mass fractions and thus the same assigned values were used. The standard deviation for proficiency assessment was set at 11 % for total As, 10 % for total and extractable Cd, 9 % for total Cu, and at 15 % for total Hg based on the modified Horwitz equation and/or the outcome of previous ILCs organised by IMEP. For total and extractable Pb, was set at 25 %. The majority of the laboratories reported uncertainties with their results and were rated with z- and ζ-scores (zeta-scores) in accordance with ISO 13528. Performances appear to be good for total & extractable Cd and total & extractable Pb, the percentage of satisfying z-scores ranging between 85 % and 89 %. Share of satisfactory z-scores are significantly lower for total As (61 %), Cu (67 %) and in particular for Hg (47 %). No distinct reason could be given, but it seems altogether that the analytical methods were not always adjusted to the inorganic test material, reflected by some influence of applied technique and inappropriate choice of reference material.JRC.DG.D.6-Food Safety and Qualit

Intrusion detection by automatic extraction of the semantics of computer language grammars

Interactions between a user and information systems are based on an inescapable architectural pattern: user data is integrated into requests whose analysis is carried out by an interpreter that drives the system’s activity. Attacks targeting this architecture (known as injection attacks) are very frequent and particularly severe. Most often, this detection is based only on the syntax of this data (e.g. the presence of keywords or sub-strings typical of attacks), with limited knowledge of their semantics (i.e. the effects of the query on the information system). The automatic extraction of these semantics is, therefore, a major challenge, as it would significantly improve the performance of Intrusion Detection Systems (IDS). By leveraging the novel advancement in Natural Language Processing (NLP) it appears feasible to automatically and transparently infer the semantics of user inputs. This Master Thesis provides a framework centred on the instrumentalization of parsers. We focused on parsers for their pivotal role as the first layer of interaction with user inputs and their responsibility for the performed operation on an information system. Our research findings indicate the possibility of constructing an intrusion detection system based on this framework. Moreover, the focus on parser technologies demonstrates the potential for dynamically preventing the processing of malicious input (i.e. creating Intrusion Prevention Systems)

IMEP-33: Total Cadmium and Lead in Baby Food - Interlaboratory Comparison Report, December 2011

The Institute for Reference Materials and Measurements (IRMM) of the Joint Research Centre (JRC), a Directorate-General of the European Commission, operates the International Measurement Evaluation Programme® (IMEP). It organises interlaboratory comparisons (ILC's) in support to EU policies. This report presents the results of an ILC which focussed on the determination of total Cd and Pb in baby food in support of Commission Regulation (EC) No 1881/2006 of 19 December 2006 setting maximum levels for certain contaminants in foodstuffs. The test material used in this exercise was baby food formula purchased in a local pharmacy and prepared by the Reference Material Unit of the IRMM for this exercise. Each participant received one bottle containing approximately 15 g of test material. Sixty-six laboratories from 23 countries registered to the exercise and 61 of them reported results. Participants were asked to analyse the measurands in the powder and in the reconstituted form. The assigned value for total Cd was determined by LGC Ltd (UK) and IRMM using direct isotope dilution inductively coupled plasma mass spectrometry. The assigned value for total Pb was determined at IRMM using the same technique as for Cd. The standard deviation for proficiency assessment ˆ was set at 22 % of the assigned value based on the modified Horwitz equation. Laboratories were rated with z- and ζ-scores (zeta-scores) in accordance with ISO 13528. Most of the participants reported uncertainties with their results. The outcome of this exercise is clearly characterised by the very low level of Cd and Pb content in the test material which triggered a high number of "less than" values, overestimation especially for lead very likely due to contamination, and a visible method influence in the case of lead. The results were also evaluated with regard to the reported limit of detection and some incoherencies were observed here as well.JRC.D.5-Food Safety and Qualit

Report of the fifth Interlaboratory Comparison organised by the Community Reference Laboratory for Heavy Metals in Feed and Food Total Cd, Pb and As as extractable Cd and Pb in Mineral Feed

