R. Jaćimović, M. Horvat, P. Vreča, V. S5bilj, T. Zuliani

Transcription

1 METROLOGY IN CHEMISTRY AT THE IJS/O-2: ADVANTAGES AND DISADVANTAGES R. Jaćimović, M. Horvat, P. Vreča, V. S5bilj, T. Zuliani Department of Environmental Sciences, Jožef Stefan Ins5tute, Ljubljana, Slovenia September th - INCC, Maresias, SP, Brazil

2 Introduction Jožef Stefan Institute (JSI) was founded in 1949 and is the largest Slovenian research organization. The Institute has more than 930 employees performing basic and applied research in the fields of natural sciences and technology (physics, chemistry, material science, nanotechnology, information and communication, technologies, nuclear science, environmental science, ) Department of Environmental Sciences (O-2) is one of the biggest research departments at JSI; 2

3 Introduction - organization of O-2 Head of the Department Prof. dr. Milena Horvat* Deputies of the Head of the Department Prof. dr. R. Milačič (at Jamova) Prof. dr. N. Ogrinc (at the Reactor Centre) 1 laboratory, 5 groups, 2 centers Located at the headquarters in Ljubljana and at the Institute's Reactor Center Podgorica 53 co-workers: Ø 27 Researchers Ø 19 Young researchers Ø 7 Technical and administrative stuff Secretary Damjana Nikovski Group for Isotope Geochemistry Assist. Prof. S. Lojen Group for Radioecology Prof. dr. B. Smodiš Group for Modelling, Risk Assessment and Environmental Impact Assessment Prof. dr. B. Kontić Centre for Radon Prof. dr. J. Vaupotič Centre for Mass Spectrometry dr. D. Žigon QA Manager: dr. Polona Vreča RS : dr. R.Jaćimović Group for Biogeochemistry Prof. dr. M. Horvat LABORATORY FOR ANALYTICAL CHEMISTRY IN ENVIRONMENT Prof. dr. R. Milačič Group for Inorganic Analytical Chemistry Prof. dr. J. Ščančar Group for Organic Analytical Chemistry Prof. dr. E. Heath Group for Radiochemistry Prof. dr. V. Stibilj RS Person in charge of work with Radiation Sources * Member of Scientific Council of IJS 3

4 Introduction Department of Environmental Sciences (O-2) Interdisciplinary research team involved in research, education and transfer of knowledge: environmental analytical chemistry, biogeochemical cycling, radiochemistry/radioecology, environment and health, waste treatment, clean technologies, modelling, risk assessment & analysis Excellent research infrastructure and equipment Accredited in 2009 in the field of chemistry, radiochemistry and radiation for samples from the environment, foodstuffs, feedstuffs and biological samples (Accreditation Certificate LP-090) Designated as DI in 2010 by MIRS, amount of substance (mass fraction of elements): sediments, soils, ores, and particulates; sewage sludge 4

5 Accreditation Certificate LP Methods: 1. Determination of strontium by beta counting 2. Determination of tritium activity by liquid scintillation counting 3. Determination of 14 C in alkaline solution 4. Determining of elemental composition of environmental samples using k 0 -INAA 5. Determination of total mercury in water samples 6. Water quality Application of inductivity coupled plasma mass spectrometry (ICP- MS) Part 2: Determination of 62 elements 7. Water quality Determination of organotin compounds Gas chromatographic method ICP-MS detection 5

6 Accreditation Certificate LP Old annex of the LP-090: : Note: only four methods are under the scope (No. 1-4), No. 5-7 were removed

7 Accreditation Certificate LP-090 Scope of the LP-090 dated : Chemistry Determination of 31 elements (Ag, As, Au, Br, Ca, Ce, Co, Cr, Cs, Eu, Fe, Hf, Hg, K, La, Mo, Na, Nd, Rb, Sb, Sc, Se, Sm, Sr, Ta, Tb, Th, U, Yb, Zn and Zr) in soil, sediments, ores, sewage sludge, biological samples, foodstuffs and fuels by k 0 -INAA Radiochemistry Determination of strontium in samples from the environment (soil, sediment, water, aerosol filter), foodstuffs, milk, feedstuffs and residue by beta counting Determination of tritium activity by liquid scintillation counting (water, urine) Determination of 14 C in alkaline solution (water, urine) 7

