Project : ENVCRM Matrix reference materials for environmental analysis. Kick-off meeting. Maria Ochsenkühn-Petropoulou, Fotios Tsopelas

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1 NATIONAL TECHNICAL UNIVERSITY OF ATHENS SCHOOL OF CHEMICAL ENGINEERING LAB. OF INORGANIC AND ANALYTICAL CHEMISTRY Project : ENVCRM Matrix reference materials for environmental analysis Kick-off meeting Maria Ochsenkühn-Petropoulou, Fotios Tsopelas TUBITAK UME Chemistry Group-Reference Materials Lab Istanbul, June 2015, Turkey.

2 Members of the NTUA team Coordinators Prof.Maria Ochsenkühn-Petropoulou Dr. Fotios Tsopelas, Lecturer Researchers Dr. Klaus- Michael Ochsenkühn Dr. Theopisti Lymperopoulou, Dr. Lamprini- Areti Tsakanika Kalliopi Mpalta, MSc

3 Contents History of NTUA Instrumentation Research fields- Publications Experience (Participation in relative research projects

4 NATIONAL TECHNICAL UNIVERSITY OF ATHENS: HISTORY The National Technical University (NTUA) is the oldest and most prestigious educational institution of Greece in the field of technology, and has contributed unceasingly to the country's scientific, technical and economic development since its foundation in It is closely linked with Greece's struggle for independence, democracy and social progress. In Greek, NTUA is called the "Ethnicon Metsovion Polytechnion" which stands for National Metsovion Polytechnic. It was named "Metsovion" to honor the donors and benefactors Nikolaos Stournaris, Eleni Tositsa, Michail Tositsas and Georgios Averof, all from Metsovo, a small town in the region of Epirus, who made substantial donations in the last half of the 19th century.

5 The Campus of the NTUA

6 THE NTUA IN NUMBERS Academic staff: 650 Total NTUA Employees: Undergraduate students: Postgraduate Students: Schools: 9 School of Chemical Engineering. School of Civil Engineering. School of Mechanical Engineering. School of Electrical and Computer Engineering. School of Architecture. School of Rural and Surveying Engineering. School of Mining Engineering and Metallurgy. School of Naval Architecture and Marine Engineering. School of Applied Mathematics and Physical Science.

7 SCHOOL OF CHEMICAL ENGINEERING, NTUA: LABORATORIES The Laboratories of the School are distributed among the four Departments. Department of Chemical Sciences: Laboratory of Inorganic and Analytical Chemistry. Laboratory of General Chemistry. Laboratory of Organic Chemistry. Department of Process Analysis and Plant Design (e.g. Laboratory of Thermodynamics and Transport Phenomena, Chemical Process Engineering). Department of Materials Science and Engineering (Laboratory of Physical Chemistry). Department of Synthesis and Development of Industrial Process (e.g. Laboratory of Biotechnology, Food Chemistry and Technology).

8 LABORATORY OF INORGANIC AND ANALYTICAL CHEMISTRY The Laboratory of Inorganic and Analytical Chemistry has the responsibility of educating students of Chemical Engineering, Mining and Metallurgical Engineering, and Civil Engineering, in the courses of Inorganic and Analytical Chemistry. The basic and applied research topics of interest to the Laboratory are: High Performance Liquid Chromatography (HPLC). Electroanalytical techniques. Modern Spectrometric techniques. Thermal Analysis Mass Spectrometry. Trace elements analysis. Speciation analysis. Environmental analysis. Metal recovery from Industrial byproducts.

9 UNIT OF INSTRUMENTAL METHODS OF ANALYSIS- ENVIRONMENT Director: Professor Maria Ochsenkühn-Petropoulou. Academic Staff: Prof. Maria Ochsenkühn- Petropoulou, Dr. Klaus- Michael Ochsenkühn, Dr. Fotis Tsopelas. Co-workers: 7 researchers (4 senior researchers with PhD and 3 PhD students). The research group "Instrumental Methods of Analysis- Environment" is part of Laboratory of Inorganic and Analytical Chemistry, NTUA. The unit possesses long experiences in the field of chemical analysis (mainly inorganic analytes and metal speciation) and environmental investigations. The Research Group is certified by the certification body TÜV HELLAS (TÜV NORD) SA for the quality management system ISO 9001:2008 / EN ISO 9001:2008 for the area "Developing and conducting chemical analyses and environmental studies.

