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XXXVIII CSI 2013 Table of Content TABLE OF CONTENT Table of Content...................................................................................
Author: Gloria Haynes
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XXXVIII CSI 2013

Table of Content

TABLE OF CONTENT Table of Content................................................................................................................. 1 Welcome! .............................................................................................................................. 2 Organising and Scientific Committee ...................................................................... 3 International Advisory Board ....................................................................................... 4 Continuation Committee................................................................................................ 4 General Information ......................................................................................................... 5 Social Programme............................................................................................................. 8 Scientific Programme ................................................................................................... 10 Liability ................................................................................................................................ 10 Sponsors and Exhibitors .............................................................................................. 11 Correspondence after the conference ................................................................. 12 Schedule of Events......................................................................................................... 13 Daily Programme............................................................................................................ 15 Poster Presentations ..................................................................................................... 25 Plenary Lecture Abstracts .......................................................................................... 30 Lecture Abstracts ........................................................................................................... 67 Address list ......................................................................................................................241 

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XXXVIII CSI 2013

Welcome Letter

WELCOME! On behalf of the Norwegian Chemical Society, University of Tromsø and the Organising Committee it is an honour and pleasure to welcome you to Tromsø and the Colloquium Spectroscopicum Internationale XXXVIII in Tromsø, Norway, June 17 – 20, 2013. This conference provides both an international and a regional forum by which researchers and users have the opportunity to share their knowledge and exchange ideas. We know that the natural beauty of the area will captivate you, but we also hope that the conference excursions, social events and farewell dinner may complement the scientific endeavours.

Yngvar Thomassen

Jon Øyvind Odland

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Walter Lund

XXXVIII CSI 2013

Committees

ORGANISING AND SCIENTIFIC COMMITTEE ORGANISERS The Colloquium Spectroscopicum Internationale XXXVIII is organised by the Norwegian Chemical Society and the University of Tromso and in collaboration with International Union of Pure and Applied Chemistry.

YNGVAR THOMASSEN

(Chairman) National Institute of Occupational Health and Norwegian University of Life Sciences, Ås, Norway

WALTER LUND

(Vice-Chairman) University of Oslo, Norway

ELIN GJENGEDAL Norwegian University of Life Sciences Ås, Norway

IVAR MARTINSEN GE Healthcare, Oslo, Norway

ARNE ÅSHEIM

(Exhibition Coordinator) Molab AS, avd. Porsgrunn, Norway

SVERRE OMANG (Treasurer) Oslo, Norway

ODDVAR RØYSETH

NIVA, Norwegian Institute of Water Research, Oslo, Norway

GEORG BECHER Norwegian Institute of Public Health, Oslo

BALÁZS BERLINGER (Secretary) National Institute of Occupational Health, Oslo

JON ØYVIND ODLAND University of Tromsø

ANNE REGINE LAGER University Hospital, Tromso, Norway

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XXXVIII CSI 2013

Committees

INTERNATIONAL ADVISORY BOARD Freddy Adams Michael Bolshov Maria Luisa de Carvalho Albert Gilmutdinov Detlef Günther Klaus Heumann Gary Hieftje Alexander A. Kamnev Ryszard Lobinski Robert McCrindle Alfredo Sanz Medel János Mink Harpal Minhas Lars-Otto Reiersen Bernhard Welz Gyula Záray

Belgium Russia Portugal Russia Switzerland Germany USA Russia France South-Africa Spain Hungary UK Norway Brazil Hungary

CONTINUATION COMMITTEE Bernhard Welz Marco Aurélio Zezzi Arruda Yngvar Thomassen Balázs Berlinger Maria Luisa de Carvalho Joaquim dos Santos

Department of Chemistry, UFSC, Brazil Institute of Chemistry, UNICAMP, Brazil National Institute of Occupational Health, Norway National Institute of Occupational Health, Norway Atomic Physics Center, University of Lisbon, Portugal Department of Physics, University of Coimbra, Portugal

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XXXVIII CSI 2013

General Information

GENERAL INFORMATION Conference Desk Participants are requested to register as soon as possible upon arrival, preferably at Radisson Blu Hotel. The conference desk will operate as follows: Sunday, June 16 16:00 - 20:00

Lobby of Radisson Blu Hotel

Monday, June 17 07:00 - 08:30

Lobby of Radisson Blu Hotel

Monday, June 17 13:00 - 18:00

Faculty of Health Sciences, First floor HE-building

Tuesday, June 18 08:30 - 18:00

Faculty of Health Sciences, First floor HE-building

Wednesday, June 19 08:30 - 18:00

Faculty of Health Sciences, First floor HE-building

Thursday, June 20 08:30 - 15:00

Faculty of Health Sciences, First floor HE-building

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XXXVIII CSI 2013

General Information

Conference Venue All oral sessions will be held in the various auditoriums of University of Tromsø: The morning plenary sessions will be held in Auditorium 1, Teorifagbygget, House 1. The afternoon sessions will be held in the Auditoriums at the Faculty of Health Sciences, First floor HE-Building, Lysgården.

"Lysgården"

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XXXVIII CSI 2013

General Information

Bus transportation from Tromsø City to University Campus Conference buses will leave from outside the main entrance of Radisson Blu Hotel every morning from Monday, June 17, including Thursday, June 20, at 08:00 and 08:30. Please consult the conference program for the bus return schedule. The public bus connection between the centre of the city and the university campus is quite good. Bus no. 20/21 leaves from Fr. Langes gate (F1) in the centre of the city, and from the university just below building 23 on the campus map. This trip takes approximately 10 minutes. The bus leaves every 15 mins from the centre of the city on weekdays. You can also take bus no. 34 – but this route takes you on a longer journey round the southern parts of the island (nice, if you are not in a hurry).

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XXXVIII CSI 2013

Social Programme

SOCIAL PROGRAMME

Monday, June 17, 19:00-24:00, the CSI-Club Sponsored by Agilents Technologies and Matriks AS and

Tuesday, June 18, 19:00-24:00, the CSI-Club The Ølhallen pub in Tromsø opened in1928 in the cellar of Macks Bryggeri, the most northerly brewery in the world. Here, in a world of what appears to be eternal candle-lit night, perched on wooden stools, every Tom, Dick and Harry in Tromsø takes his beer.This is no cool, trendy bar – Ølhallen is an original, in a class of its own. As a CSI-participant you go to Ølhallen to drink beer, Mack beer. Mack’s entire selection is available, on draught, in bottles, or both. Regular Gullmack Pilsner, the heavier Håkon beer, the dark, malty Bayer beer and all the new kinds of beer are offered, but Ølhallen’s regulars swear by Blanding: two parts dark Bayer and one part light Pilsner. Each CSI-participant is granted minimum two 0.5 L drafts free of charge! Cheaper beer is not available in town! A selection of Peppes famous pizzas will also be served free of charge. Ølhallen is at the southern end of Tromsø’s main street, Storgata 4, and is easy to find.

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XXXVIII CSI 2013

Social Programme

Wednesday, June 19, 19:45: Conference Dinner at the Fram Centre Sponsors: Agilents Technologies and Matriks AS

After an introduction to the scientific activities at the FRAM CENTRE a seafood buffet dinner will be served. Non-alcoholic and alcoholic beverages are included. NOK 500 (not included in the registration fee) The Fram Centre is based in Tromsø, and consists of about 500 scientists from 20 institutions involved in interdisciplinary research in the fields of natural science, technology and social sciences. FRAM contributes to maintaining Norway’s prominent status in the management of environment and natural resources in the North.

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XXXVIII CSI 2013

Scientific Programme

SCIENTIFIC PROGRAMME Oral Presentations Invited plenary lectures and submitted oral contributions will be 30 and 20 minutes in length, respectively (including discussion). Video projectors and computers will be provided in all lecture rooms. Posters The posters should be mounted Monday June 17, in the poster area located at the Faculty of Health Sciences, First floor HE-Building, Lysgården. Materials for poster mounting are available either from the Conference Desk or in the poster mounting area. All posters will be exhibited throughout the whole conference. Language The working language of the conference is English.

LIABILITY The Organising Committee declines any responsibility whatsoever for injuries or damages to persons or their property during the Conference.

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XXXVIII CSI 2013

Sponsors and Exhibitors

SPONSORS AND EXHIBITORS

The exhibition of scientific instrumentation, literature and consumables is located next to the auditoriums of Faculty of Health Sciences, First floor HE-Building, Lysgården.

The following companies have registered for display and demonstration: AGILENT ANALYTIK JENA BRUKER MILESTONE SRL SHIMADZU THERMO SCIENTIFIC

PERKIN ELMER PANALYTICAL CPI INTERNATIONAL GAMMADATA MAGRITEK GMBH POSTNOVA

KAISER OPTICAL SYSTEMS

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CORRESPONDENCE AFTER THE CONFERENCE

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XXXVIII CSI 2013

Schedule of Events

SCHEDULE OF EVENTS June 16-20, 2013

Time 09:00 09:15 09:30 09:45 10:00 10:15 10:30 10:45 11:00 11:15 11:30 11:45 12:00 12:15 12:30 12:45 13:00 13:15 13:30 13:45 14:00 14:15 14:30 14:45 15:00 15:15 15:30 15:45 16:00 16:15 16:30 16:45 17:00 17:15 17:30 17:45 18:00 18:15 18:30 18:45 19:00 19:15 19:30 19:45 20:00

Sunday, June 16

Monday, June 17 Opening Ceremony Aud. 1, Teorifagbygget, House 1

Tuesday, June 18 Plenary Lecture PL7-PL9 Aud. 1, Teorifagbygget, House 1

Inaugural Lecture PL1 Coffee Break,10:30-11:00 Coffee Break, 10:45-11:15

Plenary Lecture PL2-PL4

Plenary Lecture PL10-PL12

Lunch, Lysgården 12:30-13:30 Lunch, Lysgården, 13:00-14:00 Plenary Lecture PL5-PL6, Store Auditorium, Lysgården Lecture L1-L4, Aud. 3

Lecture L9-L12 Store Aud.

Lecture L18-L21 Aud. 4

Coffee Break, 16:00-16:20 Lecture L5-L8 Aud. 3 Registration Radisson Blu Hotel

Lecture L13-L17 Store Aud.

Lecture L22-L24 Aud. 4

Lecture L25-L29 Store Aud

Lecture L30-L34 Aud. 3

Lecture L35-L38 Aud. 4

Coffee Break, 15:20-15:40 CSI award Store Auditorium NKS award, Store Auditorium Award Reception Lysgården

Bus Departures, 18:15

Bus Departures, 18:15

The CSI-Club Ølhallen

The CSI-Club Ølhallen

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XXXVIII CSI 2013

Schedule of Events

Wednesday, June 19

Thursday, June 20

Plenary Lecture PL13-PL16 Aud. 1, Teorifagbygget, House 1

Plenary Lecture PL21-PL24 Aud. 1, Teorifagbygget, House 1

Coffee Break, 11:00-11:20

Coffee Break 11:00-11:20 Plenary Lecture PL25-PL26 11:20-12:20

Plenary Lecture PL17-PL19 11:20-12:50

Lunch, Lysgården, 12:20-13:20 Lunch, Lysgården, 12:50-13:50 Plenary Lecture PL27-PL28 13:20-14:20

Plenary Lecture PL20 Store Aud., 13:50-14:20

Lecture L39-L44 Aud. 3

Lecture L45-L50 Store Aud.

Lecture L51-L56 Aud. 4

Lecture L56-L63 Aud. 2

Lecture L64-L67 Store Aud.

Lecture L68-L70 Aud. 3

Closing Ceremony 15:45 Bus Departures, 16:30

Poster Discussions 16:20 (16:50) -18:30

Bus Departures, 18:30

Conference Dinner, Fram Centre, 19:45

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Time 09:00 09:15 09:30 09:45 10:00 10:15 10:30 10:45 11:00 11:15 11:30 11:45 12:00 12:15 12:30 12:45 13:00 13:15 13:30 13:45 14:00 14:15 14:30 14:45 15:00 15:15 15:30 15:45 16:00 16:15 16:30 16:45 17:00 17:15 17:30 17:45 18:00 18:15 18:30 18:45 19:00 19:15 19:30 19:45 20:00

XXXVIII CSI 2013

Daily Programme

DAILY PROGRAMME Monday, June 17, 2013 Time 09:00

Abs.

Opening Ceremony

Auditorium 1, Teorifagbygget, House 1 Chairman: Yngvar Thomassen 09:45

PL1

Inaugural Lecture

Hubble Space Telescope and Its Discoveries Richard E. Griffiths, Carnegie Mellon University, Pittsburgh, USA/NASA HQ Coffee Break

10:45

Climate Change and Spectroscopy 11:15

PL2

12:00

PL3

12:30

PL4

Auditorium 1, Teorifagbygget, House 1 Chairman: Yngvar Thomassen Climate Change and Mitigation: Carbon Capture – A Bridge Into a Low Carbon Economy Claus Jørgen Nielsen, University of Oslo, Norway Molecular - Level Analysis and Photochemical Aging of Atmospheric Organics in Ambient Particles and Aqueous Droplets Sergey A. Nizkorodov, University of California, USA Characterization of Atmospheric Aerosol Particles by Electron Microscopy Stephan Weinbruch, Technical University Darmstadt, Germany

Lunch

13:00

Faculty of Health Sciences, Lysgården. Store Auditorium – Lysgården 14:00

PL5

14:20

PL6

Time 14:40

Abs. L1

15:00

L2

15:20

L3

15:40

L4

Basic Research for Chemical Absorption of Carbon Dioxide Using NMR Spectroscopy Cristina Perinu, Telemark University College, Porsgrunn, Norway Molecular Analysis of the Organic and Elemental Carbon Fractions (EC/OC) of Ambient Particulate Matter by Coupling of a Thermal Carbon Analyzer to Photo-Ionization Mass Spectrometry Ralf Zimmermann, University of Rostock, Germany I. MATERIAL CHARACTERISATION Auditorium 3 – Lysgården Chairman: Irina Snigireva X-Ray Refractive Optics: Present Status and New Developments Anatoly Snigirev, European Synchrotron Radiation Facility, France Characterisation of Nanoparticles With Synchrotron X-Ray Standing Wave Fluorescence Roland Hergenröder, Leibniz-Institut für Analytische Wissenschaften, Dortmund, Germany NEXAFS Spectroscopic Studies of Anodized Ti-6Al-4V Alloy With the Aide of First Principles Calculations Toshihiro Okajima, Kyushu Synchrotron Light Research Center, Japan Microscale Mineral Analysis of Clay Rock Thin Sections After Sorption Experiment Using SRXRF Szabina Török, HAS Energy Research Institute, Budapest, Hungary Coffee Break

16:20 16:20

L5

16:40

L6

17:00

L7

17:20

L8

Synthesis and Characterization of Metal Nanoclusters: A New Generation of Luminescent Labels Laura Trapiella-Alfonso, University of Oviedo, Spain Advanced Inspection Technologies in Extreme Scenarios: Standoff LIBS and Underwater LIBS Javier J. Laserna, University of Málaga, Spain The UMS: A New Tool for Multi-Angle UV-VIS-NIR Photometric Spectroscopy Jan Wuelfken, Agilent Technologies,Waldbronn, Germany 57Fe-Mössbauer Study of Electrically Conductive Lithium Iron Vanadate Glass Shiro Kubuki, Tokyo Metropolitan University, Japan

17:40 18:10

Bus Departures

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XXXVIII CSI 2013

Daily Programme

Monday, June 17, 2013

Time

Abs.

14:40

L9

15:00

L10

15:20

L11

15:40

L12

Breakthrough in Sensivity for Quadrupole ICP-MS Meike Hamester, Bruker Daltonics, Germany Determination of Rare Earth Elements in Extracts from Oil Refinary Spent Catalyst by ICP-MS with a Reaction Cell Jessee Severo Azevedo Silva, Universidade Federal de Santa Catarina, Brazil Some Procedures of Reducing Matrix Effects in ICP-MS Analysis of Biological Samples Konstantin Ossipov, Lomonosov Moscow State University, Russia Development of an Analytical Method for Cd, Co, Cr, Cu, Ni and Pb Determination in Cosmetic Samples Edenir Rodrigues Pereira-Filho, Federal University of São Carlos, Brazil Coffee Break

16:00 16:20

L13

16:40

L14

17:00

L15

17:20

L16

17:40

L17

The New 8800 ICP-QQQ: Handling the Most Difficult Samples With Ease Uwe Noetzel, Agilent Technologies, Germany A Comparison of Conventional (Off-Line) and On-Line Isotope Dilution ICP-MS for the Determination of Total Selenium in Human Serum Petru Jitaru, Institut Polytechnique LaSalle Beauvais, Beauvais cedex, France From 2D Towards 3D Elemental Imaging by Laser Ablation ICP-MS - A Study of Archaeological Glass Vid S. Šelih, National Institute of Chemistry, Ljubljana, Slovenia Direct Solid Quantitative Analysis of Battery Components Using LA-ICP-MS and Development of Custom Made Solid Standard Materials Analysis of Battery Materials Björn Hoffmann, University of Münster, Germany Direct Elemental Analysis of Nanodiamonds With ICP-OES Dmitry S. Volkov, Lomonosov Moscow State University, Russia Bus Departures

18:10

Time 14:40

Abs. L18

15:00

L19

15:20

L20

15:40

L21

III. THEORETICAL, STRUCTURAL AND MODELLING STUDIES Auditorium 4 – Lysgården Chairman: Arne Bengtson Experimental Spectroscopic and Quantum Chemical Studies of the Reactivity of Alkylresorcinols in Redox Processes Alexander A. Kamnev, Institute of Biochemistry and Physiology of Plants and Microorganisms, Saratov, Russia Vibrational Spectral Analysis of the Isotopic Species of Hydrogen Sulphide, Hydrogen Selenide and Water Using the U(4) Algebraic Model Nirmal Kumar Sarkar, Karimganj College, India Theoretical Investigation of the CW Absorption, Resonance Raman and REMPI Spectroscopy of the S1 and S2 States of cis-1,3,5-Hexatriene and trans-1,3,5-Hexatriene Clemens Woywod, University of Tromsø, Norway Basis Set Extrapolation for High Resolution Spectroscopy Kiran Sankar Maiti, University of Gothenburg, Sweden Coffee Break

16:00 16:20

L22

16:40

L23

17:00

L24

18:10

II. PLASMA SPECTROCHEMISTRY Store Auditorium – Lysgården Chairman: Maria Montes-Bayón

Exploring Structure and Ultrafast Dynamics of Protein and Peptide Using Two Color 2D IR Spectroscopy Susmita Roy, University of Gothenburg, Sweden Fat Determination of Intact Food Samples with Time-Domain Nuclear Magnetic Resonance Spectroscopy and Chemometrics Fabiola Manhas Verbi Pereira, Embrapa Instrumentation, São Carlos, Brazil Diode Laser Absorption Spectrometry as a Tool for Contactless Diagnostic of a Hot Zone Michael A. Bolshov, Institute for Spectroscopy RAS, Moscow, Russia Bus Departures

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XXXVIII CSI 2013

Daily Programme

Tuesday, June 18, 2013 Pristine Environments and Spectroscopy Time

Abs.

09:00

PL7

09:30

PL8

10:00

PL9

10:30

Auditorium 1, Teorifagbygget, House 1 Chairman: Klaus Heumann Arctic – From Cold War to Arctic Melt Down: 20 Years of Arctic Monitoring and Assessment of Pollutants and Climate Change by AMAP Lars Otto Reiersen, Artic Monitoring and Assessment Programme, Oslo, Norway Spectroscopy under Ice Carlo Barbante, University of Venice, Italy Bioluminescent Ecological Assay. Features and Scope of Applications Nadezhda Kudryasheva, Siberian Federal University, Krasnoyarsk, Russia Coffee Break

11:00

PL10

11:30

PL11

12:00

PL12

FTIR Spectroscopy in Microbial Ecology: ‘Shedding IR Light’ on Cellular Metabolic Responses to Environmental Factors Alexander A. Kamnev, Institute of Biochemistry and Physiology of Plants and Microorganisms, Saratov, Russia Atmospheric Deposition of Trace Elements on the Local and Regional Scale Studied by ICP-MS Analysis of Moss Samples Eiliv Steinnes, Norwegian University of Science and Technology, Trondheim, Norway Mass Spectrometry Made Easy: The Quest for Simplicity in Forensic, Food, Pharmaceutical, Environmental, Medical and Biochemical Analysis Marcos Eberlin, Universidade Estadual de Campinas, Brazil Lunch Faculty of Health Sciences, Lysgården.

