Dokument-ID Dokumenttyp Autoren/innen Persönliche Herausgeber/innen Haupttitel Abstract Auflage Verlagsort Verlag Herausgeber (Institution) Erscheinungsjahr Titel des übergeordneten Werkes Jahrgang/Band ISBN Veranstaltung Veranstaltungsort Beginndatum der Veranstaltung Enddatum der Veranstaltung Ausgabe/Heft Erste Seite Letzte Seite URN DOI Lizenz Datum der Freischaltung OPUS4-44257 Zeitschriftenartikel Vogl, Jochen; Kipphardt, Heinrich; Richter, Silke; Bremser, Wolfram; Arvizu Torres, M.; Lara Manzano, J.; Buzoianu, M.; Hill, S.; Petrov, P.; Goenaga-Infante, H.; Sargent, M.; Fisicaro, P.; Labarraque, G.; Zhou, T.; Turk, G. C.; Winchester, M.; Miura, T.; Methven, B.; Sturgeon, R.; Jährling, R.; Rienitz, O.; Mariassy, M.; Hankova, Z.; Sobina, E.; Krylov, A. I.; Kustikov, Y. A.; Smirnov, V. V. Establishing comparability and compatibility in the purity assessment of high purity zinc as demonstrated by the CCQM-P149 intercomparison For the first time, an international comparison was conducted on the determination of the purity of a high purity element. Participants were free to choose any analytical approach appropriate for their institute's applications and services. The material tested was a high purity zinc, which had earlier been assessed for homogeneity and previously used in CCQM-K72 for the determination of six defined metallic impurities. Either a direct metal assay of the Zn mass fraction was undertaken by EDTA titrimetry, or an indirect approach was used wherein all impurities, or at least the major ones, were determined and their sum subtracted from ideal purity of 100 %, or 1 kg/kg. Impurity assessment techniques included glow discharge mass spectrometry, inductively coupled plasma mass spectrometry and carrier gas hot extraction/combustion analysis. Up to 91 elemental impurities covering metals, non-metals and semi-metals/metalloids were quantified. Due to the lack of internal experience or experimental capabilities, some participants contracted external laboratories for specific analytical tasks, mainly for the analysis of non-metals. The reported purity, expressed as zinc mass fraction in the high purity zinc material, showed excellent agreement for all participants, with a relative standard deviation of 0.011 %. The calculated reference value, w(Zn) = 0.999 873 kg/kg, was assigned an asymmetric combined uncertainty of + 0.000025 kg/kg and - 0.000028 kg/kg. Comparability amongst participating metrology institutes is thus demonstrated for the purity determination of high purity metals which have no particular difficulties with their decomposition / dissolution process when solution-based analytical methods are used, or which do not have specific difficulties when direct analysis approaches are used. Nevertheless, further development is required in terms of uncertainty assessment, quantification of non-metals and the determination of purity of less pure elements and/or for those elements suffering difficulties with the decomposition process. Bristol Institute of Physics Publishing Bureau International des Poids et Mesures (BIPM) 2018 Metrologia : international journal of pure and applied metrology 55 2 211 221 10.1088/1681-7575/aaa677 2018-02-21 OPUS4-24485 Zeitschriftenartikel Schiel, D.; Rienitz, O.; Jährling, R.; Güttler, B.; Matschat, Ralf; Scharf, Holger; Birkhahn, Jürgen; Labarraque, G.; Fisicaro, P.; Borchers, U.; Schwesig, D. Metrological concept for comparable measurement results under the European water framework directive: demonstration of its applicability in elemental analysis Within the scope of a project of the 'European Association of National Metrology Institutes' (EURAMET), a European metrological dissemination System (network) providing traceable reference values assigned to matrix materials for validation purposes is described and put to the test. It enables testing laboratories (TL) to obtain comparable results for measurements under the 'EU Water Framework Directive 2000/60/EC' (WFD) and thus, to comply with a core requirement of this very directive. The dissemination system is characterized by the fact that it is available to all laboratories throughout Europe which intend to perform measurements in the context of the WFD and that it can ensure sustainable metrological traceability to the International System of Units (SI) as a reference point for the measurement results. This Dissemination system is set up in a