10 INSTRUMENTATION OF UNIT INSTRUMENTAL METHODS OF ANALYSIS- ENVIRONMENT Inductively Coupled Plasma- Mass Spectrometer (ICP-MS) (7700 series, Agilent Technologies). Voltammetric System 797 VA Computrace (Metrohm). High Performance Liquid Chromatograph coupled to UV-Vis detector (Flexar, Perkin- Elmer and Knauer) Atomic Absorption Spectrometer (AAS/GF-AAS/HG-AAS) (Varian). Fourier Transformed Infra-Red (FT-IR) Spectrometer with ATR (Jasco). Metallographic Microscope (Zeiss) Ultrasonic bath,autoclaves, temperature controlled tube furnace, water purification system (for High Purity Water), airborne particulate (PM 10 /PM 2.5 ) sampler, electrophoresis device etc. Pilot plant for the recovery of valuable elements (rare earths) from industrial byproducts (red mud)

11 INSTRUMENTATION OF THE UNIT OF INSTRUMENTAL METHODS OF ANALYSIS- ENVIRONMENT ICP-MS (Agilent) HPLC (Perkin- Elmer) AAS/GFAAS(Varian) AAS Voltammeric analyzer (Metrohm) FTIR (Jasco) Pilot plant

12 ENVIRONMENT AND QUALITY OF LIFE LABORATORY It is a joint laboratory unit of the School of Chemical Engineering, equipped with high cost scientific instruments. It cooperates with the unit Instrumental Methods of Analysis- Environment. Its instrumentation includes: LC-MS-MS GC-MS SEM ICP-OES XRD XRF

13 INSTRUMENTATION OF ENVIRONMENT AND QUALITY OF LIFE LABORATORY Inductively Coupled Plasma- Optical Emission Spectrometer (ICP-OES) (Optima 7000 DV, Perkin- Elmer). Liquid Chromatography- Mass Spectrometer (LC-MS/ MS) (Varian). Gas Chromatography- Mass Spectrometer (GC-MS) (Varian). Ion Chromatography (IC) (BioLC, Dionex). X- Ray Diffraction Spectrometer (XRD) (D5000, Siemens and Bruker, D8 ADVANCE). X-Ray Fluorescence Spectrometer (XRF) (Advant XP, ARL). Scanning Electron Microscope coupled with Energy Dispersive X- Ray Analysis (SEM- EDAX) (Quanta 200, FEI).

14 Related to the project Research Fields Speciation Analysis (Se, As and Sn speciation) in food, environmental and biological samples. Air pollution: Airborne particulates in the Attica basin. Automobile Catalysts and Platinum Group Element Emissions. Wood pellets and particulate matter emissions. Analytical methods for the evaluation of biological properties of organometallic compounds and candidate drugs.

15 1. SPECIATION ANALYSIS Development of analytical approaches for Se, As and Sn speciation based on selective extraction- ion exchange, liquid chromatography and detection with spectrometric and electro-analytical techniques. Applications to environmental samples (water/ seawater, soil and sediments, marine organisms), food and biological samples. Participation in inter-comparison exercises for the development of certified reference materials for As, Se and Sn.

16 SPECIATION ANALYSIS: SELECTED PUBLICATIONS Exploring the elution mechanism of selenium species on liquid chromatography, F. Tsopelas, A. Tsantili-Kakoulidou, M. Ochsenkuhn-Petropoulou, Journal of Separation Science, 34, (2011). Extraction of arsenic species from airborne particulate filters. Application to an industrial area of Greece, F. Tsopelas, L.A. Tsakanika, M. Ochsenkuhn-Petropoulou, Microchemical Journal 89, (2008). Comparison of ultra-violet and inductively coupled plasma- atomic emission spectrometry for the on-line quantification of selenium species after their separation by reversed- phase liquid chromatography, F. Tsopelas, M. Ochsenkühn- Petropoulou, I. Mergias, L.A. Tsakanika, Analytica Chimica Acta 539, (2005). Speciation analysis of selenium using voltammetric techniques, M. Ochsenkühn- Petropoulou, F. Tsopelas, Analytica Chimica Acta 467, (2002). Separation of organotin compounds by ion- exchange chromatography and their determination by inverse voltammetry, K.M. Ochsenkühn, M. Ochsenkühn- Petropoulou, F. Tsopelas, L. Mendrinos, Fresenius Journal of Analytical Chemistry 369, (2001). Speciation of arsenobetaine in marine organisms using a selective leaching/digestion procedure and hydride generation atomic absorption spectrometry, M. Ochsenkühn- Petropoulou, J. Varsamis, G. Parissakis, Analytica Chimica Acta 337, (1997).