12:30

Time

Abs

13:30

L25

14:00

L26

14:20

L27

14:40

L28

15:00

L29

IV. MASS SPECTROMTRY Store Auditorium – Lysgården Chairman: Georg Becher Liquid Chromatography Mass-Spectrometry as a Tool for Detection of Chemicals Connected with Chemical Warfare Agents in Environmental and Bio Samples Igor A. Rodin, Moscow State University, Russia Collision-Induced Dissociation of Hydroxylated Polycyclic Aromatic Hydrocarbons in an Ion Trap Tandem Mass Spectrometer Xue Li, ETH Zürich, Switzerland Electrospray Ionization Mass Spectrometry Assisted by Inductively Coupled Plasma Mass Spectrometry as a Tool to Study the Se/S Substitution in Methionine and Cysteine in Se-Enriched Yeast Katarzyna Bierła, CNRS/UPPA, Laboratoire de Chimie Analytique Bio-inorganique et Environnement (LCABIE), Pau, France Identification of Original Sources of Vermilion in Antiquity Using Sulfur Isotope Ratio Analysis Takeshi Minami, Kinki University, Osaka, Japan Study of Interactions Between Reactive Gas Species and Microorganisms by Nano-Resolution Mass Spectrometry Imaging Jean-Nicolas Audinot, Centre de Recherche Public Gabriel Lippmann, Belvaux, Luxembourg

15:20

Coffee Break

15:40

Store Auditorium – Lysgården Introduced by Yngvar Thomassen and Gary Hieftje

16:40

NORWEGIAN CHEMICAL SOCIETY-DIVISION OF ANALYTICAL CHEMISTRY HONORARY AWARD

CSI AWARD

Store Auditorium – Lysgården Introduced by Elin F. Gjengedal and Freddy Adams

17:15

Award Reception Faculty of Health Sciences, Lysgården.

18:15

Bus Departures

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XXXVIII CSI 2013

Daily Programme

Tuesday, June 18, 2013

Time

Abs.

13:30

L30

14:00

L31

14:20

L32

14:40

L33

15:00

L34

V. ATOMIC ABSORPTION SPECTROMTRY Auditorium 3 – Lysgården Chairman: Robert McCrindle Solid Sampling Techniques for the Direct Elemental or Isotopic Analysis of Dried Matrix Spots Martín Resano, University of Zaragoza, Spain Low Resolution Continuum Source Electrothermal Atomic Absorption Spectrometry: Clarification of Analytical Potential Dmitri Katskov, Tshwane University of Technology, Pretoria, South Africa Trace Determination of Metals by In-Atomizer Hydride Trapping AAS: Method Development, Validation and Analytical Applications Jan Kratzer, Institute of Analytical Chemistry of the ASCR, Brno, Czech Republic Optimization Study on Determination of Inorganic Arsenic Species in Hot Chilli Pepper and Tomato Varieties by Using Microwave Assisted Digestion Followed by Flow Injection-Hydride Generation Atomic Absorption Spectrometry Saksit Chanthai, Khon Kaen University, Thailand. Preconcentration of Mercury from Natural Waters by Amalgamation of Hg2+ on Copper Powder and Hg0 on Gold Nanoparticles. Nikolay Panichev, Tshwane University of Technology, Pretoria, South Africa

15:20

Coffee Break

Time

Abs.

VI. GLOW DISCHARGE Auditorium 4 – Lysgården Chairman: Volker Hoffmann

13:30

L35

14:00

L36

14:20

L37

14:40

L38

Sampling of Liquids in Atomic Emission Spectrometry Using a Helium Atmospheric Pressure Glow Discharge José A.C. Broekaert, University of Hamburg, Germany GD TOFMS with Pulsed Combined Hollow Cathode for Direct Analysis of Dielectric Samples Alexander Ganeev, St. Petersburg State University, Russia Selective Excitation in Analytical Glow Discharges – Its Relevance in GD-OES Analysis Edward B. M. Steers, London Metropolitan University, UK Molecular Emission in GD-OES Revisited – Strategies for Background Correction Arne Bengtson, Swerea KIMAB, Kista, Sweden

15:20

Coffee Break

15:40

Store Auditorium – Lysgården Introduced by Yngvar Thomassen and Gary Hieftje

16:40

NORWEGIAN CHEMICAL SOCIETY-DIVISION OF ANALYTICAL CHEMISTRY HONORARY AWARD

CSI AWARD

Store Auditorium – Lysgården Introduced by Elin F. Gjengedal and Freddy Adams

17:15

Award Reception Faculty of Health Sciences, Lysgården.

18:15

Bus Departures

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XXXVIII CSI 2013

Daily Programme

Wednesday, June 19, 2013 Human Health and Spectroscopy Time

Abs.

09:00

PL13

09:30

PL14

10:00

PL15

10:30

PL16

11:00

Auditorium 1, Teorifagbygget, House 1 Chairman: Alexander Kamnev Confocal Spectral Imaging Technique in the Development of Photo- and Neutronsensitizers for Anticancer Therapy Alexey V. Feofanov, Lomonosov Moscow State University, Russia New Developments in Disease Recognition by Infrared and Raman Spectroscopy and Microscopy: Present Status and Future Promises János Mink, Institute of Molecular Pharmacology, Research Centre for Natural Sciences, Budapest, Hungary Metabolic Fingerprinting via Mass Spectrometric Analysis of Exhaled Breath Renato Zenobi, ETH Zürich, Switzerland Accurate Measurement of Iron Metabolism Biomarkers: New Tools and Remaining Challenges Maria Montes-Bayón, University of Oviedo, Spain Coffee Break

11:20

PL17

11:50

PL18

12:20

PL19

SALDI Mass-Spectrometry: Principles and Application for Drug Analysis Alexander Grechnikov, Vernadsky Institute of Geochemistry and Analytical Chemistry of RAS, Moscow, Russia SIMS and the Single Cell Vic Norris, University of Rouen, France High Resolution MALDI Imaging: Reliable Molecular Information at Cellular Resolution Andreas Römpp, University of Giessen, Germany Lunch Faculty of Health Sciences, Lysgården

12:50

Progress in Mass Spectrometry Time

Abs.

13:50

PL20

Store Auditorium – Lysgården Chairman: Carlo Barbante New Approaches, Plasmas, and Instrumentation for Atomic Spectrometry Steven J. Ray, Indiana University, Bloomington, USA

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XXXVIII CSI 2013

Daily Programme

Wednesday, June 19, 2013

Time

Abs.

14:20

L39

14:40

L40

15:00

L41

15:20

L42

15:40

L43

16:00

L44

VII. ENVIRONMENTAL APPLICATIONS I Auditorium 3 – Lysgården Chairman: Janos Mink Chemical Characterization of Dekati® Low Pressure Impactor (DLPI) Wall Deposits Thibaut Durand, Institut National de Recherche et de Sécurité, Vandoeuvre-lès-Nancy, France Chemical Characterization and Oxidative Potential of PM2.5 Collected in Office Buildings in Greece and The Netherlands: A Cooperative Study Tamás Szigeti, Eötvös Loránd University, Budapest, Hungary FTIR (DRIFT) Spectroscopic Analysis of Accumulation and Structural Features of Poly-3Hydroxybutyrate in Cells of Azospirillum Brasilense: Effects of Copper(II) Anna V. Tugarova, Laboratory of Biochemistry, Institute of Biochemistry and Physiology of Plants and Microorganisms, RAS, Saratov, Russia A New Hybrid Fluorometer-Spectrophotometer for Water Quality Analysis of Oil, Chromophoric Dissolved Organic Matter, Chlorophyll and -NHX Adam M. Gilmore, HORIBA Instruments Inc., Edison, USA Occurrence of Polychlorinated Biphenyls (PCBs) and Polybrominated Diphenylethers (PBDEs) in Different Fish Species from Ilha Grande Bay, Southeastern Brazil. Isabel Moreira, Pontifícia Universidade Católica do Rio de Janeiro, Brazil Application of Multi-Reflection, High Resolution Time-of-Flight-Mass Spectrometry as Detector for One- and Two-Dimensional Gas Chromatography: Characterization of Complex Mixtures Ralf Zimmermann, University of Rostock, Germany

16:20

Poster Discussions

18:30

Bus Departures

19:45

Conference Dinner

Time

Abs.

VIII. IMAGING AND MODELLING Store Auditorium – Lysgården Chairman: José Broekaert

14:20

L45

14:40

L46

15:00

L47

15:20

L48

15:40

L49

16:00

L50

New Imaging Capabilities Using LA-ICP-TOF Mass Spectrometry Detlef Günther, ETH Zürich, Switzerland Further Developments of an Energy- and Position-Sensitive XRF Imaging System Based on a THCOBRA Detector Analusia L.M. Silva, University of Aveiro, Portugal Pharmaceutical Images Harvesting and Comparison Tomáš Pekárek, Zenitva, k.s., Prague, Czech Republic Novel Multispectral Imaging Approaches For Recovering of Degraded Archaeological Wall Paintings Vincenzo Palleschi, CNR Area della Ricerca del CNR, Pisa, Italy LA-ICPMS Imaging And Nuclear Forensics: Pu Isotope Ratios In Sediments From Mayak PA, Russia Simone Cagno, Norwegian University of Life Sciences, Ås, Norway Physicochemical Investigation of The Wall Paintings of Petros Paulos Church, Ethiopia Kidane Fanta Gebremariam, Norwegian University of Science and Technology, Trondheim, Norway

16:20

Poster Discussion

18:30

Bus Departures

19:45

Conference Dinner

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XXXVIII CSI 2013

Daily Programme

Wednesday, June 19, 2013

Time

Abs.

14:20

L51

14:40

L52

15:00

L53

15:20

L54

15:40

L55

16:00

L56

IX. HUMAN HEALTH Auditorium 4 – Lysgården Chairman: Elin Gjengedal Comparison Between SR-XRF and ICP-AES Jun Kawai, Kyoto University, Japan Analysis of Bones for Forensic Studies Vincenzo Palleschi, CNR Area della Ricerca del CNR, Pisa, Italy Printable Surface Enhanced Raman Scattering Strips with In-Situ Growth of Gold Nanoparticles Wei Ju, Liao, National Yang-Ming University, Taiwan Speciation and Cobalt Toxicity on Human Lung Cells: An Interdisciplinary Study Carole Bresson, Laboratoire de Développement Analytique Nucléaire, Isotopique et Elémentaire, Gifsur-Yvette, France. Fast and Non-Destructive Quantification of Dapivirine in Hiv Preventive Intravaginal Rings by Raman Spectroscopy Lotte B. Lyndgaard, University of Copenhagen, Denmark Titanium Measurement in Biofluids by ICP-OES (Simultaneous Inductively Coupled Plasma Optical Emission) and He-CC KED Quadrupole ICP-MS János Fucskó, NMS Labs, Willow Grove, USA

16:20

Poster Discussion

18:30

Bus Departures

19:45

Conference Dinner

Time

Abs.

X. ENVIRONMENTAL APPLICATIONS II Auditorium 2 – Lysgården Chairman: Eiliv Steinnes

14:20

L57

14:40

L58

15:00

L59

15:20

L60

15:40

L61

16:00

L62

16:20

L63

Distribution and Source of Metals in Contaminated Sediments from Rivers in Coal Fields Rob McCrindle, Tshwane University of Technology, Pretoria, South Africa Interpretation of the Plastic Life Cycle Using FTIR-ATR and ICP-OES Spectrometry Albert van Oyen, CARAT GmbH, Bocholt, Germany Advanced Techniques for Environmental Analysis Using ICP-MS Shona McSheehy Ducos, Thermo Scientific, Bremen, Germany Quantitative Analysis of Heavy Elements and Semi-Quantitative Evaluation of Heavy Mineral Compositions of Stream Sediments in Japan for Construction of a Forensic Soil Database Using Synchrotron Radiation X-Ray Analyses Izumi Nakai, Tokyo University of Science, Japan Effect of Metal Stress on Pigments in Copper-Hyperaccumulating Lichens Hiromitsu Nakajima, Yokohama National University, Japan High Sensitivity and Extended Scan Speed for Dedicated Isotope Ratio Determinations René Chemnitzer, Bruker Daltonics, Bremen, Germany Determination of Heavy Metals at Ultralow Concentration Levels in Pristine Polar Snow and Ice Claude F. Boutron, University Joseph Fourier of Grenoble, France

16:50

Poster Discussion

18:30

Bus Departures

19:45

Conference Dinner

-21 -

XXXVIII CSI 2013

Daily Programme

Thursday, June 20, 2013 Material Characterisation and Spectroscopy Time

Abs.

09:00

PL21

09:30

PL22

10:00

PL23

10:30

PL24

11:00

Auditorium 1, Teorifagbygget, House 1 Chairman: Maria Luisa de Carvalho Pulsed Glow Discharge Time of Flight Mass Spectrometry: A Powerful and Versatile Tool for Elemental and Molecular Depth Profile Analysis Rosario Pereiro, University of Oviedo, Spain Coherent High Energy X-Ray Microscopy: A New Tool to Study Mesoscopic Materials Irina Snigireva, European Synchrotron Radiation Facility, Grenoble, France Analysis of Topical Biomedical and Technological Samples by Photothermal and Photoacoustic Spectroscopies Using Signal-Enhancement Techniques and Selective Reactions Mikhail A. Proskurnin, Lomonosov Moscow State University, Russia Progress and Demands in Analytical Glow Discharges Volker Hoffmann, Institute for Complex Materials, IFW Dresden, Germany Coffee Break

11:20

PL25

11:50

PL26

12:20

Development and Characterization of Materials for Advanced Power Plants Hubertus Nickel, Research Centre Jülich/University of Technology Aachen, Germany Application of Synchrotron Microprobe Techniques to Speciation of Plutonium in Argillaceous Rocks Tobias Reich, Johannes Gutenberg-Universität Mainz, Germany Lunch Faculty of Health Sciences, Lysgården

Progress in Analytical Spectrometry Store Auditorium – Lysgården Chairman: Martín Resano 13:20

PL27

13:50

PL28

An Analytical Technique on Its Way to Adulthood: Current Status and Future Perspectives of Mass Spectrometry Imaging Andreas Römpp, University of Giessen, Germany “Think Big! – Optimization of a Spectrometry Lab on the Industrial Scale Heiko Egenolf, BASF SE, Competence Center Analytics, Ludwigshafen, Germany XI. ENERGY STORAGE CHARACTERISATION Store Auditorium – Lysgården Chairman: Michael Bolshov

14:20

L64

14:40

L65

15:00

L66

15:20

L67

Characterization of Decomposition Products in Energy Storage Materials by Chromatographic Methods Sascha Nowak, University of Münster, Germany Lock-In Thermography – A Novel In-Situ Measurment Methode to Support Surface Spectroscopy for Lithium-Ion Cells Mathias Reichert, University of Münster, Germany Characterization of the Decomposition Products of a Utilized Battery Electrolyte from a Commercial Available Hybrid Vehicle with Purposeful Analytical Methods Martin Grützke, University of Münster, Germany Analysis of the Manganese Dissolution and Deposition in LiMn2O4/Li4Ti5O12 Based Lithium Ion Batteries Markus Börner, University of Münster, Germany

15:45

Closing Ceremony Store Auditorium – Lysgården

16:30

Bus Departures

-22 -

XXXVIII CSI 2013

Daily Programme

Thursday, June 20, 2013

Time

Abs.

14:20

L67B

14:40

L68

15:00

L69

XII. SPECIATION ANALYSIS Auditorium 3 – Lysgården Chairman: Yngvar Thomassen UV-Photochemical Volatile Species Generation Employed as a Derivatization Technique Between HPLC Separation and AAS Detection within Speciation Analysis of Mercury(II), Methylmercury(I), Ethylmercury(I) and Phenylmercury(I) Vaclav Cerveny, Charles University in Prague, Czech Republic Chemical Vapor Generation for Trace Analysis - Recent Developments Alessandro D’Ulivo, Institute of Chemistry of Organometallic Compounds, U.O.S. of Pisa, Italy Influence of Selenium Species in Aquaculture Feeds on the Selenium Status of Farmed Rainbow Trout Fry Simon Godin, Université de Pau et des Pays de l’Adour, France

15:45

Closing Ceremony Store Auditorium – Lysgården

16:30

Bus Departures

-23 -

-24 -

XXXVIII CSI 2013

Poster Presentations

POSTER PRESENTATIONS Abstract P1 DETERMINATION OF TRACE SULFUR IN BIODIESEL AND DIESEL STANDARD REFERENCE

MATERIALS BY ISOTOPE DILUTION SECTOR FIELD INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRY Renata S. Amais, Stephen E. Long, Joaquim A. Nóbrega and Steven J. Christopher P2

DETERMINATION OF CHROMIUM SPECIES IN THE WORKPLACE AIR M. Stanisławska, B. Janasik; R. Brodzka; W. Wąsowicz

P3

A NEW APPROACH FOR THE DETERMINATION OF ARSENIC IN THE WORKPLACE AIR. THE POSSIBILITY OF USING LA-ICP-MS TECHNIQUE. R. Brodzka, B. Janasik, M. Stanisławska, M. Trzcinka-Ochocka, W. Wąsowicz

P4

DETERMINATION OF MERCURY SPECIES IN FISH USING HPLC-ICP/MS Syr-Song Chen, Che-Lun Hsu, Wei-Min Fu, Cheng-Ming, Chu, Su-Hsiang Tseng, Ya-Min Kao, LihChing Chiueh and Yang-Chih Shih

P5

DEVELOPMENT OF A QUANTUM DOT-BASED IMMUNOASSAY FOR SCREENING OF TETRACYCLINES IN BOVINE MUSCLE Jenifer García-Fernández, Laura Trapiella-Alfonso, José M. Costa, Rosario Pereiro, Alfredo SanzMedel

P6

ICP-MS-BASED ISOTOPIC MEASUREMENTS OF ATMOSPHERIC LEAD IN POLAR REGIONS Marco Grotti, Andrea Bazzano1 and Mery Malandrino

P7

SIGNS OF SPATIAL HETEROGENEITIES WITHIN XLPE CABLE INSULATION PROBED BY SOLID STATE 1H-NMR Jobby Paul, Eddy W. Hansen, Sissel Jørgensen, Bjørnar Arstad and Aud Bouzga

P8

DELTA (13C) DETERMINATION ON BIOFUELS AND BIOPLASTIC APPLYING CAVITY RINGDOWN SPECTROSCOPY Gisele Birman Tonietto, Jose M. Godoy, Julianna M. Martins , Walquiria R. S. Ribeiro, Mara A. Silva

P9

THE STRUCTURAL AND MAGNETO-RESONANCE PROPERTIES OF THE POR-INP Suchikova Y.

P10

57FE-MÖSSBAUER,

XANES AND HR-TEM STUDIES OF ELECTRICALLY CONDUCTIVE BAOFE2O3-V2O5 GLASES

Satoru Yoshioka, Shiro Kubuki, Hitomi Masuda, Kazuhiko Akiyama, Kazuhiro Hara and Testuaki Nishida P11

MEASUREMENT OF ELEMENTAL CONTENTS IN HEMOLYMPH, MALPIGHIAN TUBULES, GUT AND URINE OF RHODNIUS PROLIXUS INVESTIGATED BY SR-TXRF Andrea Mantuano, Arissa Pickler, Regina C. Barroso, Liebert P. Nogueira, Carla L. Mota, André P. de Almeida, Delson Braz, Simone C. Cardoso, Marcelo S. Gonzalez, Eloi S. Garcia and Patricia Azambuja

P12

CHARACTERIZATION OF SILVER NANOPARTICLES BY PAGE-LA-ICP-MS Maria S. Jimenez, Maria T. Gomez, Carmen Diez, Lluis Arola, M.Josepa Salvadó, Cinta Bladé, Juan R. Castillo

P13

MERCURY LEVELS IN A POLLUTED RIVER ECOSYSTEM IN EAST BOHEMIA: FROM LONGTERM MONITORING OF TOTAL CONTENT TO SPECIATION ANALYSIS Miroslav Soukup, Inga Petry-Podgórska, Stanislav Lusk, Lukáš Vetešník, Jan Zíka, Vlasta Korunová and Jan Kratzer

-25 -

XXXVIII CSI 2013

Poster Presentations

Abstract P15 ICP-MS METHODOLOGY FOR BLOOD TRACE ELEMENTS COMPOSITION ANALYSIS FOR

PATIENTS WITH DIFFERENT STAGES OF TUMOR O.V. Kovalenko, I.V. Boltina, E.O. Pisarev, G. A.Liubchenko, L.S. Kyolodna, N.Ya. Gridina , I.V. Kalinitchenko P16

THE ISAS- X-RAY FLUORESCENCE BEAM LINE AT DELTA: POSSIBILITIES AND APPLICATIONS Roland Hergenröder, Alex von Bohlen and Martin Brücher

P17

CHEMICAL SPECIATION OF INORGANIC BERYLLIUM FOR WORKING AREAS PARTICULATE MATTER SAMPLES: SEQUENTIAL EXTRACTION PROCEDURE DEVELOPMENT AND APPLICATION Thibaut Durand and Davy Rousset

P18

SELECTIVE AND NON-SELECTIVE EXCITATION/IONIZATION PROCESSES IN AR/HE MIXED PLASMAS Sohail Mushtaq, Edward B. M. Steers, Juliet C. Pickering and Karol Putyera

P19

THE MICROWAVE PHOTOCHEMICAL REACTOR FOR THE ON-LINE OXIDATIVE DECOMPOSITION OF P-HYDROXYMERCURYBENZOATE (PHMB)-TAGGED PROTEINS AND THEIR DETERMINATION BY LC-COLD VAPOUR GENERATION ATOMIC FLUORESCENCE DETECTION. Beatrice Campanella, Jose González Rivera, Carlo Ferrari, Massimo Onor, Emanuela Pitzalis, Alessandro D’Ulivo and Emilia Bramanti