hierarchical manner and links up the level of the national metrology institutes (NMI) with that of the TLs via an intermediate level of calibration laboratories (CL) by comparison measurements. The CLs are expert laboratories with respect to the measurement of the analytes considered here (within the project, the CLs are called potential calibration laboratories (PCL)) and are additionally involved in the organization of comparison measurements within the scope of regional quality assurance (QA) systems. Three comparison measurements have been performed to support the approach. A total of about 130 laboratories participated in this exercise with the focus on the measurement of the priority substances Pb, Cd, Hg, and Ni defined in the WFD. The elemental concentrations in the water samples roughly corresponded to one of the established environmental quality standards (EQS), the annual average concentration (AA-EQS), which is defined in the daughter Directive 2008/105/EC of the WFD. It turned out that a significant number of TLs still need to improve their measurement methods in order to be able to fulfill the Minimum requirements of the WFD, in particular, with regard to the elements Cd and Hg probably due to their low EQS values. Furthermore, it became obvious that the hierarchical Dissemination system suggested here actually corresponds to the measuring capabilities of the three participating Groups (NMIs, PCLs, and TLs). Berlin Springer 2011 Accreditation and quality assurance 16 10 489 498 10.1007/s00769-011-0792-z 2016-02-19 OPUS4-36930 Zeitschriftenartikel Richter, Janine; Fettig, I.; Philipp, Rosemarie; Jakubowski, Norbert; Panne, Ulrich; Fisicaro, P.; Alasonati, E. Determination of tributyltin in whole water matrices under the European water framework directive Monitoring of water quality is important to control water pollution. Contamination of the aquatic systemhas a large effect on human health and the environment. Under the European Water Framework Directive(WFD) 2000/60/EC and the related directive on environmental quality standards (EQS) in the field of waterpolicy 2008/105/EC, the need for sensitive reference methods was highlighted. Since tributyltin (TBT) isone of the WFD listed priority substances a method was developed which is capable to qualify and quantifythe pollutant at the required low WFD EQS of 0.2 ng L⁻¹ in whole water bodies, i.e. in non-filtered watersamples with dissolved organic carbon and suspended particulate matter. Therefore special attention waspaid on the interaction of TBT with the suspended particulate matter and humic substances to obtain acomplete representation of the pollution in surface waters. Different water samples were investigatedvarying the content of organic dissolved and suspended matter. Quantification was performed usingspecies-specific isotope dilution (SSID) and gas chromatography with inductively coupled plasma massspectrometry (GC-ICP-MS). Different sample treatment strategies were evaluated and compared. Theprocess of internal standard addition was investigated and optimized, hence the equilibrium betweeninternal standards and matrix is of primary importance to perform accurate SSID. Samples spiked at EQSlevel were analyzed with a recovery between 95 and 105 %. Additionally real surface water samples wereinvestigated and the TBT concentration for the whole water body was determined and compared withconventional routine analysis method. 2016 Journal of Chromatography A 1459 112 119 10.1016/j.chroma.2016.06.068 2016-07-22 OPUS4-32696 Zeitschriftenartikel Alasonati, E.; Fabbri, B.; Fettig, Ina; Yardin, C.; Del Castillo Busto, M.E.; Richter, Janine; Philipp, Rosemarie; Fisicaro, P. Experimental design for TBT quantification by isotope dilution SPE-GC-ICP-MS under the European water framework directive In Europe the maximum allowable concentration for tributyltin (TBT) compounds in surface water has been regulated by the water framework directive (WFD) and daughter directive that impose a limit of 0.2 ng L-1 in whole water (as tributyltin cation). Despite the large number of different methodologies for the quantification of organotin species developed in the last two decades, standardised analytical methods at required concentration level do not exist. TBT quantification at picogram level requires efficient and accurate sample preparation and preconcentration, and maximum care to avoid blank