17 2. AIR POLLUTION Qualitative and quantitative analysis (heavy metals, organic species, ions) of filters from aerosol samples(pm10/pm2.5). Identification of pollution sources. Platinum Group Element Emissions from Automobile Catalysts: Development of a novel sampling system at the exhaust pipe of vehicles. Determination of platinum group elements by voltammetric techniques using ion-exchange separation/ preconcentration and GFAAS/ICP-MS. Particulate matter emissions from combustion of different types of wood pellets.

18 AIR POLLUTION: SELECTED PUBLICATIONS Influence of local and regional sources on the observed spatial and temporal variability of size resolved atmospheric aerosol mass concentrations and watersoluble species in the Athens metropolitan area, K. Eleftheriadis, K.M. Ochsenkühn, Th. Lymperopoulou, A. Karanasiou, P. Razos, M. Ochsenkühn- Petropoulou, Atmospheric Environment 97, (2014). A novel way of sampling particles containing platinum group elements from automobile catalysts, M. Paraskevas, K. Papoutsi, M. Ochsenkühn-Petropoulou, Analytical Letters 45, (2012). Determination of Pt and Pd in particles emitted from automobile exhaust catalysts using ion-exchange matrix separation and voltammetric detection, M. Paraskevas, F. Tsopelas, M. Ochsenkuhn-Petropoulou, Microchimica Acta 176, (2011). Extraction of arsenic species from airborne particulate filters. Application to an industrial area of Greece, F. Tsopelas, L.A. Tsakanika, M. Ochsenkuhn- Petropoulou, Microchemical Journal 89, (2008). Ion chromatographic and spectrometric determination of water-soluble compounds in airborne particulates and their correlations in an industrial area in Attica, Greece, Klaus-Michael Ochsenkuhn, Theopisti Lyberopoulou, Georgia Koumarianou and Maria Ochsenkuhn-Petropoulou, Microchimica Acta 160, (2008).

19 3. DEVELOPMENT OF ANALYTICAL APPROACHES FOR THE EVALUATION OF BIOLOGICAL PROPERTIES OF ORGANOMETALLIC SPECIES AND CANDIDATE DRUGS Development of liquid chromatographic techniques (reversed- phase, immobilized artificial membrane and immobilized plasma proteins columns) for the evaluation of membrane permeability, bioavailability, bioaccumulation tendency and protein binding of candidate drugs and organometallic species. Development of electroanalytical techniques for the evaluation of antioxidant activity of natural species and candidate drugs.

20 3. ANALYTICAL TECHNIQUES FOR BIOLOGICAL PROPERTIES: SELECTED PUBLICATIONS Insight into the retention mechanism on immobilized artificial membrane chromatography using two stationary phases, F. Tsopelas, N. Malaki, Th. Vallianatou, M. Chrysanthakopoulos, D. Vrakas, M. Ochsenkühn- Petropoulou, A. Tsantili- Kakoulidou, Journal of Chromatography A 1396, (2015). Antioxidant 2-hydroxy-chalcones: a study of their electrochemical behavior, O. Serifi, F. Tsopelas, A.M. Kypreou, M. Ochsenkühn-Petropoulou, P. Kefalas, A. Detsi, Journal of Physical Organic Chemistry 26, (2013) Lipophilicity, biomometic retention profile and antioxidant activity of selenium species, F. Tsopelas, A. Tsantili-Kakoulidou, M. Ochsenkühn-Petropoulou, Microchemical Journal 110, (2013). Electrochemical study of some non-steroid anti-inflammatory drugs: Solvent effect and anti-oxidant activity, F. Tsopelas, M. Ochsenkühn- Petropoulou, N. Zikos, I. Andreadou, A. Tsantili- Kakoulidou, Journal of Solid State Electrochemistry 15, (2011). Biomimetic chromatographic analysis of selenium species: Application for the estimation of their pharmacokinetic properties, F. Tsopelas, A. Tsantili- Kakoulidou, M. Ochsenkuhn -Petropoulou, Analytical and Bioanalytical Chemistry 397, (2010).

21 OTHER SCIENTIFIC ACTIVITY Founding and organization of the biannual International Conferences Instrumental Methods of Analysis-Modern Trends and Applications, IMA ( ). Chairperson: 1999, 2009, 2013, Guest editor in Analytical and Bioanalytical Chemistry (special issue for IMA 2009 and IMA 2013 conferences).