P20

STUDY OF THE INTERACTION OF CHLORINATED AND SULFOCHLORINATED PARAFFINS WITH GELATIN B AND SKIN POWDER. A MODEL FOR FATTENING IN THE LEATHER TANNING PROCESS Valentina Della Porta, Susanna Monti, Massimo Onor, Alessandro D’Ulivo, Emanuela Pitzalis, Alice D’Allara and Emilia Bramanti

P21

OPTIMIZATION OF ANALYTICAL TESTS FOR THE CHARACTERIZATION AND VALIDATION OF MERCURY-SORBENT MATRICES Massimo Onor, Emanuela Pitzalis, Alessandro D’Ulivo, Valentina Della Porta, Marco Carlo Mascherpa and Emilia Bramanti

P22

IMPROVEMENTS IN THE DETERMINATION OF SULFIDE, CYANIDE AND THIOCYANATE BY CHEMICAL VAPOR GENERATION COUPLED WITH HS-GC-MS Massimo Onor, Sara Ammazzini, Enea Pagliano, Emanuela Pitzalis, Emilia Bramanti and Alessandro D’Ulivo

P23

DEVELOPMENT AND EVALUATION OF DESOLVATION SYSTEM FOR DROPLET DIRECT INJECTION NEBULIZER Yuki Kaburaki, Tomokazu Kozuma, Akito Nomura, Takahiro Iwai, Hidekazu Miyahara, Akitoshi Okino

P24

STUDY OF THE EXCITATION PROCESSES INVOLVING OXYGEN AS AN ADDED GAS IN A NEON ANALYTICAL GLOW DISCHARGE PLASMA Sohail Mushtaq, Edward B. M. Steers and Juliet C. Pickering

P25

INVESTIGATIONS ON THE USE OF AMMONIA AS A REACTION GAS TO OVERCOME INTERFERENCES IN RARE EARTH ELEMENTS BY ICP-MS Jessee Severo Azevedo Silva, Tatiane de Andrade Maranhão, Daniel L. Galindo Borges, Vera Lucia A. Frescura and Adilson José Curtius

P26

STUDY OF TETRACYCLINE FRAGMENTATION WITH LC-MS Martin Šala, Drago Kočar, Tadeja Lukežič, Gregor Kosec and Hrvoje Petkovič

-26 -

XXXVIII CSI 2013

Poster Presentations

Abstract P27 METHOD DEVELOPMENT FOR THE ANALYSIS OF ORGANOPHOSPHORUS COMPOUNDS IN

LIPF6-BASED ELECTROLYTES Vadim Kraft, Martin Grützke, Martin Winter and Sascha Nowak P28

IN-SITU MÖSSBAUER SPECTROSCOPY AS A NON-DESTRUCTIVE TOOL TO ANALYZE LITHIUM-ION BATTERY AGING Sascha Weber, Thorsten Langer, Falko Schappacher, Rainer Pöttgen and Martin Winter

P29

COMPARISON OF VARIOUS SPECTROSCOPIC IMAGING TECHNIQUES FOR INVESTIGATION OF HG AND SE METABOLISM IN PLANT TISSUES Marta Debeljak, Johannes Teun van Elteren1, Katarina Vogel-Mikuš, Alessandra Gianoncelli, David Jezeršek

P30

SIZE CHARACTERISATION OF METALS IN TUNNEL WASH WATER AS A FUNCTION OF TIME AND DETERGENT Jon-Henning Aasum, Elin Gjengedal and Sondre Meland

P31

DIRECT DETERMINATION OF BROMINE IN PLASTIC MATERIALS BY MEANS OF SOLID SAMPLING HIGH-RESOLUTION CONTINUUM SOURCE GRAPHITE FURNACE MOLECULAR ABSORPTION SPECTROMETRY María R. Flórez, E. García-Ruiz, Martín Resano

P32

CHANGES IN CHEMICAL COMPOSITION OF URBAN PM2.5 BETWEEN 2010 AND 2013 IN HUNGARY Tamás Szigeti, Mihály Óvári, Franco Lucarelli, Gyula Záray, Victor G. Mihucz

P33

DETERMINATION OF FLUORINE USING HIGH RESOLUTION CONTINUUM SOURCE MOLECULAR ABSORPTION SPECTROMETRY (HR-CS MAS) René Nowka and Heike Gleisner

P34

DETERMINATION OF TRACE ELEMENTS IN BLACK AND WHITE PEPPERS BY XRF SPECTROMETER EQUIPPED WITH POLARIZATION OPTICS AND ITS DEVELOPMENT TO IDENTIFICATION OF THEIR PRODUCTION AREA Akiko Hokura, Megumi Shibasawa and Noriko Kuze

P35

DETERMINATION OF SELENIUM USING CHEMICAL AND PHOTOCHEMICAL VOLATILE COUMPOUNDS GENERATION COUPLED WITH ATOMIC ABSORPTION SPECTROMETRY Marcela Rybinova, Vaclav Cerveny and Petr Rychlovsky

P36

EFFECT OF ZINC IN HISTORICAL IRON BASED INK CONTAINING DOCUMENTS: A MULTISPECTROSCOPIC APPROACH Marta Manso, Ana Mafalda Cardeira, Tânia Rosado, Mara Silva, Agnès Le Gac, Sofia Pessanha, Mauro Guerra, Stéphane Longelin, Ana Teresa Caldeira, António Candeias and Maria Luísa Carvalho

P37

EVALUATION OF CALCIUM AND PHOSPHORUS IN TOOTH ENAMEL EXPOSED TO BLEACHING GEL Godinho J., Pessanha S., Silveira J, Mata A., Carvalho M.L.

P38

ASSESSMENT OF ESSENTIAL ELEMENTS AND HEAVY METALS CONTENT ON MYTILUS GALLOPROVINCIALIS FROM RIVER TAGUS ESTUARY I. Santos, M. Diniz, M. L. Carvalho, J. P. Santos

P39

CHARACTERIZATION OF CALCIUM SULPHATE AND GLUE SIZING UNDER CALCIUM CARBONATE GROUND LAYERS IN FLEMISH AND LUSO-FLEMISH PAINTINGS - ANALISYS BY SEM-EDS AND µXRD Vanessa Antunes, Maria José Oliveira, Helena Vargas , António Candeias , Maria Luísa Carvalho, Ana Isabel Seruya, João Coroado, Luís Dias, José Mirão, Vitor Serrão

-27 -

XXXVIII CSI 2013

Poster Presentations

Abstract P40 TRACE ELEMENT ENRICHMENT OF LIVING NOURISHMENT AQUATIC ORGANISMS AND

DETERMINATION OF THEIR UPTAKE BY ATOMIC ABSORPTION SPECTROMETRY Milán Fehér, Edina Baranyai, Edina Simon, István Szűcs, Péter Bársony, József Posta, László Stündl P41

APPLICATION OF NON-MEMBRANE ELECTROLYTIC CELL FOR ELECTROCHEMICAL VOLATILE SPECIES GENERATION OF TRANSITION METALS Jakub Hraníček, Andrea Kobrlová, Václav Červený, Tomáš Vacek, Tomáš Matoušek and Petr Rychlovský

P42

ASSESSMENT OF NUTRIENTS OF ESCAMOLES ANT EGGS LIMOTEPUM APICULATUM M BY SPECTROSCOPY METHODS Virginia Melo, Tomas Quirino, Concepción Calvo, Karina Sánchez and Horacio Sandoval

P43

SPECTROSCOPIC STUDY OF THE AGEING PROCESSES IN TANNIN DYED TEXTILES S. Legnaioli, G.H. Cavalcanti G. Lorenzetti, V. Palleschi, E. Grifoni, I. Degano, M. P. Colombini, E. Ribechini

P44

SPECTROSCOPIC STUDIES OF XII-XIV CENTURY ITALIAN GOLD COINS BY X-RAY FLUORESCENCE M. Baldassarri, G.H. Cavalcanti, M. Ferretti, A. Gorghinian, E. Grifoni, S. Legnaioli, G. Lorenzetti, L. Marras, E. Violano and V. Palleschi

P45

SPECTROSCOPIC STUDIES ON ETRUSCAN ARCHAEOLOGICAL FINDINGS G. Sorrentino, S. Giuntoli, M. Lezzerini, S. Legnaioli, G. Lorenzetti, G.H. Cavalcanti and V.Palleschi

P46

DETERMINATION OF METALS IN THE FOOD CHAIN USING THE HIGH SPEED SELF REVERSAL METHOD FOR BACKGROUND COMPENSATION Oppermann, Uwe and van Oyen, Albert

P47

LO-RAY-LIGH® DIFFRACTION GRATINGS IN UV-VIS SPECTROSCOPY U. Oppermann, M. Egelkraut-Holtus, and T. Fujiwara

P48

PLASTC WASTE IN THE ENVIRONMENT – A NEW CHALLENGE IN SPECTROSCOPY Oppermann, Uwe and van Oyen, Albert

P49

XRF DETERMINATION OF SILICON IN ALUMINA Michele Cowley and Johann Fischer

P50

XRF DETERMINATION OF SULPHUR IN IRON OXIDE Michele Cowley , Johann Fischer and Willemien van Schalkwyk

P51

ELEMENTAL MAPPING OF MOROCCAN ENAMELED TERRACOTTA TILE WORKS (ZELLIJ) BASED ON X-RAY MICRO-ANALYSES R. Bendaoud, A. Guilherme, A. Zegzouti, M. Elaatmani, J. Coroado, A. Le Gac,4, S. Pessanha, M. Manso, M. L. Carvalho and I. Queralt

P52

DETERMINATION OF METALS IN LARVAE USING ICP-OES Blanca Paz,.Ciro Márquez, Olga Cabrera; Lydia Romero, Carlos Enrique Díaz

P53

CHALLENGING SPATIAL RESOLUTION LIMITS OF LASER ABLATION INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRY (LA-ICP-MS) IN ELEMENTAL DISTRIBUTION MAPPING APPLICATIONS EMPLOYING ACTIVE 2-VOLUME CELL TECHNOLOGY Dhinesh Asogan, Damon Green, John Roy, Stephen Shuttleworth, Bill Spence and Peter Winship

P54

LOW VOLUME SAMPLE INJECTION FOR TRACE ELEMENT ANALYSIS EMPLOYING INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRY (ICP-MS) David Clarke, Bill Spence and Peter Winship

P55

APPLICATION OF LEAD ISOTOPE RATIO MEASUREMENTS FOR THE ORIGIN ASSESSMENT OF MARINE POLLUTION Emilia Vassileva and Anna Maria Orani

-28 -

XXXVIII CSI 2013

Poster Presentations

Abstract P56 APPLICATION OF HIGH RESOLUTION SECTOR FIELD ICP- MS FOR DETERMINATION OF

LOW LEVEL PLUTONIUM IN MARINE SAMPLES Emilia Vassileva, Eunmi Han and Isabel Levy P57

FTIR EMISSION SPECTROSCOPIC STUDY OF ALUMINA-SILICATE BASED BLACK POWDER WITH PECULIAR PROPERTIES J. Mink, J. Mihály, Cs. Németh

P58

NEW IMAGING CAPABILITIES USING LA-ICPTOF MASS SPECTROMETRY H.A.O. Wang, C. Giesen, D. Grolimund, B. Bodenmiller, D. Günther

P59

TRACE ELEMENT DISTRIBUTION OF EXTRACELLULAR PROTEINS DETERMINED IN HUMAN SERUM BY MP-AES AND GFAAS Edina Baranyai, Csilla Noémi Tóth, Mihály Braun, Tünde Tarr, István Csípő, Margit Zeher, József Posta

P60

P61

THE ANALYSIS OF DDTS AND CHLORDANES AND THEIR METABOLITES BY GAS CHROMATOGRAPHY TANDEM MASS SPECTROMETRY: COMPARING ATMOSPHERIC PRESSURE IONISATION WITH ELECTRON IMPACT AND CHEMICAL IONISATION Sandra Huber, Nicholas A. Warner, Therese Haugdahl Nøst, Ole-Martin Fuskevåg and Jan Brox PALM-TOP EPMA USING PYROELECTRIC ELECTRON BEAM FOR 100 MICROMETER BEAM SIZE Jun Kawai, Akira Imanishi, Susumu Imashuku

-29 -

XXXVIII CSI 2013

Plenary Lecture Abstracts

PLENARY LECTURE ABSTRACTS (PL1) HUBBLE SPACE TELESCOPE AND ITS DISCOVERIES Richard E. Griffiths, Carnegie Mellon University, Pittsburgh, USA/NASA HQ

-30 -

XXXVIII CSI 2013

Plenary Lecture Abstracts

(PL2) CLIMATE CHANGE MITIGATION. CARBON CAPTURE – A BRIDGE INTO A LOW CARBON ECONOMY Claus Jørgen Nielsen, Department of Chemistry, University of Oslo Climate is often defined as “average weather” and described in terms of the mean and variability of observed temperature, precipitation and wind over a period of time. The most fundamental climate descriptor is probably the Earth annual average surface temperature. This temperature is controlled by the solar energy input and the surface reflectivity of the Earth. Climate is constantly changing due to dynamic interactions between atmosphere, land surface, snow, ice, oceans, rivers, lakes, biota, and due to changes in external factors (forcings) including natural phenomena such as volcanic eruptions and solar variations, as well as human-induced changes in atmospheric composition. The radiation balance of the Earth will change as a result of changes in the incoming solar radiation, changes in the fraction of solar radiation that is reflected, and changes in greenhouse gas (GHG) concentrations. The increasing emissions of GHGs from human activities have led to a marked increase in atmospheric concentrations of the long-lived GHG gases CO2, CH4, N2O, SF6, perfluorocarbons (PFCs), hydrofluorocarbons (HFCs), chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs) and halons, and the human-induced radiative forcing of the Earth’s climate is largely due to the atmospheric increases in these. Global energy use is projected to continue to grow. With no substantial change in policies, the energy sources to run the global economy will essentially remain unchanged – the majority of our energy supply will be based on fossil fuels, with consequent implications for GHG emissions. Carbon Capture and Storage (CCS) is seen as one way to mitigate climate change, and one of the more mature post combustion CO2 capture technologies is based on amine absorbents. Given the scale of implementation of post-combustion CCS, it is likely that there will be relatively small but still significant discharges of amines to the atmosphere during operation. Quantitative knowledge about the atmospheric fate of amines including their partitioning to particles and droplets and their contribution to the formation of new particles, is therefore important to an environmental impact assessment of amine-based CO2 capture. The CO2 Technology Centre Mongstad (TCM) is the world’s largest facility for testing and improving CO2 capture. The knowledge gained will prepare the ground for CO2 capture initiatives to combat climate change. TCM is a joint venture between the Norwegian state, Statoil, Shell and Sasol. It is located at the West coast of Norway, north of the city Bergen. The main ambitions of TCM are: (1) to test, verify and demonstrate CO2 capture technology owned and marketed by vendors; (2) to reduce cost, technical, environmental and financial risks; (3) to encourage the development of the market for carbon capture technology, and (4) to stimulate international development. The centre was officially opened on May 7th 2012, and consists of two CO2 capture demonstration plants and a utility system. One plant is an amine plant designed by Aker Clean Carbon, and the other is a chilled ammonia plant designed by Alstom.

-31 -

XXXVIII CSI 2013

Plenary Lecture Abstracts

(PL3) MOLECULAR-LEVEL ANALYSIS AND PHOTOCHEMICAL AGING OF ATMOSPHERIC ORGANICS IN AMBIENT PARTICLES AND AQUEOUS DROPLETS Sergey A. Nizkorodov Department of Chemistry, University of California, Irvine, CA 92697-2025, USA Organic aerosols make up a significant fraction of the atmospheric particulate matter. They affect air quality, visibility, and regional and global climate. What makes the representation of organic aerosols in climate and air pollution models especially challenging is their dynamic nature – they continuously change their chemical composition and physical properties as a result of various “aging” processes. This presentation will discuss the effects of particle-phase photochemical and dark reactions on the molecular level chemical composition of biogenic organic aerosols. This question will be addressed with a combination of novel methods of high resolution mass spectrometry and photochemistry.

-32 -

XXXVIII CSI 2013

Plenary Lecture Abstracts

(PL4) CHARACTERIZATION OF ATMOSPHERIC AEROSOL PARTICLES BY ELECTRON MICROSCOPY Stephan Weinbruch, Martin Ebert, Konrad Kandler, and Nathalie Benker Institute of Applied Geosciences, Technical University Darmstadt, Darmstadt, Germany Characterization of atmospheric aerosol particles is of special importance in a number of fields in environmental science including:  climate research (e.g., optical properties of aerosols, cloud formation),  ecology (e.g., input of organic and inorganic pollutants into ecosystems),  public health (e.g., adverse health effects of aerosol particles),  cultural heritage preservation (e.g., degradation of monument surfaces). In these applications, characterization of individual particles by electron microscopy (scanning and transmission electron microscopy) and related spectroscopic techniques (X-ray microanalysis, electron energy loss spectroscopy) complements or even replaces bulk chemical techniques. Information obtained by electron microscopy includes size, shape, morphology, nanostructure, fractal geometry, chemical composition (elemental composition and in selected cases oxidation state), phase composition, and mixing state of particles. In addition, environmental scanning and transmission electron microscopy can be used to study thermal, hygroscopic and ice-forming properties of individual particles in situ. Application of electron microscopy is especially suited for small sample amounts (e.g., airborne sampling with high time resolution), nanoparticles (where it may difficult to obtain an appropriate mass for bulk analysis), and for investigation of processes that are scaled with the particle number or particle surface (e.g., heterogeneous ice nucleation, systemic effects after inhalation of ultrafine particles). In the present contribution, an overview of the capability of electron microscopy in particle characterization is given first. In the second part, examples of recent applications from our research group in the context of climate research are given. These examples include the role of aerosol particles in heterogeneous ice nucleation and source apportionment of soot. In the atmosphere, homogeneous ice nucleation is only observed at temperatures below -39 °C. At higher temperatures, ice nucleation requires the presence of aerosol particles which act as ice nuclei (IN). Minerals dust (especially clay minerals) and biological particles are efficient IN. In addition, lead compounds present as heterogeneous inclusions (often with diameters of a few nanometer only) seem to enhance the ice forming capability of aerosol particles substantially. Environmental scanning electron microscopy was used to determine the ice nucleation behavior different minerals in laboratory experiments (Zimmermann et al., 2007, 2008). In addition, scanning and transmission electron microscopy are used for identification of IN nuclei in various field experiments (Cziczo et al. 2009; Ebert et al., 2011). Soot (black carbon) is a strongly absorbing aerosol component. Therefore, soot deposited on snow will strongly reduce the albedo of the snow, and may also lead to increased melting. On a global scale, biomass burning, coal burning and traffic are the major sources of soot. Based on nanostructure, minor element contents and the presence of heterogeneous inclusions it is attempted to develop a fingerprint for the different soot sources.

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XXXVIII CSI 2013

Plenary Lecture Abstracts

References: Cziczo D., Stetzer O., Worringen A., Ebert M., Weinbruch S., Kamphus M., Gallavardin S.J., Curtius J., Borrmann S., Froyd K.D., Mertens S., Möhler O., and Lohmann U. (2009): Inadvertent climate modification due to anthropogenic lead., Nature Geoscience 2, 333-336. Ebert M., Worringen A., Benker N., Mertes S., Weingartner E., and Weinbruch S. (2011): Chemical composition and mixing-state of ice residuals sampled within mixed phase clouds., Atmospheric Chemistry and Physics, 11, 2805-2816. Zimmermann F., Ebert M., Worringen A., Schütz L., and Weinbruch S. (2007): Environmental scanning electron microscopy (ESEM) as a new technique to determine the ice nucleation capability of individual atmospheric aerosol particles., Atmos. Environ. 41, 8219-8227. Zimmermann F., Weinbruch S., Schütz L., Hofmann H., Ebert M., Kandler K., and Worringen A. (2008): Ice nucleation properties of the most abundant mineral dust phases., J. Geophys. Res. 113, D23204, doi: 10.1029/2008JD010655.