8 Accreditation Certificate LP for k 0 -INAA 8

9 Quality life at IJS/O-2: Year Complaints Nonconforming work Internal audits Management reviews * performed in March * 9

10 IJS-O-2 organization of ILCs IJS PT-SL1 Sewage sludge (major and trace elements) SOIL-1 Preparation and characterization of soil reference material from mercury contaminated site for comparability studies PT-WB1, PT-WB2, PT-WB3 Trace elements (Cd, Pb, Hg, As, Se, Cu, Zn) in lyophilized blood FF-3613, FF-3614, GG-0461 Trace elements (Cd, Pb, Hg, As, Se, Cu, Zn) in fresh blood PT-SED2 Determination of Trace Elements (As, Cd, Co, Cr, Cu, Mo, Ni, Hg, Pb, Zn) in Sediment 10

11 Participation in Inter-comparison studies at the highest level (until 2013) Organizer Material Year Analytes IMEP-14 Sediment 2000 Major and trace elements IRMM BAM IAEA INCT ISPRA CCQM-K44 Sewage Sludge 2006 Major and trace elements IMEP-29 Feed of plant origin 2009 Total As, Cd, Pb, Hg and Sn; Extractable Cd and Pb IMEP Total and inorganic arsenic in wheat, vegetable food and algae IMEP Determination of total As, Cd, Pb and Hg in compound feed CCQM-P34 Aluminum 2002 Fe, Cu, Mn, Cr and Zn CCQM-P 34.1 Aluminum 2003 Fe, Cu, Mn, Cr and Zn Yttrium Stabilized Zirconium Oxide 2013 Th, U and Hf CCQM-P104 Phosphogypsum 2008 As, Cd, Cr and Cu Determination of Trace Elements in IAEA-452 Biota Sample 2008 Trace elements and methylmercury INCT-OBTL-5 Oriental Basma Tobacco Leaves 2008 Inorganic trace elements INCT-PVTL-6 Polish Virginia Tobacco Leaves 2008 Inorganic trace elements ISPRA RM021 Lagon Sediment 2010 As, Cd, Ni, Pb, Cu, Co and Mn ISPRA RM039 Lake Sediment 2013 As, Cd, Ni, Pb, Cu, and Co NIM, CCQM-P128 & APMP.QM-P Pb, As measurements in cosmetic (cream) China CCQM-K106 & P Pb, As and Hg measurements in cosmetic (cream) GLHK CCQM-K89 & P Trace and essential elements in Herba Ecliptae APMP.QM-S Essential and toxic elements in Seafood CMQ, CCQM-K30.1 Pb in Wine 2012 Chile & CCQM-P12.2 & Pb, Fe, Cu and Cd in Wine NMIJ CCQM-K08 & CCQM-P Determination of arsenic species, total As and Cd in brown rice flour 11

12 Slovenian metrology system (distributed system) Traceability Ø MIRS (NMI) + 9 designated institutions (DI) Legal metrology Ø 63 private/public bodies Inspection Ø MIRS responsibility LEGAL METROLOGY MIRS DIs with ISO/IEC INSPECTION TRACEABILITY MIRS: cooperation in national and international organizations (CGPM, OIML, IAAO, EURAMET, WELMEC,..) 12

13 Slovenian metrology system Ins5tu5on Acronym Field Metrology ins5tute of the Republic of Slovenia Slovenian ins5tute of Quality and Metrology University of Ljubljana, Faculty of Electrical Engineering University of Maribor, Faculty of Mechanical Engineering MIRS MIRS/SIQ/Metrology MIRS/UL- FE/LMK MIRS/UM- FS/LTM Mass Volume Amount of Substance, Metal and Metal Aloys Electricity and Magne=sm Time and Frequency Thermometry Length Ins5tute of metals and technology MIRS/IMT/LMT Mass and related quan==es, Pressure Jožef Stefan Ins5tute MIRS/IJS/F- 2,O- 2 Ionising Radia=on Amount of Substance, Sediments, soils, ores, and par=culates Na5onal ins5tute of Chemistry MIRS/KI/L05 Amount of Substance, Water Na5onal Ins5tute of Biology MIRS/NIB/FITO Amount of Substance, Food, GMO University of Primorska, Science and Research Centre of Koper Slovenian Na5onal Building and Civil Engineering Ins5tute MIRS/UP- ZRS- IZO/LPO MIRS/ZAG/SM 480 Amount of Substance, Food, Nutri=onal cons=tuents Amount of Substance, Other materials 13