22 9 th International Conference on September 2015 Kalamata, Greece Covered topics Spectrochemical, Electrochemical, Chromatographic, Microscopic and Thermal analysis methods, Hyphenated techniques, Speciation analysis, Bioanalytics, Sample handling and preparation, Chemical and bio-sensors, Field analysis-mobile analytical instruments, Laboratory information management systems (LIMS), Miniaturized analytical systems (chips), Robotics and Automation, Quality control-quality assurance on analysis, Commercial developments and markets, Flow and micro-flow methodologies, Immunoassays, Electrophoreticseparationtechniques, Sampling techniques and strategies. Applications: Environmental analysis, Biomedical (Clinical, Ecotoxicological) analysis, Pharmaceutical analysis, Material science (Nanomaterials), Archaeometry analysis, Industrial analysis, Food analysis. Contributions from commercial organizations, including detailed descriptions of New instrumentation, Specific applications, Assessment of future commercial trends and opportunities. Organized by Technological Educational Institute of Peloponnese National Technical University of Athens A special session is going to be attributed to food analysis with emphasis to food safety, aroma compounds determination, packaging, novel foods etc. Abstract submission deadline: 15/5/2015 Under the auspices of ima2015@teikal.gr

23 A Joint Research Project for the Production and Certification of Matrix Reference Materials for Environmental Analysis A. ISLEYEN 1, J. VOGL 2, N. SCRUNDRIC 3, A. JOTANOVIC 4, T. NÄYKKI 5, M. HORVAT 6, A. ZOŃ 7, E. BULSKA 8, M. OCHSENKÜHN- PETROPOULOU 9, S. Z. CAN 1, M. BİLSEL 1, K. HAFNER 4, N. PERKOLA 5, B. ARI 1, M. TUNÇ 1, B. BİNİCİ 1 alper.isleyen@tubitak.gov.tr 1 TÜBİTAK UME-National Metrology Institute-TURKEY 2 BAM-Federal Institute for Materials Research and Testing-GERMANY 3 DMDM- Directorate of Measures and Precious Metals-SERBIA 4 IMBIH- Institute of Metrology-BOSNIA and HERZEGOVINA 5 SYKE-Finnish Environment Institute-FINLAND 6 IJS-Institute Jozef Stefan-SLOVENIA 7 GUM-Central Office of Measures-POLAND 8 UWAR-University of Warsaw-POLAND 9 NTUA-National Technical University of Athens-GREECE Reliable analysis of chemical indicators in water, sediment and soil samples for the purpose of environmental pollution assessment poses one of the greatest analytical challenges, having in mind the complexity of sample matrix and low concentrations of pollutants. Organics (pesticides, PAHs, PCBs, etc.) and heavy metals (Hg, Cd, Ni, Pb and As) represent target parameters. Laboratories performing sampling and tests in this field regulated by respective EU directives [1], need strong support in terms of providing them with appropriate matrix CRMs enabling the process of quality control. NMIs and DIs with proven metrological capabilities for the production and certification of such materials are necessary for the provision of quality data. This project is aiming to develop capacity to produce CRMs for environmental analysis by transferring the theoretical and practical know-how between the partners and combining their skills to focus on environmental CRM production in accordance with ISO Guide 34 [2]. Production process includes good manufacturing practices for processing materials, method development and validation for homogeneity, stability and characterisation tests, characterisation of selected analytes together with additional information about matrix constituents, the calculation of individual uncertainties (between units inhomogeneity, long term stability, characterisation) and combination of uncertainties to determine overall uncertainty of the matrix reference materials. Inter laboratory comparison registered as EURAMET project is set as the ultimate project outcome, confirming the partners capabilities in applying newly acquired skills. References [1] Water Framework Directive 2008/105/EC Annex II: Priority substances and other pollutantshttp://ec.europa.eu/environment/water/water-framework/priority_substances.htm [2] ISO Guide 34:2009 General Requirements for the Competence of Reference Material Producers

24 EXPERIENCE IN RELATIVE SCIENTIFIC PROJECTS (CRMs) Interlaboratory proficiency tests SCHEMA (Scheme for Chemical Measurements Assessment) ( ). Feasibility studies for speciated CRMs for arsenic in chicken, rice, fish, soil and selenium in yeast and cereal, SEAS Project (2001), EC Contract Ref: G6RD, CT 2001 (Coordinator: University of Plymouth). Measurements and Testing Programme ( ): Certified reference materials: butyl- and phenyl- tin compounds in mussel and sediment (BCR), EU Project MAT 1-CT Coordinator: Institute for Environmental Studies/ IVM Vrije Universiteit, Amsterdam. Measurements and Testing Programme ( ): Arsenic speciation project No. 336, Bureau of Reference Communities (BCR). Measurements and Testing Programme ( ): Butyltin speciation Project No. 313, Bureau of Reference Communities (BCR).