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XXXVIII CSI 2013

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(PL5) BASIC RESEARCH FOR CHEMICAL ABSORPTION OF CARBON DIOXIDE USING NMR SPECTROSCOPY Cristina Perinu,1 Bjørnar Arstad,2 Aud M. Bouzga,2 Klaus J. Jens1 1 2

Faculty of Technology, Telemark University College, Kjølnes ring 56, 3901 Porsgrunn, Norway SINTEF Materials and Chemistry, Forskningsveien 1, 0314 Oslo, Norway

e-mail: [email protected] Nowadays, there is strong concern with the anthropogenic CO2 (carbon dioxide) emission activities, mainly the combustion of fossil fuels and chemical transformation, which is driving the global warming. Several options for the reduction of CO2 emissions have been proposed. Among them, post-combustion capture (PCC) technology based on the chemical absorption of CO2 in aqueous amines is considered the most feasible and robust technology to be applied in short-term on a larger scale. The process of chemical absorption in PCC involves the reaction of CO2 with an amine solvent to form an intermediate compound which, with the application of heat, will be regenerated to give the original solvent and a CO2 stream (that will be transported for storage). However, the main drawbacks still limiting the application on an industrial scale are represented by the high energy demand for CO2 release and amine regeneration, the corrosivity of the amine solution and the tendency of degradation. In order to develop novel absorbents and improve the efficiency of PCC technology, an accurate understanding of the fundamental chemical processes (such as equilibriums, kinetics and thermodynamics) involved in the capture and release of CO2 in aqueous amine solvents is of paramount importance. Reliable estimates of the liquid phase composition (identification and quantification, called speciation) are a prerequisite both to perform chemical investigations and develop theoretical models for kinetic and thermodynamic studies. In the present context, speciation is rather involved since several parallel reactions that give rise to a large number of species occur. For primary (RNH2) and secondary amines, the following main equilibrium reactions are considered to take place in the liquid phase: 2 RNH2 + CO2(aq) RNHCOO- + RNH3+ RNHCOO- + H2O  RNH2 + HCO3HCO3- + H2O  CO32- + H3O+ RNH3+ + H2O  RNH2 + H3O+

(1) (2) (3) (4)

Within the analytical techniques used to chemically investigate these multi-equilibrium systems, Nuclear Magnetic Resonance (NMR) is considered to be the most valuable and successful tool because direct qualitative and quantitative information about all the species formed during the absorption and desorption of CO2 can be gathered (including unknown compounds, degradation and/or secondary products). By speciation, relationships between amine structures can be unveiled, hypothesis on reaction mechanisms may be proposed and other information on factors influencing reactions may be obtained. In the present work, a NMR investigation on a series of aqueous primary alkalonamines as absorbents for CO2 capture is carried out in order to understand the influence of the amine chemical structure on the absorption of CO2. By proper optimization of NMR parameters, extensive quantitative 13C NMR experiments to determine the concentrations of all the species at the equilibrium and consequentially the carbamate hydrolysis constant (2) are performed. These data will be used for the establishment of the linear free-energy relationships between the different amines. Moreover, further NMR experiments are also acquired to support the quantitative results in revealing relationship between amine structures and deriving hypothesis on reaction mechanisms. In the context of the present contribution, the methods used to carry out quantitative NMR experiments and the main results showing the influence of structural change on the activities of amines in CO2 capture will be presented. Moreover, some considerations on the important contribution that NMR can give in the investigation of chemical equilibriums to improve amine characteristics and rationalize the development of high performance CO2 absorbents will be discussed.

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XXXVIII CSI 2013

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(PL6) MOLECULAR ANALYSIS OF THE ORGANIC AND ELEMENTAL CARBON FRACTIONS (EC/OC) OF AMBIENT PARTICULATE MATTER BY COUPLING OF A THERMAL CARBON ANALYZER TO PHOTO-IONIZATION MASS SPECTROMETRY J.Grabowskia, T.Streibela, J.Chowb, L.-W. Chenb, M.Sklorza, J. Passiga H. Czecha, O. Sippulaa and R.Zimmermanna Joint Mass Spectrometry Centre of University of Rostock, Chair of Analytical Chemistry, Rostock/Germany and Helmholtz Zentrum München,CMA, Neuherberg/Germany (O.S. on leave from University of Eastern Finland), Contact: [email protected] DRI-Desert Research Institute, Reno, NV, USA Carbonaceous material in airborne particulate matter (PM) is of increasing interest due its adverse health effects and its potential influence on the climate. Its analytical ascertainment on a molecular level is still challenging. Hence, analysis of carbonaceous fractions for many studies is often solely carried out by determining sum parameters such as the overall content of organic carbon (OC) and elemental carbon (EC) as well as the total carbon content, TC (sum of OC and EC). The used thermal analyzing procedure, however, allows to get additional interesting information: By defining different thermal OC fractions (i.e. temperature steps in the thermal analyzer) also information on the refractory properties of the carbonaceous material is obtained. In this context it is particularly interesting to investigate the release and formation behaviors of the evolved molecular species responsible for the different OC and EC fractions. Thus after initial promising results of a pre-study [1] in the current work a thermal EC/OC carbon analyzer (Model DRI 2000) and a homebuilt photoionization time-of-flight mass spectrometer (PI-TOFMS) were hyphenated [2] to investigate individual organic compounds in particular from the different OC fractions The carbon analyzer enables the stepwise heating of quartz filter samples loaded with PM and provides the sum values of the carbon release (Used temperature steps: “Improve protocol” [2]: OC1 - 120 °C, OC2 - 250°C, OC3 - 450°C OC4 - 550°C). With the on-line coupled PI-TOFMS now in addition the organic compounds which are released during the thermal profile are detectable in real time. This is possible by the soft photo ionization methods (SPI - single photon ionization and REMPI - resonanceenhanced multi photon ionization) which are suppressing fragmentation upon ionization. The two instruments were coupled by a newly developed interface and characterized with standard substances. The final thermal EC/OC-analyzer-PI-TOFMS hyphenated instrument then was applied to several types of PM filter samples, such as ambient aerosol, gasoline/diesel emissions and wood combustion emission. Ambient filter samples e.g. showed a strong impact of organic wood combustion markers. This was revealed by comparison to the thermal release signatures of pure cellulose, lignin and wood combustion PM with samples of ambient air PM. At higher temperatures (450 °C) often a shift to smaller molecules is visible in the mass spectra. This is due to the thermal decomposition of larger oligomeric or polymeric molecular structures comparable to lignocelluloses and similar oxygenated humic-like substances. PM from vehicle exhaust (gasoline and diesel with 10% biodiesel) was analyzed. Gasoline PM exhibited large polycyclic aromatic hydrocarbons, whereas diesel PM showed a much higher total organic content in the REMPI measurements. The detected pattern (SPI) revealed a strong influence of the biodiesel content on the nature of the organic PM material. Finally the added value of this specialized thermal analysis technology for the field of environmental research is discussed. The health effects of organic fractions in anthropogenic aerosols are currently further investigated in the framework of the Helmholtz Virtual Institute of Complex Molecular Systems-Aerosols and Healt in Environmental Health, HICE (www.hice-vi.eu). References: [1] T. Streibel et al., (2006). Anal. Chem. 78, 5354-5361; [2] J. Grabowsky et al. (2011). Anal Bioanal Chem 401, 3153–3164

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(PL7) ARCTIC – FROM COLD WAR TO ARCTIC MELT DOWN 20 YEARS OF ARCTIC MONITORING AND ASSESSMENT OF POLLUTANTS AND CLIMATE CHANGE BY AMAP Lars Otto Reiersen, Artic Monitoring and Assessment Programme, Oslo, Norway Introduction AMAP was initiated in 1991 by Ministers from the eight Arctic countries (Canada, Denmark, Finland, Iceland, Norway, Russia, Sweden and USA) that today is the Arctic Council. AMAP was tasked to monitor and assess the pollution of the Arctic, including effects on ecosystems and humans. In 1993, AMAP was asked to include assessments of climate change - including UV/ozone and its effects on Arctic ecosystems and humans. Since 1993 AMAP has delivered more than 30 scientific and technical assessments. During the first ten years the main focus was on contaminants like persistent organic pollutants (POPs), heavy metals (especially mercury, lead and cadmium), radionuclides, acidification (especially forest death around smelters) and petroleum hydrocarbons. During the following ten years the climate change got increasing priority, and today it is the combined effects of climate, pollutants and other stressors that have the main focus. Over all the years, the effects due to pollution and climate change on humans, especially the Arctic indigenous peoples has been a priority area in relation to their food security and life style and to provide advice to health workers. Materials and methods AMAP has developed strict Guidelines for the work to be done, both for the monitoring part, the assessment and data handling. AMAP recommend methodologies accepted by international scientific communities and other international organization to achieve comparable data. There are special requirements for QA/QC programmes and reporting to Thematic Data Centers. The Guidelines are updated when new components are added or new methods accepted. All of these Guidelines are available from AMAP web site www.amap.no . Results The assessments have documented that a range of contaminants: POPs, mercury, radionuclides and acidifying components have been and still are transported into the Arctic area and deposited in the environment. Some of these contaminants accumulate in food chains, and some also bio-magnify in species that feed high in the food chain, including humans. POPs accumulate mainly in the marine food web and are bound to lipids (fat), with potential to affect high trophic level predators such as polar bears and killer whales, but also indigenous human populations that consume marine mammals as part of their traditional diet. The same goes for mercury which also accumulates in fish and marine mammals, whereas for radionuclides, the terrestrial food chain is most affected and indigenous people living on reindeer meat are the most exposed groups. Effects due to the exposure to POPs and methyl mercury have been documented in Arctic animals (e.g. polar bear and glaoucous gulls) and humans. This paradoxical situation –- where Arctic people that hardly used and had little benefit from products containing these harmful contaminants, are among the most highly exposed groups to these contaminants anywhere on the planet - has resulted in the so-called “the Arctic dilemma”. The marine food chain is rich in fat, which provides energy as well as essential vitamins for humans. POPs accumulate in the blubber and mercury in the meat of Arctic marine organisms - two main components of a diet that can be a key to survival under the harsh conditions that exist in the Arctic. The last eight years have been among the warmest years ever recorded in the Arctic since 1880. The -37 -

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melting of the Greenland ice sheet and Arctic mountain glaciers and ice caps have increased over the last decades, the permafrost is thawing and the sea ice has been thinner and the extent of the summer sea ice reduced since satellite observations started in the 70-ties. Combined effects with Short Lived Climate Forces (black carbon, ozone, etc.) and feedback mechanisms (reduced albedo and increased heat adsorption) have been documented in the latest reports. Climate models predict temperature increases that may have a dramatic effect on the ice and snow conditions in large parts of the Arctic on time scales as short as a few decades. The melting of multiyear land ice and thawing of permafrost is remobilizing contaminants that has been deposited. AMAP has also reported an interesting link between climate change and the transport of contaminant and precipitation over the Arctic – combined effects. In May this year AMAP delivered the first assessment on Arctic Ocean Acidification (AOA). The climate change is affecting the Northern areas and it is creating challenges and opportunities. Challenges for the local people to continue the traditional life style, e.g. when sea ice is no longer close to the coast bring seals to the hunters, and then change in snow and permafrost are affecting terrestrial ecosystems and thereby herding, hunting and food storage. Opportunities are for increased sea transport, mining and oil and gas exploration and exploitation, tourism, etc. The results from AMAP have played a significant role in the establishment of international protocols and conventions to handle pollution, e.g. the Århus protocol and the Stockholm convention. AMAP has established a close cooperation with UNEP Chemicals to achieve a better control for global emission of mercury and a new global agreement to reduce emission of mercury will be signed this autumn – the Minamata agreement. AMAP is at present implementing a scientific project assessing the combined effects of climate change and contaminants on human health – the ArcRisk project to be presented in January 2014. AMAP together with international organizations has put priority on analysing the combined effects of several stressors or drivers on Arctic ecosystems, the human health and the societies. We intend to perform a significant work on the effects and adaptation to the Arctic Change issue the next five years. All AMAP assessment reports are available from the AMAP web site www.amap.no .

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XXXVIII CSI 2013

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(PL8) SPECTROSCOPY UNDER ICE Carlo Barbante - Institute for the Dynamics of Environmental Processes –CNR ,University of Venice, Italy - Department of Environmental Sciences, Informatics and Statistics, University of Venice, Italy - Centro Linceo interdisciplinare B. Segre, Accademia Nazionale dei Lincei, Rome, Italy Polar ice caps are among the best archives of atmospheric composition of the past. Analysing the snow layers continuously deposited during centuries and millennia, it is possible to reconstruct the chemical composition of the atmosphere of our planet. Many chemical species are entrapped in gaseous or particulate phases into the snow and ice and thanks to sophisticated analytical techniques we are able to quantify their fluxes on the Earth’s surface. In addition, ice caps sometime conceal enormous undisclosed subglacial lakes, buried under hundreds meters of ice, which have preserved fossil liquid water for millions of years. The analysis of these matrices, the purest water on the Earth’s surface, poses a real challenge to analytical chemists that have to develop ultrasensitive analytical methods and stringent protocols to avoid sample contamination. In this talk I will review the recent developments in the speciation analyses of these ultra-clean matrices. In particular I’ll present a novel method coupling a high-performance liquid chromatography with ion chromatography and inductively coupled plasma mass spectrometry, which allows the determination of iodine (I) and bromine (Br) species (IO3−, I−, Br−, BrO3−). Iodine and bromine species participate in key atmospheric reactions including the formation of cloud condensation nuclei and ozone depletion. Additional examples on the state of the art in this field of research will also include the iron speciation analysis using Collision Reaction Cell-Inductively Coupled Plasma-Mass Spectrometry (CRC-ICP-MS) that we have recently applied to Antarctic ice samples. This has shown the importance of moving a step forward from the traditional elemental analyses in snow and ice cores, applying the elemental speciation approach to these extremely diluted chemical matrices.

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XXXVIII CSI 2013

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(PL9) BIOLUMINESCENT ECOLOGICAL ASSAY. FEATURES AND SCOPE OF APPLICATIONS Nadezhda Kudryasheva1,2 1

Institute of Biophysics SB RAS, Akademgorodok, 50/50, Krasnoyarsk, 660036, Russia Siberian Federal University, Svobodniy Pr., 79, Krasnoyarsk, 660041, Russia e-mail: [email protected]

2

Luminous marine bacteria can emit green light as a result of enzymatic chemiluminescent (i.e. bioluminescent) reactions involved in metabolic processes. Bacterial bioluminescent spectra are wide and asymmetric, their maxima are around 490-500 nm. The spectral shape is stable, but luminescent intensity is highly sensitive to toxic compounds. This is why bacterial bioluminescent assays have been widely used to monitor environmental toxicity for more than forty years, and now they are conventional and important biotechnological applications of the bioluminescence phenomenon. The tested parameter here is the luminescent intensity that can be easily measured instrumentally. The advantages of bioluminescent assays are high sensitivity, simplicity and rapidity of measurements (1–3 min), and availability of simple devices to register toxicity. Bioluminescent assay systems can be based on biological objects of different levels of organization – bacteria-based or enzyme-based bioassays, providing for a study of the effects of toxic compounds on cells or enzymes, respectively. Bioluminescent assays are classified as biological assays. Interrelations between biological and chemical assays have been intensively discussed till now. As a matter of fact, the main feature of all bioassays is an integral response that accounts for nonadditivity of the effects of numerous environmental pollutants and natural components. It implies that the toxic effect of a sum of compounds can be higher or lower than the sum of the effects of these compounds taken separately. Chemical analyses per se do not evaluate hazard to living organisms; they take no account of non-additivity of the effects and differences in the sensitivity of various organisms. Additionally, in should always be implied that chemical assays were initially calibrated using a standard biological test system under standard environmental conditions. It is supposed that only a combination of chemical and biological methods can provide complete information on the ecological state of a medium. This combination should involve bioassays of different sensitivity to toxic compounds. Analyses of complex results of biological and chemical assays require understanding the mechanisms of toxic effects in organisms. It is known that toxic effects of exogenous compounds are determined by physicochemical characteristics of the compounds in aqueous solutions; the effects can be classified as physical, chemical and/or biochemical ones in the bioluminescent assay systems. Basing on a broad investigation of effects of model toxic exogenous compounds on bioluminescent assay systems, classification of the effects on the bioluminescent enzyme reaction is suggested. Five mechanisms are discussed (Fig.1): (1) change in electron-excited states’ population and energy transfer, (2) change in the efficiency of the S-T conversion in the presence of an external heavy atom, (3) change in the rates of coupled reactions, (4) interactions with enzymes and variation of the enzymatic activity, (5) nonspecific effects of electron acceptors.

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Chemical reaction

S2* T2*

Effects of exogenous compounds: 1. electron-excited states population 2. S-T conversion 3. coupled reactions 4. enzymes 5. electron density distribution (all stages of the bioluminescent process)

S1* T1 hv S0

Bioluminescent emitter Fig.1. Classification of effects of exogenous compounds at different stages of bioluminescent process. Effects of different groups of exogenous compounds were discussed according to the classification suggested. Energy transfer processes (mechanism 1) contribute to the bioluminescent intensity change in the presence of exogenous compounds with the energy of electron-excited states lower than that of the bioluminescent emitter. Fluorescent exogenous compounds of this kind can provoke changes in bioluminescent spectra. Iodine- and bromine-substituted exogenous compounds change the efficiency of the S-T conversion (mechanism 2), but the contribution of this mechanism is much lower than that of mechanism (4). Organic and inorganic oxidizers (quinones, metals with variable oxidation numbers, etc.) produce specific changes in bioluminescence kinetics: a bioluminescent induction period appears; its value depends on concentration and redox potential of the oxidizers. A competition of the oxidizers with FMN for NADH in the reaction of NADH:FMN-oxidoreductase is responsible for these changes (mechanism 3). Such specific kinetic changes make a bioluminescent enzymatic assay specific to oxidizers: oxidative toxicity of solutions can be evaluated using the bioluminescent induction period, while general toxicity – using the maximal luminescent intensity. Interactions with enzymes (mechanism 4) is a prevalent mechanism for most exogenous compounds; its efficiency depends on the hydrophobicity of organic exogenous compounds, atomic weight of haloid substituents, or electron-accepting properties of metal ions. Interactions of exogenous compounds with enzymes studied using time-resolved fluorescent techniques are discussed. Mechanism 5 is specific for solutions of polar exogenous compounds, e.g., metal salts. Bioluminescent assays were found to be sensitive to alpha- and beta-radionuclides. The role of peroxides (mechanism 3) and electron transfer (mechanism 5) in bioluminescence activation and inhibition in radionuclide’ solutions are under discussion. Acknowledgements: The work was supported by Grant from the RFBR (N 13-04-01305) and the Programme ‘Molecular & Cellular Biology’ of the Russian Academy of Sciences.

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XXXVIII CSI 2013

Plenary Lecture Abstracts

(PL10) FTIR SPECTROSCOPY IN MICROBIAL ECOLOGY: ‘SHEDDING IR LIGHT’ ON CELLULAR METABOLIC RESPONSES TO ENVIRONMENTAL FACTORS Alexander A. Kamnev, Laboratory of Biochemistry, Institute of Biochemistry and Physiology of Plants and Microorganisms, Russian Academy of Sciences, 410049 Saratov, Russia e-mail: [email protected]; [email protected] Infrared (IR) spectroscopy, from its early decades up to now, has been used as a routine technique for structural analysis in materials science. The main advantage of this type of vibrational spectroscopy techniques representing, on the other hand, its complicacy is that virtually all major chemical functional groups of the sample under study contribute to the resulting spectrum. The latter includes not only bands featuring all possible vibration modes ‘visible’ in the IR, but also reflects all possible non-covalent interactions between functional groups in a sample which affect bonding energies and, therefore, vibrational frequencies. Moreover, IR spectroscopy is, in my opinion, one of the most ‘provocative’ spectroscopic techniques. While in most others a wrong methodology or sample preparation would result in obtaining a clearly poor or no spectrum, a ‘rich’ IR spectrum could almost always be recorded. However, in order for the IR spectrum to represent the real ‘state of the matter’, both the sample preparation and the methodology used for recording a spectrum should be absolutely adequate and ‘compatible’ with each other. Finally (last but not at all least!), the most creative and often complicated part is the interpretation of the spectrum thus obtained, which may appear to be quite a challenging task. All the aforementioned features of IR spectroscopy are even more important in modern Fourier transform IR (FTIR) spectroscopy featured by significantly improved instrumental capabilities, greatly enhanced sensitivity and signal-to-noise ratio. Its applications in biological fields, commonly characterised by extremely sophisticated and highly heterogeneous samples (from biomacromolecules to cells and tissues), yet steadily grow. For instance, while the first IR spectroscopic studies of microbiological objects appeared already in the middle of the XX century, the real development of efficient bioanalytical applications in microbiology started after the 1980s with FTIR spectrometers becoming more available. In our laboratory, for over a decade we have been conducting collaborative research on microbial cellular metabolic responses to various environmental factors using FTIR spectroscopy as the main analytical tool [1–4] or in combination with other techniques [5–7]. In this talk, representative examples will be given illustrating the fascinating possibilities of FTIR spectroscopy in microbial ecology related to analysing fine structural and quantitative modifications of major cellular components which reflect microbial adaptation to unfavourable conditions. These include modifications of cellular proteins with a redistribution of their secondary structure components as a response to stress factors or molecular signals; biosynthesis and intracellular accumulation of biopolyesters, fine changes in their structure and degree of crystallinity as a microbial adaptation strategy to nutritional and other stresses. The FTIR methodology used in these studies included the diffuse reflectance (DRIFT) mode. This method allows the microbiological samples under study, usually dry biomass, to be analysed without using highly polar matrices such as KBr and thus to avoid uncontrollable and often quantitatively unpredictable shifts of vibrational bands of some polar functional groups, especially those involved -42 -

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in H-bonding. This is most important for analysing intracellular proteinaceous components, the secondary structure of which is formed by various types of H-bonds between polypeptide chains. However, for microbial intracellular polyester granules, both conventional strong H-bonding (involving water molecules remaining within the granules as a result of polycondensation) and weak C–H...O bonds play a significant role. Our studies mostly involved bacteria of the genus Azospirillum [1–6] which are capable of establishing effective associative symbioses with higher plants and therefore belong to the diverse family of plant-growth-promoting rhizobacteria (PGPR). This feature, together with their high adaptability and resistance to stresses, is of significant importance for agricultural biotechnology, including PGPR-assisted phytoremediation of contaminated soils. Thus, these bacteria have been attracting the steadily increasing attention of researchers already for over three decades. Another advantage of these microorganisms is that some of their ubiquitous species, e.g. A. brasilense, comprise different strains which occupy different ecological niches in the rhizosphere of host plants. Such strains may be used as model microorganisms exhibiting different ecological behaviour under similar stress conditions owing to their different adaptation strategies. The author’s research related to FTIR spectroscopy in microbiology has been supported in part within the recent years by grants from NATO (Projects LST.NR.CLG.981092 and ESP.NR.NRCLG 982857), from The Siberian Health International LLC (Novosibirsk, Russia; Call for Projects, 2012) as well as under the Agreement on Scientific Collaboration between the Russian and Hungarian Academies of Sciences for 2011–2013 (Project # 28). 1. Kamnev A.A., Sadovnikova J.N., Tarantilis P.A., Polissiou M.G., Antonyuk L.P. Microb. Ecol., 2008, 56: 615-624. 2. Kamnev A.A. Spectroscopy Int. J., 2008, 22: 83-95. 3. Tugarova A.V., Kamnev A.A., Tarantilis P.A., Polissiou M.G. Eur. Biophys. J., 2011, 40 (Suppl. 1): S240. 4. Kamnev A.A., Tugarova A.V., Tarantilis P.A., Gardiner P.H.E., Polissiou M.G. Appl. Soil Ecol., 2012, 61: 213-216. 5. Kamnev A.A., Tugarova A.V., Antonyuk L.P., Tarantilis P.A., Kulikov L.A., Perfiliev Yu.D., Polissiou M.G., Gardiner P.H.E. Anal. Chim. Acta, 2006, 573-574, 445-452. 6. Kamnev A.A., Tugarova A.V., Kovács K., Kuzmann E., Biró B., Tarantilis P.A., Homonnay Z. Anal. Bioanal. Chem., 2013, 405: 1921-1927. 7. Kamnev A.A., Tugarova A.V., Selivanova M.A., Tarantilis P.A., Polissiou M.G., Kudryasheva N.S. Spectrochim. Acta Part A: Mol. Biomol. Spectrosc., 2013, 100: 171-175.