14 BIPM Amount of substance categories QM_categories.pdf 14

15 BIPM Signatories of the CIPM MRA Accessed on Slovenia >> Associate of the CGPM Contact: MIRS Tkalska ulica 15 SI-3000 Celje Tel.: Fax: Web: The CIPM MRA was signed on: 23 June 2003 by: I. SKUBIC (MIRS) Signatory: Metrology Institute of the Republic of Slovenia (MIRS), Celje Designated institute(s): For ionizing radiation; chemistry (sediments, soils, ores, sewage sludge): MIRS/Jozef Stefan Institute/Low and Medium Energy Physics F2, Environmental Sciences O2 (MIRS/IJS/F-2,O-2), Ljubljana (from 5 March 2010) For pressure: MIRS/Institute of Metals and Technology/Laboratory of Pressure Metrology (MIRS/IMT/LMT), Ljubljana For amount of substance (water): MIRS/National Institute of Chemistry/Laboratory for Environmental Sciences and Engineering (MIRS/KI/L05), Ljubljana (from 5 March 2010) For amount of substance (food: GMOs): MIRS/National Institute of Biology/Department of Biotechnology and Systems Biology (MIRS/NIB/FITO), Ljubljana (from 5 March 2010) For electricity and magnetism; time and frequency: MIRS/Slovenian Institute of Quality and Metrology/Metrology (MIRS/SIQ/Metrology), Ljubljana For temperature and humidity: MIRS/University of Ljubljana, Faculty of Electrical Engineering/Laboratory of Metrology and Quality (MIRS/UL-FE/LMK), Ljubljana For length: MIRS/University of Maribor, Faculty for Mechanical Engineering/Laboratory for Production Management (MIRS/UM-FS/LTM), Maribor For amount of substance (food: non-gmo): MIRS/University of Primorska, Science and Research Centre of Koper/Olive Oil Testing Laboratory (MIRS/UP-ZRS/LPOO), Koper (from 5 March 2010) For amount of substance (cements): MIRS/Slovenian National Building and Civil Engineering Institute/Laboratory for Cements, Mortars and Ceramics (MIRS/ZAG/SM 480), Ljubljana (from 5 March 2010) 15

16 The BIPM Kay comparison database (KCDB), accessed on Chemistry: Slovenia Category CMC Advance materials Biological fluids and materials Food Fuels Gases High purity chemicals Inorganic solutions Metals and metal alloys Organic solutions Other materials Sediments, soils, ores, and particulates Surface, films, and engineered nanomaterials Water No No 1 CMC (MIRS/NIB/FITO001, GMOs) No No No No 1 CMC (MIRS/SKM-1, Precious metals) No No No No 2 CMCs (MIRS/KI-1a, Contaminated water, chloride MIRS/KI-2a, Contaminated water, sulphate) 16

17 IJS/O-2 activities as DI q In 2010 the IJS/O-2 has been designated as a holder of national measurement standard in the field of Metrology in Chemistry for the amount of substance in soils, sediments, ores, sewage sludge. q This allowed us to participate in key and supplementary comparisons of the CCQM (Consultative Committee for Amount of Substance Metrology in Chemistry), APMP (Asia-Pacific Metrology Programme), etc. and in their pilot studies. q Participation in CCQM key comparisons may open the door to publishing the calibration and measurement capabilities (CMCs) of the lab in Appendix C of the BIPM key comparison database (KCDB) under the Mutual Recognition Arrangement of the International Committee for Weights and Measures (CIPM MRA). 17

18 IJS/O-2 activities as DI q To have our own CMCs is important not only at national level, but also to justify the status of DI in the KCDB. q Unfortunately, until 2005 no CCQM study in the BIPM category for which IJS/O-2 is designated has been organized. q Although we have participated with great success in numerous KC for other matrices, we cannot officially demonstrate calibration and measurement capability. q In the real terms of metrology principles in chemistry the usefulness of the BIPM list for the amount of substance categories is questionable, especially in case the analytical method is not matrix dependant, such as INAA. q CCQM approved on NAA as a primary ratio method. 18