contamination. To meet the WFD requirement, a method for the quantification of TBT in mineral water at environmental quality standard (EQS) level, based on solid phase extraction (SPE), was developed and optimised. The quantification was done using species-specific isotope dilution (SSID) followed by gas chromatography (GC) coupled to inductively coupled plasma mass spectrometry (ICP-MS). The analytical process was optimised using a design of experiment (DOE) based on a factorial fractionary plan. The DOE allowed to evaluate 3 qualitative factors (type of stationary phase and eluent, phase mass and eluent volume, pH and analyte ethylation procedure) for a total of 13 levels studied, and a sample volume in the range of 250-1000 mL. Four different models fitting the results were defined and evaluated with statistic tools: one of them was selected and optimised to find the best procedural conditions. C18 phase was found to be the best stationary phase for SPE experiments. The 4 solvents tested with C18, the pH and ethylation conditions, the mass of the phases, the volume of the eluents and the sample volume can all be optimal, but depending on their respective combination. For that reason, the equation of the model conceived in this work is a useful decisional tool for the planning of experiments, because it can be applied to predict the TBT mass fraction recovery when the experimental conditions are drawn. This work shows that SPE is a convenient technique for TBT pre-concentration at pico-trace levels and a robust approach: in fact (i) number of different experimental conditions led to satisfactory results and (ii) the participation of two institutes to the experimental work did not impact the developed model. Amsterdam Elsevier B.V. 2015 Talanta 134 576 586 10.1016/j.talanta.2014.11.064 2016-02-20 OPUS4-37407 Zeitschriftenartikel Alasonati, E.; Fettig, I.; Richter, Janine; Philipp, Rosemarie; Milačič, R.; Sčančar, J.; Zuliani, T.; Tunç, M.; Bilsel, M.; Gören, A.; Fisicaro, P. Towards tributyltin quantification in natural water at the Environmental Quality Standard level required by the Water Framework Directive The European Union (EU) has included tributyltin (TBT) and its compounds in the list of priority water pollutants. Quality standards demanded by the EU Water Framework Directive (WFD) require determination of TBT at so low concentration level that chemical analysis is still difficult and further research is needed to improve the sensitivity, the accuracy and the precision of existing methodologies. Within the frame of a joint research project "Traceable measurements for monitoring critical pollutants under the European Water Framework Directive" in the European Metrology Research Programme (EMRP), four metrological and designated institutes have developed a primary method to quantify TBT in natural water using liquid-liquid extraction (LLE) and species-specific isotope dilution mass spectrometry (SSIDMS). The procedure has been validated at the Environmental Quality Standard (EQS) level (0.2 ng L−1 as cation) and at the WFD-required limit of quantification (LOQ) (0.06 ng L−1 as cation). The LOQ of the methodology was 0.06 ng L−1 and the average measurement uncertainty at the LOQ was 36%, which agreed with WFD requirements. The analytical difficulties of the method, namely the presence of TBT in blanks and the sources of measurement uncertainties, as well as the interlaboratory comparison results are discussed in detail. Elsevier B.V. 2016 Talanta 160 499 511 10.1016/j.talanta.2016.07.056 2016-09-20 OPUS4-34015 Zeitschriftenartikel Labarraque, G.; Oster, C.; Fisicaro, P.; Meyer, Christian; Vogl, Jochen; Noordmann, J.; Rienitz, O.; Riccobono, F.; Donet, S. Reference measurement procedures for the quatification of platinum-group elements (PGEs) from automotive exhaust emissions The major source of the anthropogenic platinum group element (PGE) emission is attributed to the use of catalytic converters in automobiles. This paper describes the work performed by three National Metrology Institutes (Laboratoire national de métrologie et d’essais, by the Physikalisch-technische bundesanstalt, Bundesanatalt für materialforschung und prûfung), in the framework of the Joint Research Project 'PartEmission' under the European Metrology Research Program. An analytical procedure based on a cationic exchange protocol and the isotope dilution or standard