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(PL11) ATMOSPHERIC DEPOSITION OF TRACE ELEMENTS ON THE LOCAL AND REGIONAL SCALE STUDIED BY ICPMS ANALYSIS OF MOSS SAMPLES Eiliv Steinnes1, Hilde Thelle Uggerud2, Torunn Berg1 and Katrine Aspmo Pfaffhuber2 1

Department of Chemistry, Norwegian University of Science and Technology, NO-7491 Trondheim, Norway 2 Norwegian Institute for Air Research, NO-2027 Kjeller, Norway e-mail: [email protected] Naturally growing moss is a useful substrate for large-scale studies of atmospheric deposition of trace elements. Starting in 1977 the temporal trends of trace element deposition has been studied every five years in Norway using this approach. Since 1990 ICPMS has been the analytical technique of choice for this purpose, and in the most recent survey in 2010 the geographical trends were reported for as much as 53 elements in Hylocomium splendens moss samples from 464 sites situated all over the country. Since 2000 results from these campaigns are reported to the joint European deposition survey employing moss biomonitoring. Extensive contamination by a number of metals in the south of Norway from trans-boundary pollution has been substantially reduced over time. Starting in 2000 the moss sampling technique was also used for mapping metal deposition patterns around 15 major industrial point sources, including aluminium and ferroalloy smelters, cement mills, and copper-nickel smelters. The most severe contamination was observed in the vicinity of two Russian smelters situated close to the Norwegian border. Appreciable deposition of some metals was also observed locally around metal industries at Mo i Rana and Odda. Results from such multi-element studies of moss samples do not necessarily represent contribution from air pollution only. Previous studies by the authors comparing concentrations in moss with atmospheric deposition rates from precipitation sampling over a corresponding time period showed significant positive correlations for trace elements such as V, As, Cu, Zn, Mo, Cd, Sb, Tl, Pb, and Bi. For some elements the content in moss is affected by uptake from the growth substrate, as in the case of K, Ca, Mn, Rb, Cs, Ba, and partly Cu and Zn. Another source is local windblown soil dust, such as for Ti, Fe, REE, Th, and U. Finally contribution from the marine environment is important for the supply of some elements to the moss, such as B, Na, Mg, and Sr. Principal component factor analysis is a convenient tool for distinguishing contributions of elements from different pollution sources and separating natural and anthropogenic contributions to the element distribution in moss samples.

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XXXVIII CSI 2013

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(PL12) MASS SPECTROMETRY MADE EASY: THE QUEST FOR SIMPLICITY IN FORENSIC, FOOD, PHARMACEUTICAL, ENVIRONMENTAL, MEDICAL AND BIOCHEMICAL ANALYSIS Marcos N. Eberlin Universidade Estadual de Campinas, Brazil Mass spectrometry is generally viewed as a highly complex and demanding technique, full of difficulties and apprehensions, particularly for the non expert. Ease and simplicity are therefore infrequently used descriptors of MS but a series of revolutionary developments are turning a complex technique into a model of simplicity making MS easier than ever. Focusing on spray-based ambient desorption/ionization techniques, I will illustrate using applications in forensic, food, pharmaceutical, environmental, medical and biochemical analysis, that previously unthinkable goals for MS, that is: a) to bring it to the real world open atmosphere environment; b) to perform fast, selective and highly sensitive chemical and biochemical MS analysis with ease while c) avoiding pre-separation and sample work-up for samples at their natural environment And therefore, at the end, that the task of making MS accessible at wherever MS is needed and by whoever needs it – has become fully feasible. The applications that will be highlighted will illustrate that, without compromising the unique combination of high speed, selectivity, sensitivity and separation competences, simplicity has become a new MS attribute – a 5th “S” in the unique 5S set of MS trademark features. Immediate MS can now also be performed by non-specialists with ease and simplicity using no preseparation and sample work-up protocols. We can now offer mass spectrometry to the “masses” – wherever it is needed and to whoever needs it.

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XXXVIII CSI 2013

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(PL13) CONFOCAL SPECTRAL IMAGING TECHNIQUE IN THE DEVELOPMENT OF PHOTOAND NEUTRONSENSITIZERS FOR ANTICANCER THERAPY Alexey V. Feofanov1,2, Anastasija V. Efremenko1,2, Anastasija A. Ignatova1,2, George V. Sharonov1 and M.V. Astapova1 1

Shemyakin-Ovchinnikov Institute of Bioorganic Chemistry, Russian Academy of Sciences, ul. Miklukho-Maklaya 16/10, 117997 Moscow, Russia 2 Biological Faculty, Lomonosov Moscow State University, Vorobyevi Gori 1, Moscow, 119992, Russia e-mail: [email protected] Photosensitizers and neutronsensitizers are compounds that are non-toxic themselves for cells, but able to accumulate in cancer cells and kill them in the course of irradiation with photons and neutrons, respectively. Photosensitizers are essential component of photodynamic therapy (PDT). Photoinduced cell death occurs because of generation of reactive oxygen species by a photosensitizer. Boron-bearing neutronsensitizers are used for boron neutron capture therapy (BNCT). Neutronsensitizer that contains nonradioactive 10B isotopes interacts with thermal neutrons, and excited boron nuclei break into high energy α and 7Li particles, which destroy cells. Efficiency and selectivity of cancer treatment depends critically on enhanced accumulation of such sensitizers in cancer cells as compared to normal cells. Development of new improved photo- and neutron- sensitizers is an actual pharmaceutical task. Reactive oxygen species other than 1O2 NH

photons 3

O2

H

H3C H3CO2C

N

N HN

H

fluorescen O

1

H3CO2C HN

680 700 720 740 760 780 , nm

O2

Photodynamic therapy linker

α γ

neutrons

10

В Boron

7

680 700 720 740 760 780 , nm

Li neutron

capture

Photosensitizers are fluorophores that absorb light and fluoresce in red and far region (650-850 nm). Therefore, fluorescence microscopy can provide useful data about accumulation and distribution of photosensitizers in cells and tissues, can greatly help in a structural optimization of new photosensitizers. Since many porphyrin-based photosensitizers were found to accumulate in malignant cells, an idea appeared to conjugate boron nanoparticles with porphyrin derivatives for improved boron delivery in cancer cells. And again, fluorescence microscopy can assist in the development of such fluorescent nanoconjugates-neutronsensitizers. Microenvironment and molecular interactions of fluorophores affect quantum yield, maximum and shape of fluorescence spectra. Therefore, spectral characteristics of fluorescent sensitizers should be

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XXXVIII CSI 2013

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known in biological environment in order to use correctly fluorescence techniques in the studies of sensitizer cellular uptake, localization, pharmacodynamics and pharmacokinetics. A powerful tool being able to resolve this problem is a confocal spectral imaging (CSI) technique. The CSI technique measures a two-dimensional set of spectra with a three-dimensional spatial resolution from a tissue section or an intact living cell treated with a sensitizer. After, a decomposition procedure is applied: each original spectrum is decomposed into a sum of the reference spectra with appropriate coefficients. The reference spectra come from detailed in vitro study of spectral changes induced by environmental factors and molecular interactions of fluorescent sensitizer. The decomposition coefficients are used to create spectral images describing subcellular (tissue) quantitative distribution of the sensitizer. The CSI technique is utilized by us in order to: analyze and compare ability of sensitizers to penetrate in cancer cells; identify and map molecular interactions of sensitizers in cells; quantify accumulation, localization and retention of sensitizers in cells and tissues; reveal chemical modifications of sensitizers in cellular environment; analyze photostability of sensitizers. The CSI technique helps us to perform a multiparametric selection of leading sensitizers, opens a way to their structure-functional optimization. Features of the CSI technique are illustrated with our data obtained in the course of development and studies of advanced sensitizers for photodynamic and boron neutron-capture anticancer therapies.

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XXXVIII CSI 2013

Plenary Lecture Abstracts

(PL14) NEW DEVELOPMENTS IN DISEASE RECOGNITION BY INFRARED AND RAMAN SPECTROSCOPY AND MICROSCOPY: PRESENT STATUS AND FUTURE PROMISSES

János Mink1,2, Veronika Gombás2, Judith Mihály1, Csaba Németh1 and László Hajba2 1

Institute of Molecular Pharmacology, Research Centre for Natural Sciences, Hungarian Academy of Sciences, H-1525 Budapest, Hungary. 2 Research Institute of Chemical and Process Engineering, Faculty of Information Technology, University of Pannonia, H-8201 Veszprém, Hungary. e-mail: [email protected]

The fast development of infrared and Raman spectroscopic instrumentation during the past decades has made possible their application to complex problems of biology and medicine. With the availability of ultraviolet and near infrared laser excitation to replace the traditional visible lasers, the problem of background fluorescence of biological Raman samples can be avoided. The new methods of spectral manipulation and decoding the enormous informational content of vibrational spectra is aided by the availability of high-power computer workstations and advanced algorithms for data processing. The progress has been especially manifested in the field of cancer diagnostic. In this paper we try to summarise the progress achieved over the past ten years in applying vibrational spectroscopy to problems of medical diagnostic including our novel achievements. It was recently discovered in our laboratory that the infrared spectra of human skin (measured on forearm) and hair fibre showed definite correlations with the general physiological condition of the human organism. Especially strong spectral deviations were observed in case of cancerous patients even in very early stage of the illness. More than 3000 patients have been examined and based on our spectral library and developed special spectral data processing it can be suggested as a good screening methodology adequate for mass measurements. Both the developing process of the certain illness and the process of recovery can be clearly monitored. Future perspectives and limitations will be discussed. Beside the “screening“capabilities of the general health condition unique illness specific infrared signals have been observed by skin measurement of diabetic patients. Due to the great interest in dermatology and in cosmetic industry, reflective FTIR spectroscopic studies of human skin have been widely published ([1-3] and references therein). Accordingly to our best knowledge there are no publications about detection of diabetes based on mid-infrared spectra of human skin but great number of papers report about human blood measurements. Infrared spectra were compared for 39 patients suffering from diabetes and 59 healthy persons by principal component analysis (PCA). The chemometric analysis results in separation of healthy and diabetic patient’s spectra, i.e. the spectral features of healthy and diabetic patients resulted in plot of scores that fall in two sets within their respective group. The ‘infrared diagnosis’ results were compared with the genuine medical diagnosis, and among the 39 patients’ skin samples no one was misclassified. In some cases diabetes was detected in very early stage. Consequently FTIR detection can be used for prevention, early diagnosis and monitoring the status of diabetes as well. 1. Ch. Xiao, D.J. Moore, C.R. Flach, R. Mendelsohn, Vibrational Spectroscopy, 38, 151-158, 2005. 2. R. Mendelsohn, C. R. Flach and D. J. Moore, Biochimica et Biophysica Acta (BBA) Biomembranes, 1758, 923-933, 2006. 3. A. N. Crowson, Modern Pathology 19, S155–S163, 20064. G. Hosafci, O. Klein, G. Oremek, W. Mantele, Anal. Bioanal. Chem., 387, 1815-1822, 2006.

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XXXVIII CSI 2013

Plenary Lecture Abstracts

(PL15) METABOLIC FINGERPRINTING VIA MASS SPECTROMETRIC ANALYSIS OF EXHALED BREATH

Renato Zenobi, Pablo Martinez-Lozano Sinues, Lukas Bregy, Xue Li, and Jingjing He Department of Chemistry and Applied Biosciences, ETH Zurich, CH-8093 Zurich, Switzerland. e-mail: [email protected] Ambient ionization mass spectrometry offers attractive new perspectives for real-time, on-line metabolic fingerprinting of the exhaled breath of patients as well as healthy individuals. Ion formation at ambient pressure avoids problems with limited detection sensitivity and scope arising from introducing breath into a low pressure environment for ionization. We are using a nanoESIbased secondary electrospray ionization (SESI) as well as a dielectric barrier discharge (DBD) plasma ionization [1] maintained in an active sampling capillary to achieve efficient ambient ionization of compounds in exhaled breath. ppb … ppt limits of detection can be achieved, and compounds with molecular weights up to 400 Da are observed. With this technology, several interesting questions about metabolic signatures in the body can be addressed: Is there a core pattern for individual phenotypes visible in mass spectrometric “breathprints” [2]? Can diurnal changes be monitored via exhaled breath [3]? Can diseases be diagnosed via exhaled breath, and if yes, which ones? Can proper drug use (or drug abuse) be detected via analysis of the chemical composition of exhaled breath? These studies have obvious ramification for using exhaled breath as a non-invasive alternative to the analysis of blood or urine in medical diagnosis, doping control, forensics, and other areas. Capillary containing DBD

Figure: photograph of the DBD source mounted on the inlet of a Synapt G2S instrument.

Breath inlet

References: [1] M.M. Nudnova, L. Zhu, and R. Zenobi, Active Capillary Plasma Source for Ambient Mass Spectrometry, Rapid Commun. Mass Spectrom. 26, 1447-1452 (2012). [2] P. Martinez-Lozano Sinues, M. Kohler, and R. Zenobi, Human Breath Analysis May Support the Existence of Individual Metabolic Phenotypes. PLoS ONE 8(4): e59909. doi:10.1371/journal.pone.0059909 (2013). [3] P. Martinez-Lozano Sinues, M. Kohler, and R. Zenobi, Monitoring Diurnal Changes in Exhaled Human Breath, Anal. Chem. 85, 369-373 (2013).

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XXXVIII CSI 2013

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(PL16) ACCURATE MEASUREMENT OF IRON METABOLISM BIOMARKERS: NEW TOOLS AND REMAINING CHALLENGES

Maria Montes-Bayón, Tobias Konz, Alfredo Sanz-Medel. Department of Physical and Analytical Chemistry. Faculty of Chemistry. University of Oviedo. Iron balance is tightly regulated in our organism and such regulation occurs exclusively at the site of absorption, as there is no physiological process to excrete the iron excess. The majority of iron absorption occurs via enterocytes in the proximal small intestine and is then transported to other sites within the body by transferrin, the main Fe transporter in human serum. Ferroportin is a newly identified iron efflux pump that mediates the export of iron from the enterocyte into the blood stream for transferrin binding. While much remains to be discovered regarding the control of iron balance, hepcidin, a recently discovered 25 amino acid protein, is believed to be critical to this process. Hepcidin serves as a negative regulator, and when elevated, results in reduced intestinal iron absorption and macrophage iron release [1]. Tranferrin carries Fe to, among others, the liver where the metal is stored in Ferritin. Ferritin makes iron available for critical cellular processes while protecting lipids, DNA, and proteins from the potentially toxic effects of iron. Alterations in ferritin are seen commonly in clinical practice, often reflecting perturbations in iron homeostasis or metabolism. Therefore, for a better understanding of the iron metabolism disorders the development of analytical strategies that permit the specific monitoring of new biomarkers with high accuracy and precision in mandatory. In this work we will illustrate the new tools for characterization of hepcidin based on mass spectrometric (MS) and immunochemical assays. In addition, the quantitative determination of ferritin in human serum as well as its Fe binding characteristics will be introduced as potential specific biomarkers of iron metabolic diseases. [1] Kroot JJC, Tjalsma H, Fleming RE, Swinkels DW (2011) Clin Chem 57:1650-166

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XXXVIII CSI 2013

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(PL17) SALDI MASS-SPECTROMETRY: PRINCIPLES AND APPLICATION FOR DRUG ANALYSIS

Alexander Grechnikov Vernadsky Institute of Geochemistry and Analytical Chemistry of RAS, Kosygin str., 19, 119991 Moscow, Russia e-mail: [email protected] The development of laser-assisted mass spectrometric techniques has resulted in new opportunities, approaches, and methods. Surface-Assisted Laser Desorption-Ionization (SALDI) is an excellent example, which holds great promise for analytical applications. In SALDI the gas-phase ions are formed from molecules deposited on a particular surface substrate that is irradiated with a pulsed laser. This process does not require the entrainment action of an added matrix compound for desorption and ionization. This lecture consists of three parts. In the first part the main factors determining the analytical performance of SALDI are reviewed and analyzed. These factors are the following: - electronic structure of SALDI active materials; - laser irradiation parameters; - surface chemistry of SALDI active substrates; - basicity of analyte. The results and experiences from rather extensive SALDI experiments are reported. A very strong dependence of SALDI ion generation on the electronic, physical, and chemical properties of the substrates are demonstrated. The sensitivity of silicon based SALDI for about 50 compounds with varying proton affinity ranging from 800 to 1000 kJ/mol was determined, and it was found that the ion signal showed an exponential dependence on compound proton affinity. Based on experimental results and quantum chemical calculations, a model for SALDI ion generation from silicon surfaces is proposed. The details about the current state of SALDI instrumentation will be discussed in the second part of the lecture. Main concepts of SALDI realization in a comparatively simple, affordable, and highly efficient instrument are reviewed. The traditional approach for SALDI analysis is the use of a standard MALDI ion source. Two novel strategies for the construction and application of SALDI instruments are presented. The first strategy is based on a combined gas chromatography (GC) – SALDI time-of-flight mass-spectrometry. The second one includes novel methods of surface activation and sample deposition with the rotating ball inlet. It is shown that SALDI has excellent potential both for powerful liquid chromatography-SALDI MS and gas-phase SALDI MS analysis. The SALDI technique is applicable to a broad range of analytical problems and areas, including ambient air analysis, organic mass spectrometry and biochemical analysis. The third part of the lecture is focused mainly on drug analysis. Various examples including the rapid screening of pharmaceutical products without any sample pretreatment, GC-SALDI mass spectrometry of amphetamine-like drugs, protein analysis and the determination of metal-organic complexes are presented. It is shown that with simple preparation steps, biological samples can be analyzed using the SALDI technique with the detection limits at a subfemtomole level. This work was partially supported by the Program for basic researches of the Presidium of RAS №9.