19 NAA: A primary method of measurement 19

20 IJS/O-2 activities as DI q The k 0 -INAA method used at our Institute is multielement technique and in principle independent from sample matrix. q For more than 20 years the k 0 -INAA is in use at our Institute and it is optimized for use of TRIGA Mark II reactor and absolutely calibrated HPGe detectors. q We participated in homogeneity testing, characterization and feasibility studies for production of IRMM, IAEA, ISPRA, BAM and INCT reference materials for mass fractions of elements (31 elements) of various origins: q Characterization of 18 different RMs during last 4 years e. g. ERM -EF411 (hard coal), ERM -EF412 (brown coal) and ERM -EF413 (furnace coke), ISPRA RM021 (Lagon Sediment), ISPRA RM039 (Lake Sediment) q The results obtained were in very good agreement with assigned values, regardless of the matrix. 20

21 CCQM: K and P comparisons Participation in Key comparisons and Pilot studies during last 3 years: CCQM-K30.1 Pb in Wine (Final report 2013) CCQM-K89 APMP.QM-S5 CCQM-K108 CCQM-K106 Trace and Essential Elements in Herba Ecliptae (As, Ca, Cd, Pb and Zn) (Final report 2013) Essential and Toxic Elements in Seafood (As, Cd, Fe and Zn) (Final report 2013) Determination of arsenic species, total As and Cd in brown rice flour (in progress) Pb, As and Hg measurements in cosmetic (cream) (in progress) CCQM-P12.2 Analysis of Pb, Fe, Cu and Cd in Wine (Final report 2012) CCQM-P128 Cosmetic (cream) (Final report 2012) 21

22 CCQM-K89 El. Content u (k=1) JSI - method As 1.34 µg/g 0.03 µg/g ICP-MS 1.39 µg/g 0.06 µg/g k 0 -INAA* Ca 25.7 mg/g 1.1 mg/g FAAS* mg/g 0.87 mg/g k 0 -INAA Cd 3.97 µg/g 0.06 µg/g ICP-MS 4.41 µg/g 0.23 µg/g k 0 -INAA* Pb 8.78 µg/g 0.29 µg/g ICP-MS Zn 50.6 µg/g 1.5 µg/g ICP-MS* 52.7 µg/g 1.4 µg/g k 0 -INAA * result is not included in the calculation of KCRV 22

23 Sources of uncertainties included in the combined uncertainty estimation CCQM-K89: k 0 -INAA Uncertainty component Analyte As Ca Cd Pb Zn Masses of sample and standard (Al-0.1%Au alloy) X X X X Au composition in Al-0.1%Au alloy X X X X T 1/2 for analyte and Au X X X X Irradiation, decay and measuring times for analyte and Au X X X X Neutron flux parameters (f and α) X X X X k 0 -factor for analyte X X X X Q 0 -factor for analyte and Au X X X X Ē r effective resonance energy for analyte and Au X X X X COI for analyte X X X X Detection efficiency for analyte and Au X X X X St. dev. of 7 independent measurements X X X X 23

24 Sources of uncertainties included in the combined uncertainty estimation CCQM-K89: ICP-MS and FAAS Uncertainty component Analyte As Ca Cd Pb Zn Sample mass X X X X X Digestion of the samples X X X X X Dilution X X X X X Standard deviation of 8 independent measurements (ICP-MS) X X X X Standard deviation of 6 independent measurements (FAAS) X 24

25 CCQM-K89 JSI(1): k 0 -INAA; JSI(2): ICP-MS 25

26 CCQM-K89 JSI(1): k 0 -INAA; JSI(2): FAAS 26

27 CCQM-K89 JSI(1): k 0 -INAA; JSI(2): ICP-MS 27

28 CCQM-K89 JSI: ICP-MS 28

29 CCQM-K89 JSI(1): k 0 -INAA; JSI(2): ICP-MS 29

30 Conclusions q Results obtained by validated methods at IJS/O-2 are in good agreement with assigned values. q In addition, results obtained from k 0 -INAA, non matrix dependant analytical method, argues for re-consideration of the BIPM list of amount of substance categories. q Limited scope of designation in the BIPM database (only amount of substance in sediments, soils, ores, and particulates) q Possible solutions: q Enlarge the scope of designation in the BIPM database to allow the expertise in metrology in chemistry, amount of substance, mass fraction of elements (to add at least biological fluids and materials, and food) of the MIRS/IJS/O-2 to be more effective in areas of need at the national and international level. q Preparation and organization of CCQM-K comparison for soil (in progress, co-operation between JSI/O-2 and CENAM (CCQM-K127 Trace elements in soil)). 30