25 INTERLABORATORY PROFICIENCY TESTS SCHEMA (Scheme for Chemical Measurement Assessment) SCHEMA Title Elements Determination of Cd and Pb migration in ceramic articles Cd, Pb Determination of heavy elements in drinking waters Determination of heavy metals in foodstuffs (tea leaves, potato) Cd, Pb, Cr, Cu, Ni, As, Sb, Al, Mn, Fe Cd, Pb, Cr (tot), Cr (VI), Cu, Ni, As

26 QUANTIFICATION OF Cr AND Ni IN DRINKING WATER BY ICP-OES AND ICP-MS (INTERCOMPARISON EXERCISE- SCHEMA 2201)

27 z-score of participant laboratories in SCHEMA (Determination of Cd migration in ceramic articles) (Total participants: 15)

28 z-score of participant laboratories in SCHEMA Determination of Cd in tea leaves (Total participants : 13)

29 TIN SPECIATION IN SEDIMENT (INTERCOMPARISON EXERCISE) Sample: Freshwater sediment CRM No 646 of Bureau of Reference Communities (BCR). Analytical Approach: Leaching with 0.5 M HCl Quantitative recovery of dibutyltin (DBT) and triphenyltin (TPT). Detection with voltammetric techniques. Species Results (ng Sn g -1 dry sediment) Deviation Our laboratory Mean value of intercomparison exercise (%) DBT ± ± TPT 9.8 ± ± K.M.Ochsenkuehn,M Ochsenkuehn-Petropoulou, F.Tsopelas, L.Mendrinos Different Behavior of organotin compounds by anodic stripping voltammetry and their quantification after partial ion exchange separation Mikrochim Acta 136(2001)

30

31 ARSENIC SPECIATION IN SOIL CANDIDATE REFERENCE MATERIAL ( SEAS Project / INTERCOMPARISON EXERCISE) Sample: Candidate Reference Material Soil IPL-1 Analytical Approach: Leaching with conc. HCl Quantitative recovery of As species. Detection with ICP-OES and HG-ICP-OES As species Results: μg As/ g dry sample Deviation Our laboratory (ICP-OES, HG- ICP-OES) Mean value of intercomparison exercise (%) Total As 606 ± ± As(III) 17 ± 5 18 ± As(V) 496 ± ± MMA 65 ± ± DMA 67 ± ±

32 TOTAL As IN SOIL MIX 2 Graph from SEAS project

33 SELENIUM SPECIATION IN YEAST CANDIDATE REFERENCE MATERIAL ( SEAS Project / INTERCOMPARISON EXERCISE) Analytical Approach: Enzymatic extraction with Protease XIV Analysis with HPLC combined with ICP-OES detector. Se Species Our laboratory (μg Se/g dry sample) SEAS Mean value (μg Se/g dry sample) Total Se ± ± Deviation (%) Se-Met ± ± Se(IV) 22.2 ± ± F.Tsopelas, M.Ochsenkuehn-Petropoulou, I.Mergias, L.Tsakanika Comparison of ultra-violet and inductively coupled plasma-atomic emission spectrometry for the on-line quantification of selenium species after their separation by reversed-phase liquid chromatography Anal Chim Acta 539 (2005)

34 CHEMICAL METROLOGY IN GREECE Reference laboratory: General Chemical State Laboratory, it belongs to the Ministry of Economy and Finance. Greek Accreditation Body: ESYD (Hellenic Accreditation Body).. Labs in charge: Laboratories of Universities and Research Centers and Private labs accredited.

35 CRMs NEEDS FOR GREECE There is NO organization to produce CRMs in Greece Cr(VI) in environmental matrices (water/ wastewater, sludge and sediments). Heavy metals in wastewaters and soils/ sediment/ sludge with certified values in different levels (lower and higher concentration of pollutants). Fresh waters with certified values in a range of heavy metals. Toxic metals in soils and sludge with certified levels (e.g. As, Hg and Cr(VI)).

36 ENVIRONMENTAL THREATS FOR GREECE (WATER- SEDIMENTS/ SOILS) Heavy metals and metalloids: Cr(VI), Ni, Pb, Cd, As. Nitrates. Pesticides. Pharmaceutical and personal care products residues. Microcystins/ neurotoxins.

37 EXPECTATIONS FROM THE PROJECT Sharing of state-of-the-art knowledge and techniques between participants. Dissemination of experience among labs from different countries. Results meriting publication in impacted scientific journals and participation in related international conferences. Preparation of valid CRMs. Great cooperation- Perspectives for establishment of new projects.

38 Thank you for your attention!

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