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XXXVIII CSI 2013

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(PL18) SIMS AND THE SINGLE CELL

Vic Norris1 Ghislain Gangwe Nana2, Armelle Cabin2, Jean-Nicolas Audinot3, David Gibouin2, Rabah Boukherroub4, and Camille Ripoll2 1

Theoretical Biology Unit, University of Rouen, 76821, Rouen, France Equipe Assemblages Moléculaires: Modélisation et Imagerie SIMS, Laboratoire MERCI EA 3829, University of Rouen, 76821, Rouen, France 3 Institut de Recherche Interdisciplinaire (IRI, USR-3078) and Institut d’Electronique, de Microélectronique et de Nanotechnologie (IEMN, CNRS-8520), Cité Scientifique, Avenue PoincaréB.P. 60069, 59652 Villeneuve d’Ascq, France 4 Département Science et Analyse des Matériaux, Centre de Recherche Public Gabriel Lippmann, 4422 Belvaux, Luxembourg 2

e-mail: [email protected] Secondary Ion Mass Spectrometry (SIMS) is particularly suited for addressing a number of fundamental problems in biology. One of these problems is how cells reconcile the conflicting strategies required to grow in favourable conditions and to survive in harsh conditions. Using the model bacteria, Bacillus subtilis and Escherichia coli, we find evidence that a partial solution to this problem occurs at the level of the population. Cells were labelled with 13C-glucose and 15Nammonium chloride as sources of carbon and nitrogen for times ranging from a tenth of a generation to three generations; this was followed by the use of a NanoSIMS 50 to locate the incorporated isotopes and to obtain isotope ratios. This dynamic SIMS analysis revealed a remarkable metabolic heterogeneity consistent with (1) some cells growing rapidly to profit from the availability of nutrients and (2) other cells growing slowly in readiness for an environmental challenge. These results complement other results revealing population heterogeneity obtained using fluorescence microscopy to localise RNA and proteins, as in the case of the toponome, and using optical microscopy and nanodevices to study growth rates, as in the case of the suspended microchannel resonator. Where does this heterogeneity come from? This question is related to the more general problem of how cells manage to generate coherent, reproducible behaviours (i.e., phenotypes) at all; the root of the problem here is that even bacterial cells can produce tens of thousands of types of molecules and macromolecules and therefore appear to be able to generate hyperastronomical numbers of combinations of these products; the result ought to be a phenotype space so vast that coherent phenotypes rarely recur. A partial solution to this problem of phenotype space may involve the extended assemblies of molecules and macromolecules, known as hyperstructures, which have been proposed to constitute a level of intracellular organisation between the lower level of the gene or protein and the higher level of the cell itself. This solution would help with the phenotype problem by attributing behaviour to the action of a much smaller number of combinations of scores of hyperstructures. Again, using 15Nlabelling and detection on the 50 nm scale by dynamic SIMS, we find evidence in a population of E. coli growing in steady state that hyperstructures exist in different metabolic states within the same cells. We argue that this is consistent not only with the hypothesis that hyperstructures limit phenotype space but also with the hypothesis that hyperstructures control the bacterial cell cycle. The cell cycle in bacteria consists essentially of three events: the initiation of replication of the chromosome, the segregation of the chromosomes, and division of the cell. Although the cell cycle -52 -

XXXVIII CSI 2013

Plenary Lecture Abstracts

has been intensively studied, surprisingly, the nature of the fundamental control of the cell cycle remains unknown. One possibility is that this control is based on the dynamics of hyperstructures and, further, that the cell cycle itself serves to generate the heterogeneous population needed to ensure growth in heaven and survival in hell. By combining the isotope labelling of DNA, the combing of this DNA on silicon surfaces, caesium flooding and analysis by SIMS, we have developed a technique that may allow, on the scale of 150 base pairs, the quantification of DNA replication in individual chromosomes and the localisation of the molecules and macromolecules that bind to the origin of replication and to other regions on the DNA. This techique should therefore facilitate the testing of hypotheses for the control of the initiation of DNA replication.

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XXXVIII CSI 2013

Plenary Lecture Abstracts

(PL19) (HIGH RESOLUTION)2 MALDI IMAGING: RELIABLE MOLECULAR INFORMATION AT CELLULAR RESOLUTION Andreas Römpp and Bernhard Spengler Institute of Inorganic and Analytical Chemistry, Justus Liebig University, Schubertstrasse 60, D35392 Giessen, Germany e-mail: [email protected] Mass spectrometry imaging is a versatile and powerful analytical technique. Our work is focused on further increasing the biologically relevant information that can be obtained by mass spectrometry imaging. Here we present a number of improvements in instrumentation, sample preparation, measurement parameters and data processing. The discussion will be based on phospholipids in mammalian samples, but the method was also successfully used for other applications including insect and plant specimen. MS imaging experiments were performed with a high resolution atmospheric-pressure imaging source [Römpp et al., 2010] attached to ‘LTQ Orbitrap’, ‘Exactive Orbitrap’ or ‘Q Exactive’ mass spectrometers (Thermo Scientific GmbH, Bremen). Pixel size was between 2 and 10 µm. Mass accuracy was better than 2 ppm (root mean square) under imaging conditions. Tentative identification based on accurate mass was confirmed by on-tissue MS/MS experiments. A dedicated sample preparation protocol was established for the analysis of cell cultures. Phospholipids and smaller metabolites such as nucleic acids and cholesterol were imaged in single cells. A full metabolic profile was obtained from a single 7 µm pixel. Phospholipids were investigated in detail in mouse brain and human tumor samples. Proteins were analyzed after on-tissue tryptic digestion at 25 μm pixel size. MS image analysis for all these experiments showed excellent agreement with histological staining evaluation. In addition it provided highly specific molecular information. In many cases signals with very similar mass (∆m/z 100 µm depth and the multielement capability (including the light elements) make this method unique among the other techniques for elemental analysis and has led to the introduction of this method for quality control in many industrial laboratories.

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Since the introduction of radio-frequency (rf) discharges the analysis of non-conductors became possible. In combination with the feature to analyze extremely thin layers in the nm range, new demands for the glow discharge sources and power supplies exist. Sources for small and non-flat samples are needed and sputter craters with diameters up to 0.3 mm are possible nowadays. The investigation of the electrical characteristics, sputtering rates and crater shapes helps to find similarities and differences e.g. with the well-tried 4 mm sources (see Fig. 1).

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Figure 1: DC-GD-OES intensity-time profile of a hard drive at 1000 V, 3 hPa left:  4 mm, 56 mA, right:  0.3 mm, 0.25 mA For the analysis of non-conductors many investigations about rf-discharges and the corresponding equipment were going on, because the discharge should be stable in milliseconds. After the application of matched rf-generators also free running generators are now commercially applied. More recently IFW and Ingenieurbüro Birus have developed a frequency controlled system. Its advantage for special applications will be shown. More and more pulsed dc- and rf-discharges are applied in GD-OES and -MS. On the one hand, pulsed discharges reduce the thermal stress of the sample. On the other hand, this type of discharge offers a lot of additional possibilities - e.g. to optimize the crater shape or to get molecular and elemental information in glow discharge mass spectrometry (GD-MS). Up to now only pulsed dcdischarges are commercially available in GD-MS and rf at all is offered by just one GD-MS

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producer. Applications of pulsed rf-GD-OES in the field of solar cell development will be shown. The measurement of the electrical discharge parameters proved to be very essential for the optimization of the equipment and for the evaluation of the analytical results. As an example in Fig. 2 the influence of the duty cycle on the discharge conditions is shown for pulsed rf at constant voltage and pressure.

Figure 2: Ionic part of the I-U characteristics of an rf-discharge at 3.4 MHz at different pressures and duty cycles (50 µs constant pulse length, cycle during the last µs). Those people, who deal with electron microscopy, know that existing sample preparation methods such as polishing, chemical etching, and ion beam etching are laborious and time consuming. Sputtering in the glow discharge has a great number of attractive features and thus lends itself to a fast and simple sample preparation. The low energy of the sputtering ions and atoms together with the high erosion rate make glow discharges useful for the preparation of samples, which are afterwards analyzed by Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Electron BackScatter Diffraction (EBSD) etc. This part of the presentation is dedicated to possibly new applications of the glow discharge sputtering. A new source for the preparation of TEM-samples will be presented.

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XXXVIII CSI 2013

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(PL25) DEVELOPMENT AND CHARACTERIZATION OF MATERIALS FOR ADVANCED POWER PLANTS Hubertus Nickel Research Centre Jülich and University of Technology Aachen, Germany The development of modern combined cycle power plants with high thermal efficiency requires constructional materials of high strength and improved resistance against aggressive service atmospheres. After giving an introduction into the actual situation of energy resources world wide the talk concerns questions of material research for combined steam and gas turbine cycle power plants. 1) An increase of thermal efficiency of fossil fuel fired steam power plants can be achieved by increasing steam temperature and pressure. This requirement has provided the incentive for the development of 9 wt.-% chromium steels towards improved creep rupture strength as well as oxidation resistance in combustion gases. During the last decades such steels have been developed for power plant construction. Results of experiments using 18O isotopes and simulated combustion gases will be discussed with respect to oxidation mechanism of 9 wt.-% Cr steels. Also the investigation to improve these 9 wt.% Cr steels and the use of Ni-based alloys like Inconel 617 for applying higher steam temperature and pressure will be shown. 2) The increase of efficiency of large land-based stationary gas turbines for electric power generation requires increased gas inlet temperature. Gas temperature higher than 1300 °C can only be handled using air-cooled structures to keep the metal temperature below 1000°C. Only columnar grained directionally solidified (DS) or single crystal (SC) superalloys possess required creep strength and thermo-mechanical fatigue resistance. Superalloys like IN 792 DS or CMSX-4 SC with excellent mechanical properties have been developed. But the increase of component surface temperatures leads to an enhanced oxidation attack in stationary gas turbines of thermal barrier coating consisting usually of ZrO2+8-wt.-%Y2O3 on top of a MCrAlY (with M=Ni and/or Co) bond coat. Air plasma spraying (APS) and electron beam physical vapour deposition (EB-PVD) are discussed with respect to new coating materials and improved corrosion resistance. One of our research was directed to the improvement of the high temperature properties of MCrAlY alloys by addition of minor alloying elements to clarify the effect of yttrium, silicon and titanium additions on corrosion resistance. The corrosion mechanisms as well as the microstructure stability of the high temperature materials and the protective coatings were studied by combining the results of kinetic studies with extensive analytical investigations using techniques like SNMS, SIMS, SEM, TEM, Rutherford backscattering (RBS), Laser Raman Spectroscopy (LRS) as well as X-ray diffraction.

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XXXVIII CSI 2013

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(PL26) APPLICATION OF SYNCHROTRON MICROPROBE TECHNIQUES TO SPECIATION OF PLUTONIUM IN ARGILLACEOUS ROCKS Tobias Reich1, Ugras Kaplan1, Samer Amayri1, Jakob Drebert1 and Daniel Grolimund2 1 2

Institute of Nuclear Chemistry, Johannes Gutenberg-Universität Mainz, 55099 Mainz, Germany Swiss Light Source, Paul Scherrer Institut, 5232 Villigen PSI, Switzerland

e-mail: [email protected] In several European countries, e.g., France, Germany and Switzerland, argillaceous rocks are considered as a potential host rock for the construction of nuclear waste repositories. Detailed information on the interaction between the clay and plutonium, which is a major contributor to the radiotoxicity of spent nuclear fuel after storage times of more than 1,000 years, is required for the safety assessment of future nuclear waste repositories. The interaction between redox-sensitive plutonium and natural clay has been investigated in batch and diffusion experiments and by X-ray techniques. Opalinus Clay (OPA, Mont Terri Rock Laboratory, Switzerland), which was used as a reference for natural clay, consists of different clay minerals (66%), quartz (14%), calcite (13%), iron(II) minerals (4%) and traces of other minerals and organics. Due to this mineralogical heterogeneity, a combination of different synchrotron based techniques with micrometer resolution was used to study the sorption and diffusion of Pu(V) and Pu(VI), which have a high solubility at near neutral pH conditions. Different thin sections of OPA were contacted with 20 µM Pu(V) or Pu(VI) solutions at pH 7.6 under aerobic conditions for several days. In the diffusion experiment, plutonium was allowed to diffuse from a reservoir with 20 µM Pu(V) into an intact OPA bore core during one month before it was removed from the diffusion cell. The thin sections and small pieces of the bore core were investigated at the microXAS beamline at the Swiss Light Source using monochromatic synchrotron radiation with a beam size of typically 3  1.5 µm2. Micro-X-ray fluorescence (µ-XRF) mappings of both sorption and diffusion samples showed heterogeneous distributions of plutonium and other heavy elements (Ca, Mn, Fe, Sr) contained in OPA. Regions with high concentrations of plutonium, which frequently occurred in close vicinity to areas enriched in iron, were investigated by Pu LIII-edge micro-X-ray absorption near-edge structure (µ-XANES) spectroscopy. By comparing these XANES spectra to those of reference spectra of plutonium in different oxidation states, it was shown that the highly soluble Pu(V) and Pu(VI) species were reduced to the less soluble tetravalent oxidation state in all investigated samples. In some areas also Pu(III) was identified, although Pu(IV) remained the dominating oxidation state. To obtain further information about the minerals present in areas enriched in plutonium, micro-X-ray diffraction (µ-XRD) was applied. In addition to the clay mineral illite, siderite (FeCO3) could be identified near plutonium spots by µ-XRD in several thin section samples, indicating that this Fe(II) mineral acts as a reducing agent and causes the immobilization of plutonium in OPA. The examples given in this presentation illustrate that µ-XRF, µ-XANES, and µ-XRD are a powerful combination of techniques for studying the speciation and migration behaviour of actinides and other heavy toxic metals in heterogeneous natural systems like argillaceous rocks with high spatial resolution.

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XXXVIII CSI 2013

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(PL27) AN ANALYTICAL TECHNIQUE ON ITS WAY TO ADULTHOOD: CURRENT STATUS AND FUTURE PERSPECTIVES OF MASS SPECTROMETRY IMAGING Andreas Römpp Institute of Inorganic and Analytical Chemistry, Justus Liebig University, Schubertstrasse 60, D-35392 Giessen, Germany e-mail: [email protected] Mass spectrometry imaging (MS imaging) is the method of scanning a sample of interest and generating an image of the intensity distribution of a specific analyte ion. A full mass spectrum is generated for each position sequentially. In contrast to most histochemical techniques, mass spectrometry imaging can differentiate (amino acid) modifications and does not require labelling of compounds. Matrix-assisted laser desorption/ionization (MALDI) and secondary ion mass spectrometry (SIMS) are the most widely used ionization techniques for mass spectrometry imaging, but a number of alternative techniques have been developed in recent years. In particular, atmospheric pressure ionization techniques such as desorption electrospray (DESI), low-temperature plasma (LTP) and laserspray are increasingly operated in imaging mode. Each of these techniques has specific analytical capabilities that are highly complementary. While SIMS has been routinely used in material science for many years, the situation is much more challenging for MS imaging of biological (tissue) samples. Mass spectrometry imaging has seen impressive instrumental and methodological progress in the last decade. The number of groups who are working on this topic is constantly increasing. However, the field is very diverse and results are often highly dependent on the experience of the operator. In order to become a (more) routinely used method, the MS imaging workflow needs to be more robust and user-friendly. An activity that targets these issues is the EU-funded COST action (European Cooperation in Science and Technology) „Mass Spectrometry Imaging: New Tools for Healthcare Research” (BM1104). This network, which includes more than 30 MS imaging groups, aims to establish MS imaging as a routine method in clinical research. This includes setting up best practice examples for sample preparation and measurement protocols as well as by providing reference sample material for quality control. Mass spectrometry imaging produces large and complex data sets, and thus efficient strategies for processing and analyzing data are essential. A common data format for the flexible exchange and processing of mass spectrometry imaging data was developed: imzML (www.imzml.org). Data sets from more than 10 different MS imaging platforms (including MALDI, SIMS, DESI and LA-ICP) have been converted into imzML so far. A growing number of software tools support imzML (including commercial and open-source software packages). This allows for choosing from a variety of options to display and process MS imaging data. Users are no longer limited to proprietary software, but are able to use the processing software best suited for a specific question or application. A common data format is not a mere technical detail, but has significant impact on practical work: fully searchable mass spectrometry imaging data can be shared with collaborators in biological or clinical labs without being restricted to proprietary vendor software. Additional aspects of MS imaging that will be discussed include quantitation, on-tissue digest of proteins, compound identification and ‘round-robin’ experiments.

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(PL28) “THINK BIG! – OPTIMIZATION OF A SPECTROMETRY LAB ON THE INDUSTRIAL SCALE Heiko Egenolf BASF SE, Competence Center Analytics, GMC/E - M320, 67056 Ludwigshafen, Germany e-mail: [email protected] BASF is the world’s leading chemical company: The Chemical Company. Its portfolio ranges from chemicals, plastics, performance products and crop protection products to oil and gas. We combine economic success with environmental protection and social responsibility. Through science and innovation, we enable our customers in nearly every industry to meet the current and future needs of society. Our products and solutions contribute to conserving resources, ensuring nutrition and improving quality of life. We have summed up this contribution in our corporate purpose: We create chemistry for a sustainable future. BASF had sales of €72.1 billion in 2012 and more than 110,000 employees as of the end of the year. Further information on BASF is available on the Internet at www.basf.com. With the Competence Center Analytics, BASF operates a central unit with 350 employees that are solving all analytical problems of research, development, and production. Three factors determine the excellence of an analytical service provider; quality, speed and analysis costs. Short turnover times in compliance with the requisite quality standards at reasonable prices are key factors determining long-term success in the analytical market. The high amount of analysis samples processed at the Competence Center Analytics – approx. 250,000 per year – requires efficient organization of the structures and workflows in the laboratories. Using the example of the atomic spectrometry lab, some insights will be given into the method portfolio covering “routine” tasks as well as customized solutions for special analytical problems. In addition, the optimization of an industrial analysis lab is explained. One key feature has been the development and construction of several robotic analysis systems for sample preparation and measurement. The modes of operation for automated sample preparation of both organic and inorganic samples are demonstrated, and the benefits of the robotic systems are explained.

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XXXVIII CSI 2013

Lecture Abstracts

LECTURE ABSTRACTS (L1) X-RAY REFRACTIVE OPTICS: PRESENT STATUS AND NEW DEVELOPMENTS Anatoly Snigirev European Synchrotron Radiation Facility (ESRF), 38043 Grenoble, France e-mail: [email protected] Soon after the first experimental demonstration of X-ray focusing by refractive lenses at the ESRF in 1996, it became immediately clear that the refraction-based methods traditionally used in the visible light regime can be successfully applied for X-rays. The use of X-ray refractive optics has rapidly expanded and they are now in common use on various beamlines at 15 synchrotrons in 10 countries. Firstly, this dramatic progress was driven by the unprecedented properties of X-ray beams delivered by third generation synchrotron sources such as very low emittance coupled with high brilliance. Secondly, refractive optics offers number of advantages over the existing optics taking into account applicability, tunability and diversity in terms of energy range, focal distance and focal spot. The talk will give a short overview of ongoing and future activities on the development of refractive optics at the ESRF. Over the past, most of our developments were driven by the demands of the Upgrade Program. The significant progress has been made in extending the diapason of applications of the refractive lenses in terms of energy range and tunability. The applicability of Be lenses has been extended to softer X-rays - down to ~2 keV opening new opportunities for spectroscopy and diffraction applications. On the nano-beam front we have taken steps to improve the performance of the planar Si lenses. The resolution below 100 nm has been demonstrated at 30-50 keV. Finally we will shortly present the latest developments of new techniques based on refractive optics: A coherent diffraction microscopy for mesoscopic materials, photonic and colloidal crystals. A new concept of a dark-field diffraction microscopy for 3D stress mapping of single grains. An in-line multi-lens interferometry for nano-scale measurements and coherence diagnostics.

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Lecture Abstracts

(L2) CHARACTERISATION OF NANOPARTICLES WITH SYNCHROTRON X-RAY STANDING WAVE FLUORESCENCE Roland Hergenröder and Martin Brücher Leibniz-Institut für Analytische Wissenschaften-ISAS, Interface Processes, Bunsen-Kichhoff Str.11, 44139 Dortmund, Germany e-mail: [email protected] Since the development of total reflection X-ray fluorescence (TXRF) spectroscopy in 1971, measurements basing on the generation of a Standing Waves interference pattern produced by total X-ray reflection (XSW) have found a wide range of applications. The main advantage of this powerful technique is the extremely low detection limit of the analyte, made possible by a greatly reduced spectral background compared to conventional X-ray fluorescence analysis. Furthermore, the absence of any matrix effects makes TXRF suited for exact quantitative analyses. If the TXRF set-up is equipped with a high resolution goniometer and if a coherent X-ray radiation source like a synchrotron can be applied, then the method can be extended to provide high resolution in-depth profiles of elemental distributions of surfaces. The sub-nanometre wavelength domain of X-ray provides a spatial resolution on molecular scale. Main advantages of this technique are low detection limit and sub-nanometer resolution, enabling space-resolved measurements on molecular scale.[1-3] In X-ray standing wave (XSW) experiments need a beam of coherent and monochromatic X-rays, hitting a flat surface under grazing incidence that is totally reflected. In the overlap of incoming and reflected beam, an interference pattern of alternating minima (nodes) and maxima (antinodes), the X-ray Standing Waves field, is generated. (see Figure 1)

Figure 1 Angular and vertical distribution of intensity in a 15 keV X-ray Standing Waves field generated inside a poymer layer on a reflecting substrate. At cpolymer  0.07°, the incoming X-rays are refracted into the layer and interfere after reflection at the layer/substrate interface. (b) The scheme visualizes the refraction and reflection of

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Atoms or ions within the interference volume are excited to fluorescence depending on the local intensity I(α,z) of the XSW field. The position of the fluorescence maxima depends on the incident angle α, so by recording fluorescence spectra with a stepwise variation of α between the single measurements, the distribution of elements above the reflecting surface is scanned vertically. The XSW method has successfully been applied to the investigation of particles, layered structures, electric double layers, adsorbates and biofilms. Here, the versatility of this method is demonstrated by examples from Determination of element-specific nanoparticle size distributions. Metallic nanoparticles produced by laser ablation under varying liquid conditions are dried on a silicon wafer. The median size of such particle is known to be under 20 nm und therefore difficult to determine. XSW enables a direct measurement of the vertical mass distribution on the surface which then can be fitted to different assumed distribution of spheres. As a result a best-fit size distribution function is provided. No not verifiable ad-hoc assumption about the distribution is necessary. Because fluorescence is element specific the additional advantage to measure elementally mixed particle distribution is provided. Measurements of elemental distribution at the solid/ liquid are presented. Measuring the distribution of elements contained in a liquid contacting directly a solid surface is another interesting application. Numerous natural and technological processes are taking place on surface. Bulk concentration of a liquid gives only limited information of the relevant concentration of compounds in proximity to the surface. Electrostatic interaction may considerably modify the concentration (e.g. electric double layer, stern layer) and an in-situ measurement of the distribution above the surface is of great interest. Measurement of hydrophobic/ hydrophilic and chemically (“soft”) surface is presented. A.von Bohlen, M. Krämer, C. Sternemann, M. Paulus, Spectrochim. Acta, Part B 2009. P. Wobrauschek, H. Aiginger, Analytical Chemistry 1989, 47, 852. M. J. Bedzyk, D. H. Bilderback, G. M. Bommarito, M. Caffrey, J. S. Schildkraut, Science 1988, 241, 1788.