addition using an Inductived Coupled Plasma Mass Spectrometer, ICP-MS, for the quantification of the elements Pt, Pd and Rh from automotive exhaust emissions is described. Results obtained on a road dust certified reference (BCR 723) material showed a good agreement with the certified values, at ng/g levels, and relative expanded uncertainties within the range of 7-10%. Analysis of filters impacted with automotive exhaust particle emissions (from a diesel engine) showed the amount of collected PGE at levels of 10-1000 pg/filter. Their quantifications followed the developed analytical protocol that had been carried out with relative expanded uncertainties in the range of a few per cent up to 20% per filter. Nevertheless, a lack of homogeneity between the filters was observed, making the comparison between the project partners difficult in the sake of the validation of their analytical procedures on real samples. New York, NY Gordon and Breach 2015 International journal of environmental analytical chemistry 95 9 777 789 10.1080/03067319.2015.1058931 2016-02-20 OPUS4-30458 Zeitschriftenartikel Rienitz, O.; Schiel, D.; Görlitz, V.; Jährling, R.; Vogl, Jochen; Lara-Manzano, J.V.; Zon, A.; Fung, W.-H.; Buzoianu, M.; De Sena, R.C.; Dos Reis, L.A.; Valiente, L.; Yim, Y.-H.; Hill, S.; Champion, R.; Fisicaro, P.; Bing, W.; Turk, G.C.; Winchester, M. R.; Saxby, D.; Merrick, J.; Hioki, A.; Miura, T.; Suzuki, T.; Linsky, M.; Barzev, A.; Máriássy, M.; Cankur, O.; Ari, B.; Tunc, M.; Konopelko, L.A.; Kustikov, Y.A.; Bezruchko, M. Final report on CCQM-K87: Mono-elemental calibration solutions The aim of this comparison was to demonstrate the capability of national metrology institutes to measure elemental mass fractions at a level of w(E) ≈ 1 g/kg as found in almost all mono-elemental calibration solutions. These calibration solutions represent an important link in traceability systems in inorganic analysis. Virtually all traceable routine measurements are linked to the SI through these calibration solutions. Every participant was provided with three solutions of each of the three selected elements chromium, cobalt and lead. This comparison was a joint activity of the Inorganic Analysis Working Group (IAWG) and the Electrochemical Analysis Working Group (EAWG) of the CCQM and was piloted by the Physikalisch-Technische Bundesanstalt (PTB, Braunschweig, Germany) with the help of the Bundesanstalt für Materialforschung und -prüfung (BAM, Berlin, Germany), the Centro Nacional de Metrología (CENAM, Querétaro, Mexico) and the National Institute of Standards and Technology (NIST, Gaithersburg, USA). A small majority of participants applied inductively coupled plasma optical emission spectrometry (ICP OES) in combination with a variety of calibration strategies (one-point-calibration, bracketing, calibration curve, each with and without an internal standard). But also IDMS techniques were carried out on quadrupole, high resolution and multicollector ICP-MS machines as well as a TIMS machine. Several participants applied titrimetry. FAAS as well as ICP-MS combined with non-IDMS calibration strategies were used by at least one participant. The key comparison reference values (KCRV) were agreed upon during the IAWG/EAWG meeting in November 2011 held in Sydney as the added element content calculated from the gravimetric sample preparation. Accordingly the degrees of equivalence were calculated. Despite the large variety of methods applied no superior method could be identified. The relative deviation of the median of the participants' results from the gravimetric reference value was equal or smaller than 0.1% (with an average of 0.05%) in the case of all three elements. Bristol Inst. of Physics Publ. 2012 Metrologia 49 08010, 1A (Technical Supplement 2012) 1 104 10.1088/0026-1394/49/1A/08010 2016-02-20 OPUS4-40245 Posterpräsentation Fisicaro, P. Collaborative study on mercury and methylmercury quantification in fish samples from the German Environmental Specimen Bank Mercury in its many chemical forms is highly toxic to human, animal and environmental health. The assessment of the ongoing effect of mercury on humans and the environment remains of high importance and is critically dependent on accurate measurements to assess concentrations and trends. 2017 European Winter Conference on Plasma Spectrochemistry Sankt Anton am Arlberg, Austria 19.02.2017 24.02.2017 2017-05-15