The Institute for Reference Materials and Measurements (IRMM) of the Joint Research Centre, a Directorate-General of the European Commission, operates the Community Reference Laboratory for Heavy Metals in Feed and Food (CRL-HM). One of its core tasks is to organise interlaboratory comparisons (ILCs) among appointed National Reference Laboratories (NRLs). This report presents the results of the fifth ILC of the CRL-HM which focused on the determination of total Cd, Pb and As and extractable Cd and Pb in mineral feed according to Directive 2002/32/EC1 of the European Parliament and of the Council on undesirable substances in animal feed. The test material used in this exercise was a commercial mineral feed for piglets provided by AGES, Zentrum Analytik und Mikrobiologie, in Austria. The material, naturally contaminated, was processed, bottled, labelled and dispatched by the Reference Materials Unit of the IRMM. The samples were dispatched on the second half of October 2008. Each participant received one bottle containing approximately 30 g of test material. Thirty-one participants from 25 countries registered to the exercise of which 29 submitted results for total Cd and for total Pb, 22 submitted results for total As and 27 submitted results for extractable Cd and for extractable Pb. Two laboratories did not submit results due to a break down in the instruments that were to be used for the analyses. The assigned values (Xref) for total and extractable Cd and Pb were provided by IRMM using isotope dilution-inductively coupled plasma-mass spectrometry (ID-ICP-MS). The analytical uncertainty of Xref, uchar, was calculated according to the ISO Guide to the Expression of Uncertainty in Measurement (GUM)2. The assigned value for total arsenic was provided by the Studiecentrum voor Kernenergie (SCK-CEN) using neutron activation analysis. The analytical uncertainty of Xref, uchar, for total arsenic was calculated according to GUM3,4. Homogeneity and stability studies were subcontracted to Bayer Antwerpen. The uncertainties of the respective assigned values, uref, were calculated combining the analytical uncertainty, uchar, with a contribution for the between-bottle homogeneity, ubb, and for the short term stability of the test material, usts. Participants were invited to report the uncertainty of their measurements. This was done by 25 laboratories for total Cd, 24 laboratories for total Pb, 18 laboratories for total As, 22 laboratories for extractable Cd and 21 laboratories for extractable Pb. The laboratory performance was evaluated using z and zeta scores in accordance with ISO 135285. The standard deviations for proficiency assessment (also called target standard deviation) were calculated using the modified Horwitz equation6 and were between 15 and 16 % for all the measurands .JRC.D.4 - Isotope measurement

IMEP-113: determination of total cadmium and lead in baby food - Interlaboratory Comparison Report - December 2011

This report presents the results of the thirteen proficiency test (PT) which focussed on the determination of total Cd and Pb in baby food according to Commission Regulation (EC) No 1881/2006 of 19 December 2006 setting maximum levels for certain contaminants in foodstuffs. The test material used in this exercise was baby food formula purchased in a local pharmacy and prepared by the Reference Material Unit of the IRMM for this exercise. Each participant received one bottle containing approximately 15 g of test material. Thirty five laboratories from 26 countries registered to the exercise and all of them reported results. Participants were asked to analyse the measurands in the powder and in the reconstituted form (powder diluted with water, 1:8 fold, to mimic the product as consumed). The assigned value for total Cd was determined by LGC Ltd (UK) and IRMM using direct isotope dilution inductively coupled plasma mass spectrometry. The assigned value for total Pb was determined at IRMM using the same technique as for Cd. The standard deviation for proficiency assessment was set at 22 % of the assigned value based on the modified Horwitz equation. Laboratories were rated with z- and ζ-scores (zeta-scores) in accordance with ISO 13528. The outcome of this exercise is clearly influenced by the very low level of Cd and Pb content in the test material which triggered: - a high number of "less than" values; - overestimated values especially for lead very likely due to contamination. Reported results were satisfactory for total cadmium in both forms, (powder and in the reconstituted formula).JRC.D.5-Food Safety and Qualit