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XXXVIII CSI 2013

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(L3) NEXAFS SPECTROSCOPIC STUDIES OF ANODIZED Ti-6Al-4V ALLOY WITH THE AIDE OF FIRST PRINCIPLES CALCULATIONS Toshihiro Okajima1,2, Yoshiteru Mizukoshi3 and Naoya Masahashi3 1

Kyushu Synchrotron Light Research Center, 8-7 Yayoigaoka, Tosu, Saga, 741-0005, Japan Research Center for Synchrotron Light Applications, Kyushu University, 6-1 Kasugakohen, Kasuga, Fukuoka 816-8505, Japan 3 Kansai Center for Industrial Materials Research, Institute for Materials Research, Tohoku University, 1-2 Gakuen-cho, Naka-ku, Sakai, Osaka, Japan 2

e-mail: [email protected] Introduction Titanium dioxide (TiO2) is a well-known photocatalyst. Many efforts including doping ions to TiO2 have been paid for the improvement in the visible light response of the photocatalytic activities. More recently, Mizukoshi et. al. reported that the visible light response was improved in the anodized Ti-6Al-4V (hereafter described as Ti64) alloy [1], which is one of the commonly used Ti alloys due to its balanced workability and strength. The anodization can lead TiO2 containing V, but the details of V are not elucidated. In the present study, we investigated the local structures of V ion in the anodized Ti64 alloy by a combination of NEXAFS spectroscopy and first-principles DFT calculations. Experimental and computational procedures Anodization of Ti64 plate was carried out in an aqueous solution of acetic acid (2M) using a Pt mesh electrode as the cathode. The oxidation was conducted for 0.5 h. The anodized Ti64 was annealed at 723 K for 5 h in air [1]. V and Ti K-edge NEXAFS spectra were measured at the beamline BL11 of Kyushu Synchrotron Light Research Center with convergent electron yield (CEY) mode for Ti64 plates before and after anodization and with transmission mode for reference samples. The theoretical V K-edge NEXAFS spectra were also obtained with GGA using full-potential augmented plane wave plus local orbitals (APW + lo) calculations [2]. The core-hole effects were fully taken into account in the present calculations. The theoretical spectral profiles were obtained by a product of the radial part of the transition matrix element and the corresponding projected partial density of state. Each of calculated spectrum was broadened by the Gaussian function of =1.0 eV full width at half maximum. Results and Discussions The measured Ti K-edge and V K-edge NEXAFS spectra of before and after anodized Ti64 plates are shown in Figures 1 and 2, respectively. The Ti K-edge spectra obtained from some reference samples are also shown in the Figure 1. The Figure 2 (c) shows the calculated V K-edge NEXAFS spectrum for V substitutional model. In the model, a Ti4+ ion in the 2×2×1 surpercell of an anatase type TiO2 unit cell were substituted by a V5+ ion. The V ion is 4-fold coordinated with O ions in the alloy. In Figure 1, the spectral features of Ti64 alloy before and after anodization are drastically changed, and are similar to those of Ti metal and anatase type TiO2, respectively. These results show that Ti metals in Ti64 alloy are oxidized to anatase type TiO2 by anodization. This result consistent with that obtained from XRD shown in previous paper [1]. The spectral features in V K-edge NEXAFS region shown in Figure 2 (a) and (b) also change between before and after the anodization. The V in Ti64 alloy before anodization exists in a metal from the spectral features. On the other hand, it is

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thought that the V in Ti64 alloy after anodization is oxidized. However, the V ion is not simply oxidized state such as VO2, V2O3 and V2O5 from the comparisons of the spectral features previously reported for reference samples [3]. On the comparison of V K-edge region between the anodized Ti64 alloy and the calculation, the spectral features around 5490 to 5510 eV are similar between both spectra. However, the differences are seen clearly at pre-edge region around 5470 eV between both spectra. This result shows that the V substitutional model is not suitable to explain the local structures of V ions in the anodized Ti64 alloy. We will discuss the local structures of V ion in the anodized Ti64 alloy and also discuss the mechanism of improvement in the visible light response of the photocatalytic activities in the presentation.

Acknowledgment This work was supported in part by Izumi Science and Technology Foundation. References [1] Y. Mizukoshi and N. Masahashi, Chem. Lett., 41, (2012), 544. [2] P. Blaha, et. al., WIEN2k, an augmented plane wave +local orbitals program for calculating crystal properties, Karlheinz, Achwarz, TechnicalUniversitat Wien, Austria, 2001. [3] J. Wong, F.W. Lytle, R.P. Messmer and D.H. Maylotte, Phys. Rev. B30, (1984), 5596.

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(L4) MICROSCALE MINERAL ANALYSIS OF CLAY ROCK THIN SECTIONS AFTER SORPTION EXPERIMENT USING SRXRF János Osán1, Annamária Kéri1, Daniel Breitner1, Margit. Fábián1, Rainer Dähn2 and Szabina. Török1 1 2

Environmental Physics, HAS Energy Research Institute, H-1121 Budapest, Hungary Laboratory for Waste Management , Paul Scherrer Institute, CH-5232 Villigen PSI, Switzerland

e-mail: [email protected] Argillaceous rock of the Boda Claystone Formation (BCF) is considered in Hungary as suitable host rock formations for the deep geological disposal of radioactive waste. The most important chemical characteristics in this respect is their generally strong radionuclide retention property due to the high sorption capacity. Consequently, the physico-chemical parameters of this process have to be studied in great detail. Synchrotron based XRF and XRD have sufficient sensitivity to study these processes on the microscale without the need to use radioactive substances. The present study focuses on the interaction of escaped ions with the host-rock surrounding the planned high-level radioactive waste (HLW) repository. The aim of our study is to investigate the uptake mechanisms of key ions presents at high conectration in such wastes. For this reason, combined synchrotron-radiation micro-XRF mapping, micro-XRD measurements were performed on thin sections subjected to sorption experiments using 5 µm spatial resolution at the ANKA FLUO beamline (Karlsruhe, Germany). Inactive Cs(I), Ni(II ) and natural U(VI) were selected for the experiments chemically representing key radionuclides. The thin sections were prepared from geochemically characterized cores from drillings of BCF. Thin sections were prepared on 350-µm thick high-purity silicon wafers as acceptable backing for XRD. The average thicknesses of the sections are 30-60 µm. Samples were subjected to 72-hour sorption experiments with one ion of interest added, using synthetic porewater solution. The elemental micro-XRF maps taken usually on several thousand pixels indicate a correlation of Cs, Ni and with Fe- and K-rich regions suggesting that these elements are predominantly taken up by these phases. Micro-XRD can identy the mineral composition of the particular interesting pixel. However, XRD takes at least one order of magnitude longer counting time so it can be only performed on limited number of pixels. When multivariate mathematical statistics is used for the processing of elemental maps significant information can be obtained in most cases that can be related to the uptake of element by a particular mineral phase. Factor profiles obtained by positive matrix factorization show which elements of the rock-forming minerals are present together with the (sorbed) element (of interest), delivering information on the mineral phases responsible for the uptake. In addition, cluster analysis was found to be a useful tool for semi-quantitative calculation of the uptake capacity of regions dominated by different mineral phases. The presence of mineral phases was verified by micro-XRD.

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XXXVIII CSI 2013

Lecture Abstracts

(L5) SYNTHESIS AND CHARACTERIZATION OF METAL NANOCLUSTERS: A NEW GENERATION OF LUMINESCENT LABELS Laura Trapiella-Alfonso1,2, Mónica Fernández-Ujados1, Mario Menéndez-Miranda1, José M. Costa1, Rosario Pereiro1, M.A. Habeeb Muhammed2,3, Hedi Mattoussi2, Alfredo Sanz-Medel1. 1

Department of Physical and Analytical Chemistry, University of Oviedo, Avd. Julián Clavería 8, 33006 Oviedo, Spain. 2 Department of Chemistry and Biochemistry, Florida State University, 95 Chieftan Way, Tallahassee, Florida 32306, United States. 3 Present address: Department für Physik and CeNS, Ludwig-Maximilians-Universtität München, Amalienstr. 54, D-80799 München, Germany e-mail: [email protected]  The advance in nanomaterials research has brought about a new class of fluorescent nanoprobes known as metal nanoclusters (NCs). Being composed of several to tens of atoms NCs present distinct optical, electrical, and chemical properties as compared to other large-scale nanomaterials or bulk materials with the same chemical composition. NCs exhibit luminescence from ultraviolet to the near infra-red regions,  large Stokes shifts, two-photon absorption, lack of intermittency, low photobleaching, electroluminescence and huge surface-to-volume ratio. Moreover, their tunable emission is size, core composition and environment dependent. All those features make them promising materials for developing a new generation of sensors, catalysts, optoelectronic devices or for biological applications. Thus, NCs can be treated as alternatives to quantum dots and organic dyes, being highly attractive for bio-imaging and bio-labeling applications due to their smaller size and because they do not present the stigma of potential toxicity often attributed to some luminescent quantum dots. As this is a new nanomaterial class, they also offer a great and challenging fundamental problem to understand cluster growth, stability, and functionality. In this communication we present a simple and efficient synthetic route approach for the preparation of Ag1 and Cu nanoclusters in aqueous media. For both type of nanomaterials, the synthesis process is based on the direct reduction of the metal in the presence of thiotic acid (TA)-appended poly(ethylene glycol) (PEG) ligands, requiring to ensure slight different experimental conditions, depending on the nanocluster composition (Cu or Ag), such as different metal:ligand ratios, temperature and reaction times. The TA-PEG ligand acts as a strong metal affinity anchor onto the metal surface while promoting aqueous compatibility over a broad range of conditions (pH, ionic strength media, cell culture media) and reduce significantly the nonspecific interaction in biological systems. The above route also allows easy surface-functionalization of the NCs with reactive groups (e.g. carboxylic acid or amine). We will describe in detail the proposed synthetic route along with the structural, optical and spectroscopic characterization of these materials. Additionally, some insights about the mechanism involved in the growth of these nanomaterials could be provided (see Fig. 1). These studies were carried out by three different ways: (1) optical monitoring of the synthesis; (2) size focusing methodology; (3) asymmetrical flow field-flow fractionation technique (AF4) coupled to several detectors (UV-vis, Fluorimeter and ICP-MS). The results obtained are in agreement among them, confirming that the synthesis of the metal clusters was driven by the previous formation of the corresponding metal nanoparticle. Finally, photostability and long-term storage stability of the new synthesized fluorescent nanoclusters were investigated, in order to establish its manipulation and its possible applications. Different behaviours versus UV irradiation were observed depending on the core composition. -73 -

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While AgNCs loss their optical properties after 30 min of UV irradiation, CuNCs seem to be highly photostable, retaining their optical properties after 24 hours of continuous UV exposition. Observed AgNCs optical properties degradation could be a result of three possible issues: (1) the liberation of free silver ions from the core that implies the total destruction of the NC; (2) the aggregation of the NCs catalized by UV light or (3) the formation of a higher-size nanostructure driven by a photoreaction. To try to elucidate which process is the responsible, we make use of the AF4 technique, coupled to different molecular and elemental detectors, and the HR-TEM as confirmatory analysis. We can conclude that the most probable mechanism explaining the reduced photostability of AgNCs could be a fusion of nanoclusters, catalyzed by UV irradiation, resulting in larger-size non-fluorescent silver nanostructures.

Figure 1. Proposed mechanism for the synthesis of metal nanocluster.

So we can conclude that these new nanoprobes have a great promising applicability in different fields such as sensors, catalyst or labels for bioanalytical applications. 1

M.A. Habeeb Muhammed, Fadi Aldeek, Goutam Palui, Laura Trapiella-Alfonso, Hedi Mattoussi, Growth of in-situ functionalized luminescent silver nanoclusters by direct reduction and size focusing, ACS Nano, 2012, 6, 8950-8961

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(L6) ADVANCED INSPECTION TECHNOLOGIES IN EXTREME SCENARIOS: STANDOFF LIBS AND UNDERWATER LIBS J.J. Laserna, J. Moros, F.J. Fortes, I. Gaona, S. Guirado and J. Serrano Department of Analytical Chemistry, University of Málaga, Málaga, Spain e-mail: [email protected] Development and application of advanced laser technologies for materials characterization offers quick-turn-around, cost-effective solutions to a variety of research and technical problems in diverse application areas, including process monitoring technologies, environment, cultural heritage, defence and security, and steel products and processes. Among the techniques available for field operation, laser-induced breakdown spectroscopy (LIBS) constitutes one of the most advanced solutions for real world problems. Standoff inspection of materials at distances up to 100 m based on LIBS will be presented. Also, systems for underwater analysis of materials at depth of up to 50 m in the ocean will be discussed. The underlying technology used in both approaches and a survey of its applications in the inspection of cultural heritage assets and in the detection of explosives and other threats will be presented.

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XXXVIII CSI 2013

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(L7) THE UMS: A NEW TOOL FOR MULTI-ANGLE UV-VIS-NIR PHOTOMETRIC SPECTROSCOPY David L Death1, Robert J Francis1, Cameron Bricker1, Travis Burt1 and Jan Wuelfken2

1 Agilent Technologies Australia, 679 Springvale Road, Mulgrave VIC 3170, Australia [email protected] 2 Agilent Technologies Sales & Service GmbH & Co. KG, Hewlett-Packard Straße 8, 38179 Waldbronn, Germany [email protected] Abstract: The UMS is a new, high performance, Cary UV-Vis-NIR spectrophotometer system which provides a wide range of functionality for the routine measurement of both reflectance and transmittance of specular and/or diffuse samples. 1. Introduction The Universal Measurement Spectrophotometer (UMS) is a versatile new system designed for Multi-Angle Photometric Spectroscopy applications. Multi-angle Photometric Spectroscopy (MPS) measures the reflectance and/or transmittance of a sample across a range of angles from near normal1 to oblique incidence. The UMS combines both reflection and transmission measurements from the same patch of a sample’s surface in a single automated platform for angles of incidence in the range 5°≤|i|≤85°2 (I.E. angles on either side of beam normal noted as +/-). The UMS also functions as a goniometer providing further capability for diffuse reflectance measurements of nonspecular surfaces and diffuse transmittance measurements of translucent materials. The addition of an automated polarizer further enables accurate measurement at S, P or user specified polarization angles. 2. Optical Characterization of thin films Reflection (R) and transmission (T) are the most fundamental measurements available for characterizing optical materials and coatings. Historically the characterization of optical materials and coatings for precision optics has been largely accomplished on the basis of normal and near normal incidence measurements due to the experimental simplicity of such an approach. This simplicity, however, is not without compromise. Normal incidence transmission measurements are typically conducted in the sample chamber of a spectrophotometer whilst near normal reflectance measurements require the use of a suitable reflectance accessory. A consequence of this approach is that there is never any guarantee that reflectance and transmission measurements are made from exactly the same patch on the sample due to sample repositioning during the significant changes in instrument configuration between R and T measurements. The Agilent Technologies Universal Measurement Spectrophotometer provides multi-angle measurement capability for both specular reflectance and direct transmittance measurements in a single fully automated unit without the need to reposition the sample. For example figure 2 shows sequential measurements made on the same patch of sample of 1 mm thick fused silica without repositioning of the sample. This simple measurement of the transmission and reflection from a 1mm thick plate of fused silica was conducted at angles of incidence ranging from 0 to 82° in transmission and 6 to 82° in reflection in both S and P polarization. The physical size of the silica 1

 Near normal for reflectance, Normal incidence for transmittance. 

2

 In Reflection.  0°≤|i|≤85° direct transmission. 

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sample limited the measurable range of angle of incidence to 82° without the incident beam falling off the sample surface. The measurements shown include contributions from both the front and internal rear surface reflections and transmissions. The individual points represent the measured values and the underlying solid lines indicate the total reflectance and total transmittance predicted by the Fresnel equations.

Figure 1. Reflectance and transmittance of a 1mm thick silica sample plate as a function of angle of incidence. The solid lines are calculated from the Fresnel equations the symbols are values measured using the UMA. Measurement wavelength: 500nm; Physical size of the Silica sample limited AOI range to 0-82°. For materials and coatings routinely used in normal or near normal incidence applications it makes sense to analyze their performance at or near normal incidence. However the analysis of optical coatings routinely employed over a range of oblique angles requires a degree of extrapolation from data collected solely at near normal incidence. Further as the complexity of the coatings increase to include multiple stacks and/or absorbing layers the ambiguity introduced by this extrapolation becomes progressively worse [1]. Such analysis is typically used to fine tune coating parameters and/or reverse engineer coatings to enable a better understanding of those parameters and to improve production of desired performance [2]. The accurate characterization of the optical parameters of materials used in thin film production is thus a critical factor for improving thin film performance. Recent work has demonstrated the utility of increasing the range of data available for use in reverse engineering films to extract optical parameters. The inclusion of MPS data at angles greater than normal and near normal incidence lessens ambiguities in analysis providing better reverse engineering of complex thin films [2]. Additionally multi-angle photometric spectroscopic data has also provided insight into oscillations in the total losses in thin dielectric films [3]. This talk will further examine the utility of multi-angle photometric spectroscopy data provided by the UMS for the accurate characterization of a number of different sample types. 3. Conclusion The measurement of spectral data across a wide range of angles of incidence (multi-angle photometric spectroscopy) provides for better characterization of the performance of materials and coatings employed for precision optics. These data can also assist in the validation of optical coating designs by reducing the uncertainties encountered in reverse engineering of coating parameters. The UMS is a new, high performance, Cary UV-Vis-NIR spectrophotometer which provides a wide range of functionality for the routine measurement of multi-angle photometric spectra for both reflectance and transmittance of specular and/or diffuse samples. It will prove to be a valuable tool for the characterization of optical materials, coatings and components in a wide range of industrial and laboratory applications. -77 -

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(L8) 57

FE-MÖSSBAUER STUDY OF ELECTRICALLY CONDUCTIVE LITHIUM IRON VANADATE GLASS

Shiro Kubuki1, Koken Matsuda1, Kazuhiko Akiyama1 and Testuaki Nishida2 1

Department of Chemistry, Graduate School of Science and Engineering, Tokyo Metropolitan University, Minami-Osawa 1-1, Hachi-Oji, Tokyo 192-0397, JAPAN 2 Department of Biological and Environmental Chemistry, Faculty of Humanity-Oriented Science and Engineering, Kinki University, Kayanomori 11-6, Iizuka, Fukuoka 820-8555, JAPAN e-mail: [email protected] Vanadate glass has an electrical conductivity () of 10-7-10-5 Scm-1 caused by small polaron hopping from VIV to VV. Nishida et al. firstly reported that a remarkable increase in  took place from the order of 10-8 to 10-3 Scm-1 in K2O-Fe2O3-V2O5 glasses after isothermal annealing at temperatures between glass transition temperature (Tg) and crystallization temperature (Tc) [1]. Kubuki et al. revealed that xLi2O•(20-x)BaO•10Fe2O3•70V2O5 glass showed a larger increase in  from the order of 10-4 to 10-1 S cm-1 after isothemal annealing [2]. Structural relaxation of these vanadate glasses, i.e., a decrease in the local distortion of FeIIIO4 and VO4 tetrahedra constituting the glass network was successfully elucidated by 57Fe-Mössbauer study [1-3]. Vanadate glass with higher  will contribute to the development of cathode-active material for secondary battery of high performance. In order to reveal the relationship between  and structural change of vanadate glass in more detail, characterization of 20Li2O•10Fe2O3•70V2O5 glass (20LFV glass) was carried out by means of 57FeMössbauer spectroscopy and dc-probe method. In Fig. 1,  of 20LFV glass is plotted against different annealing temperatures. When 20LFV was annealed for 100 min at 400, 410, 430 and 450 oC, increased from 2.4×10-2 to 2.1×10-2, 5.8×10-2 and 1.0 ×10-1 S cm-1, respectively. On the other hand, a gradual decrease in  was observed from 3.4×10-2 to 7.5×10-2, 2.0×10-2, 1.0×10-2 and 1.2×10-2 S cm-1 when it was annealed at 460, 470, 480, 490 and 500 oC. These results indicate that change of  in annealed 20LFV glass depends on the annealing temperature.

Figure 1 Electrical conductivity () of 20Li2O•10Fe2O3•70V2O5 glass annealed for 100 min at different temperatures.

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Mössbauer spectra of 20LFV glass annealed at temperature for 100 min between 400 and 500 oC are shown in Fig. 2. One paramagnetic doublet due to distorted FeIIIO4 tetrahedra was observed with identical isomer shift () value of 0.39 mm s-1 and decreasing quadrupole splitting () from 0.67 to 0.52 mm s-1 when the annealing temperature was changed from 400 to 450 oC (Fig. 2 a-d). On the other hand, three paramagnetic doublets with  and  of 0.40 and 0.25 mm s-1, 0.38 and 0.60 mm s-1, and 0.31 and 1.11 mm s-1, respectively were observed when annealed for 100 min above 460 oC (Fig. 2 e-h). In these samples, absorption area of outer-most and inner-most peaks was increased

(a)

(e)

(b)

(f)

(c)

(g)

(d)

(h)

57 with an2increase of annealing temperature and became identical to each other, which is ascribed to Figure Fe-Mössbauer spectra of 20Li2O•10Fe 2O3•70V2O5 glass annealed for 100 min at the precipitation of semiconducting (a) 400, (b) 410, (c) 430, (d) 450, (e) 460, (f) 470, (g) 490 and (h) 500 oC.

FeVO4 [4, 5]. These results indicate that isothermal annealing of 20LFV glass at temperature higher than 460 oC results in the precipitation of FeVO4. It is considered that isochronal annealing of 20LFV glass at 400-450 oC causes an increase of  due to the structural relaxation, as was confirmed from the decrease in  (Fig. 2a-d), while it decreases owing to the precipitation of semiconducting FeVO4 particles when annealed above 460 oC. References [1] T. Nishida, J. Kubota, Y. Maeda, F. Ichikawa and T. Aomine, J. Mater. Chem., 6 [12], 18891896 (1996). [2] S. Kubuki, Y. Tomota, R. Yoshimura, Z. Homonnay, K. Sinkó, E. Kuzmann and T. Nishida, Journal of Physics: Conference Ser., 217, 012026 (2010). [3] S. Kubuki, H. Sakka, K. Tsuge, Z. Homonnay, K. Sinkó, E. Kuzmann, H. Yasumitsu and T. Nishida, J. Ceram. Soc. Jpn., 115 [11], 776-779 (2007). [4] L. M. Levinson and B. M. Wanklyn, J. Solid State Chem., 3, 131-133 (1971). [5] V.D. Nithya and R. Kalai Selvan, Physica B, 406 (2011) 24–29.

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(L9) BREAKTHROUGH IN SENSIVITY FOR QUADRUPOLE ICP-MS Meike Hamester1, René Chemnitzer1 and Søren Dalby2 1 2

Bruker Daltonics, Fahrenheitstrasse 4, 28359 Bremen, Germany Bruker Daltonics, Kallerupvej 39 d, 2640 Hedehusene, Denmark

e-mail: [email protected]

Quadrupole ICP-MS became a robust analytical instrument to measure almost all elements of the periodic table and in almost any matrix. Sensitivity specifications increased with every new generation but high resolution magnetic sector field ICP-MS still exceeded sensitivities of quadrupole ICP-MS by far. However, the combination of a high efficient interface, an sophisticated ion optical system with a robust plasma could demonstrate for the first time ever that quadrupole ICP-MS (Bruker aurora Elite) can get clearly ahead of sensitivity specifications of magnetic sectorfield ICP-MS. More important: without compromising other parameter such as background, spectral interferences, or stability. The presentation will describe the technical layout of the high sensitivity ICP-MS (Bruker aurora Elite) and will elaborate for which applications such high sensitivity is beneficial (e.g. nanoparticles, laser ablation but also isotope ratio analysis.

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(L10) DETERMINATION OF RARE EARTH ELEMENTS IN EXTRACTS FROM OIL REFINARY SPENT CATALYST BY ICP-MS WITH A REACTION CELL Jessee Severo Azevedo Silva1, Tatiane de Andrade Maranhão2, Fernando J. S. Oliveira3, Vera Lucia A. Frescura1 1

Universidade Federal de Santa Catarina, Florianópolis, SC, Brazil Universidade Federal do Rio Grande do Norte, Natal, RN, Brazil 3 Petróleo Brasileiro S.A, Gerência de Meio Ambiente, Rio de Janeiro, RJ, Brazil 2

e-mail: [email protected] One primary process used in petroleum refining industry is the fluid catalytic cracking (FCC). Many catalysts are impregnated with rare earth elements (REE) in order to improve their cracking characteristics. With repetitive usage, the catalyst loses its activity and is rejected as a waste. Every year, hundreds of thousands of spent catalysts are produced and their applications and re-use are proposed, mostly as filler in cement. The use of FCC spent catalyst as a source of REE could be a very interesting application, considering the recovery and recycling concept. In order to evaluate the potential application of FCC spent catalyst as a REE source, studies were performed both to determine the concentration of REE in spent catalyst samples and the feasibility of their extraction. The FCC spent catalyst samples were digested in a microwave oven in a medium containing nitric and hydrochloric acids, hydrogen peroxide and HF. After the digestion procedure has been carried out, boric acid was added in excess and a second procedure, assisted by microwave irradiation, was carried out aiming at the dissolution of the REE complexes and to assure the complete elimination of fluoride ions. This treatment guaranteed the complete digestion of the samples and eliminated the risks of damage to the ICP-MS sample introduction system. Prior to the determination by ICP-MS, studies using a reaction cell with ammonia as the reaction gas were conducted. Four elements, Gd, Lu, Nd and Yb, required the use of ammonia to overcome polyatomic interferences. The optimized flow rates were 0.4 mL min-1 for Nd and Yb and 0.6 mL min-1 for Gd and Lu. The average concentration, in µg g-1, for ten FCC spent catalyst samples are shown in Figure 1.All sixteen REE found in nature were present in the samples. The most significant element present in spent catalyst samples was lanthanum, with an average concentration of about 2.4% m/m. Other REE, as for instance Ce, Nd and Gd, were found in significantly high concentrations. Since FCC catalysts are impregnated with REE, it should be expected that obtaining REE from these samples will imply in a less expensive and easier process, when compared to their extraction from natural sources. In this sense, studies of extraction media, acid concentration, extraction time and temperature were carried out. After each study the analyte concentrations were measured by ICP-MS using the same method described before. The four media evaluated, HNO3, HCl, HNO3:HCl (1:3) and HNO3:HCl (3:1), at a temperature of 100 ºC for three hours, were very efficient in extracting the analytes, but nitric acid was the medium with the higher extraction potential as can be seen in Figure 2. In this medium, the extraction percentage, compared with the concentration obtained for the digested sample, was higher than 80% for nine elements, including three elements for which the percentage was higher than 95% (La, Gd and Nd).

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24000

La; Pr;

Ce; Sm;

Nd; Y;

Gd; Others

250

Extraction percentage

Average concentration, g g

-1

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HNO3

HNO3:HCl 3:1 HNO3:HCl 1:3

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Extraction media

-1

Figure 1. REE average concentrations, in µg g , for ten FCC spent catalyst sample by ICP MS.

Figure 2. Extraction media evaluation using one FCC sample at a temperature of 100 ºC.

Another study was carried out to evaluate if the extraction would be advantageous at lower concentration of HNO3. The same sample was submitted to extraction in nitric acid at concentrations of 1.4, 3.5, 7.0 and 10.5 mol L-1 for three hours at a temperature of 100 ºC. The results presented in Figure 3 show that even at low concentrations of HNO3 a good recovery of REE from FCC spent catalyst sample can be achieved. La; Pr;

Ce; Sm;

Nd; Y;

60

Gd; Others

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Extraction percentage

100 80 60 40 20 0

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-1

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HNO3 Concentration, mol L

Extraction time (at 30 C), min

Figure 4. Study of REE extraction time using a FCC spent catalyst sample in a 1.4 mol L-1 HNO3 medium, at a temperature of 30 ºC.

Figure 3. HNO3 concentration study for REE extraction in a FCC sample at a temperature of 100 ºC.

Two other studies were performed. Firstly, the extraction was carried out using the lower concentration of HNO3, 1.4 mol L-1, at 100 ºC in intervals from 30 min to 180 min. The time was not an important factor in the extraction process, since no significant difference in the concentrations obtained within the studied time range was observed. Good recoveries were accomplished even after 30 min extraction. The second study was similar to the first, but at a temperature of 30 ºC. The results, shown in Figure 4, demonstrate that the temperature is a key factor in extracting REE from FCC spent catalyst samples. However, the previous conditions, which employ low acid concentration, low temperature and a short time result in significant extraction of the analytes, and it may appear as a more attractive approach, particularly considering that the process could be repeated one or two times to increase the extraction. Taking into account that hundreds of thousands of FCC spent catalyst are generated every year as waste, requiring investments in their treatment, the use of this material could be a very interesting and cheap a source of REE, especially La, and also be in agreement with the recycling concept.

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XXXVIII CSI 2013

Lecture Abstracts

(L11) SOME PROCEDURES OF REDUCING MATRIX EFFECTS IN ICP-MS ANALYSIS OF BIOLOGICAL SAMPLES Konstantin Ossipov1, Irina F. Seregina1, Mikhail A. Bolshov1, 2 1

Chemistry Department, Lomonosov Moscow State University, 1-3 Leninskie Gory, 119991 Moscow, Russia 2 Institute for Spectroscopy, Russian Academy of Sciences, 142190 Moscow, Troitsk, Fizicheskaya 5, Russia e-mail: [email protected] Inductively coupled plasma – mass spectrometry (ICP-MS) has already established itself as a routine method for analysis of biological samples. ICP-MS is widely used in clinical laboratories on account of indisputable advantages: multielemental determination, high sensitivity, high throughput and possibility of small volume sample analysis. However, spectral interferences and matrix effects can significantly complicate the determination of elements in such samples as blood, plasma, urine and hair and affect the accuracy of the results. In spite of great number of investigations the new approaches to suppress or account for the interferences in bio-samples analysis are still actual. Two techniques of bio-samples pre-treatment are mostly used – 1) acid mineralization (in open or closed vessels or MW digestion), and 2) dilution by the mixture of reagents (Triton X-100-EDTAbutanol) for whole blood or 1% HNO3 1:10 for urine and plasma. The second technique is evidently simpler and less time consuming and successfully applied for the analysis of urine, plasma, lyophilized blood. But there are number of biological samples, which cannot be diluted - hair, dried blood, etc. The goal of this work is the investigation of the factors affecting the accuracy of the analysis of such bio-samples by MW digestion-ICP-MS technique. First experiments showed the noticeable (up to 30-40%) decrease of the Cu and Zn concentrations measured in blood samples after mineralization as compared to simple dilution of the same samples. Internal standards (IS) with different first ionization potentials were used to overcome this effect. It was shown that application of IS Rh (7.46 eV) is preferable only for elements with approximately the same IP (Co, Cu, Mn, Pb, Cr, Al) under conditions of optimal sensitivity (RF power 1440 W and nebulizer gas flow rate 1.2 L min-1). The discrepancy for elements with high IP (As, Se, Zn, Cd) cannot be fully eliminated even using IS Be (9.32 eV), while for Co, Cu, Mn, Pb, Cr, Al a 40-50% increase in relative signals is observed. The main reason of remaining difference between mineralization and dilution techniques might be high acidity of the digested samples. It was estimated that the residual content of nitric acid in digested solutions is 10-15% (v/v) for blood and 10% (v/v) for urine samples while 1% HNO3 solutions are used for dilution. The variation of ICP and sample introduction parameters is known as the strategy to overcome the acidic effect. Contrary to the published recommendations the decrease of RF power to 900 W had no effect on the measured analytes concentrations. The nebulizer gas flow rate did affect the analytical signals. The maximal RF power of 1440 W and the nebulizer gas flow rate of (0.8 – 1.0) L min-1 were found as the optimal parameters. Combination of application of the optimal parameters and IS provides adequate accuracy of the determination for Al, Cr, Mn, Co, Cu, Zn, As, Se, Cd, Pb in blood and hair samples. The accuracy of the developed strategy was proved by the analysis of the standard reference samples of blood (Seronorm Trace Elements Whole Blood, Norway) and hair (GBW 07601, China).

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XXXVIII CSI 2013

Lecture Abstracts

(L12) DEVELOPTMENT OF AN ANALYTICAL METHOD FOR Cd, Co, Cr, Cu, Ni and Pb DETERMINATION IN COSMETIC SAMPLES Amanda dos Santos Augusto, Érica Ferreira Batista and Edenir Rodrigues Pereira-Filho Federal University of São Carlos, Chemistry Department, P.O. Box 676, Zip Code 13565-905 São Carlos – São Paulo State, Brazil e-mail: [email protected] This study presents a method for metals determination in some cosmetic samples such as, blush and eye shadow products. Elements as Cd, Co, Cr, Cu, Ni and Pb were determined using a ICAP 6000 series, Thermo Scientific ICP OES (Inductively Coupled Plasma Optical Emission Spectrometry) and the most favourable working conditions were identified using desirability function [1] combined with a fractional factorial design (29-5 = 16 experiments). An aqueous multi element standard solution containing 1 mg/L of each analyte was introduced in the equipment and two responses were observed: signal area and relative standard deviation (RSD) for each analyte in the 16 experiments. Nine variables were investigated and a total of 78 responses were recorded. Four variables presented significant contrasts (Integration time for low wavelengths, flow rate during the analyses, radio frequency power and flow rate of nebulisation gas). The most favourable condition was identified when the highest signal and the lowest RSD were observed. Table 1 shows the final conditions. Table 1: Experimental conditions obtained for Cd, Co, Cr, Cu, Ni and Pb determination in ICP OES. Most favourable  (nm) in Axial and Radial condition views Integration time for low (variable 1) 5 s for both Cd: 228.802; and high (2) wavelengths Co: 228.616; Cr: 357.869; Flow rate of sample introduction (3) 4.2 mL/min Cu: 324.754; Flow rate during the analyses (4) 2.1 mL/min Ni: 341.476; Time for stabilization pump (5) 25 s Pb: 220.353. Radio frequency power (6) 1150 W Flow rate of auxiliary gas (7) 0.25 L/min Flow rate of nebulisation gas (8) 0.65 L/min Flow rate of coolant gas (9) 16 L/min

Variables

The sample preparation procedure was performed using a microwave oven system (Berghof, Speedwave) and the conditions were also studied using a full factorial design (24 = 16 experiments). Sixteen experiments were performed in order to see the effects of four variables: HNO3 concentration (2 or 7 mol/L), sample mass (150 or 250 mg), power and temperature microwave oven program. Two millilitres of H2O2 was also added in each experiment, the microwave oven power and temperature did not present significant effects in the studied range and the following conditions were fixed: between 800 and 1400W for power and between 180 and 210oC for temperature. Nitric acid concentration and sample mass presented significant effects and these variables were fixed at 2 mol/L and 250 mg, respectively when residual carbon content (RCC), residual acidity and analytes recovery were observed. Residual carbon content was calculated after C determination using ICP OES ( = 193.091 nm) [2] at a linear range of 15 to 1000 mg/L (LOD = 5.0 mg/L in Axial and Radial views). The RCC observed for the best condition was 2.8 ± 0.4 % (m/v, n = 5) and the residual acidity ranged between 90 to 105%. Cobalt, Cr, Ni and Pb concentration were not observed

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XXXVIII CSI 2013

Lecture Abstracts

in any sample. Copper and Cd were detected in blush and eye shadow samples, respectively. Table 2 shows the results obtained for the determinations of Cu and Cd. Table 2: Cu and Cd concentrations obtained for blush and eye shadow samples. Sample Blush

[Analyte] (mg/kg), n = 3 Cu = 0.96 ± 0.01 (Axial)

Recovery (%) LOQ (mg/kg) 114 (Conc. added = 6 0.2 µg/L) Eye shadow Cd = 1.04 ± 0.06 (Axial) 87 (Axial) 0.01 (Axial) and 0.1 Cd = 1.15 ± 0.09 (Radial) 96 (Radial) (Radial) (Conc. added = 20 µg/L) References: [1] Derringer, G.; Suich, R.; J. Qual. Technol.; 1980 12, 214. [2] Gouveia, S. T.; Silva, F. V.; Costa, L. M.; Nogueira, A. R. A.; Nóbrega, J. A.; Anal. Chim. Acta; 2001, 445, 269; Acknowledgments: The authors are grateful to Thermo Scientific for the instruments, Fapesp (12/10680-6 and 12/01769-3) and CAPES for the financial support.

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XXXVIII CSI 2013

Lecture Abstracts

(L13) THE NEW 8800 ICP-QQQ: HANDLING THE MOST DIFFICULT SAMPLES WITH EASE Uwe Noetzel1 and Ed McCurdy 2 1 2

Agilent Technologies, Germany, Agilent Technologies, UK.

e-mail: [email protected] ICP-MS has been widely accepted for inorganic analysis in reason to its fast, sensitive and multielemental capacities. However, the plasma, solvent and sample matrix give rise to polyatomic interferences on many analytes, so modern quadrupole ICPMS instruments employ a collision/reaction cell (CRC) to reduce these interferences. Indeed collision mode (using He cell gas) is used successfully in ICP-QMS to remove polyatomic interferences in high matrix samples since many years. However He mode cannot provide effective removal of intense interferences on some key analytes such as P, S and Se, or enable ppt-level analysis in high-purity materials. For ultra-trace analysis with ICP-QMS, reaction mode (using a reactive cell gas) can be more efficient than He mode, but often gives erratic results due to unpredictable reaction processes and cell-formed product ions. The 8800 employs MS/MS to solve these problems, enabling reaction mode to be used to its full potential. The 8800 ICP-QQQ features an additional quadrupole mass analyser (Q1) in front of the ORS3 cell and analyser quadrupole (Q2). This configuration is called MS/MS or tandem MS. Combining the proven capabilities of ICP-MS with the unique power of MS/MS, the 8800 ICPQQQ is a new analytical tool that can handle even the most difficult samples and applications with ease. In the current presentation, few examples will be given to illustrate the increase of performances that can be expected from the new 8800 ICP-QQQ.

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XXXVIII CSI 2013

Lecture Abstracts

(L14) A COMPARISON OF CONVENTIONAL (OFF-LINE) AND ON-LINE ISOTOPE DILUTION ICP-MS FOR THE DETERMINATION OF TOTAL SELENIUM IN HUMAN SERUM Petru Jitaru1,2, Caroline Oster2, Guillaume Labarraque2, Maria Estela del Castillo, Sophie VaslinReimann2 and Paola Fisicaro2 1 HydrISE, Institut Polytechnique LaSalle Beauvais, 19 rue Pierre Waguet, 60026 Beauvais cedex, France 2 Laboratoire National de Métrologie et d’Essais (LNE), Department of Biomedical and Inorganic Chemistry, 1 rue Gaston Boissier, 75024 Paris Cedex 15, France Selenium is one of the most widely investigated of all the trace element nutrients in the last decades, mainly due to its role in cancer prevention. It has been demonstrated that most biological functions attributed to Se are mediated by the selenoproteins. For biomedical applications, the serum selenoproteins, namely glutathione peroxidase (GPx) and selenoprotein P (SelP) as well as the Secontaining protein, selenoalbumin (SeAlb) are of main interest for the assessment of the Se status. Accurate determination of the selenoproteins is still challenging, especially because of the lack of standards commercially available as well as the difficulty of their preparation in-house. In these circumstances, the only method nowadays available for the quantification of selenoproteins is the on-line (post-column) isotope dilution (ON-IDMS) after their HPLC separation and further (on-line) detection by ICP-MS. Briefly, this technique relies on spiking the eluted species post column with an isotopically enriched material (‘spike’), which is generally an inorganic species of the analyte. It is worth to emphasize that ON-IDMS is not recognized as a primary method of chemical analysis, as it is the case of the conventional off-line IDMS (OFF-IDMS) where the analytes (the total element or specific chemical species) are mixed with the spikes prior to the ICP-MS (total element) or HPLCICP-MS (species-specific) measurements. Therefore, validation of ON-IDMS is required, especially when applied to bio-inorganic speciation analysis. Nevertheless, for such applications, the validation of ON-IDMS can be tentatively carried out only against a primary method such as OFF-IDMS applied for total element determination. This study presents a comparison between OFF-IDMS (primary method) and the ON-IDMS for the determination of total selenium in human serum. Firstly, the serum was analyzed OFF-ID-ICP-MS using two sample preparation procedures. In a first instance, the serum was digested by an acidic microwave treatment in order to destroy the proteins and hence obtain the (total) inorganic selenium. In parallel, the serum was diluted (1:25) with ultra-pure water before total selenium quantification by OFF-ID-ICP-MS. The latter approach, apart from being considerably more simple and rapid, provided also a 7 times signal enhancement hence leading to significant increase in the precision of the isotopic ratios measurements. Therefore, in view of comparison of OFF-IDMS and ON-IDMS methods, the whole serum was diluted with ultrapure water and analyzed further on. Each analysis step was repeated at least three times, and a complete uncertainty budget was evaluated for each analysis. The two methods developed in this study, namely OFF-IDMS and ON-IDMS were applied to the analysis of three commercially available serums with certified (BCR-637, IRMM, Geel, Belgium) or indicative (Seronorm Trace Elements-Level 1 and Level 2 serums, SERO AS, Billingstad, Norway) values for total selenium. Both methods provided results in good agreement with the certified and indicative values, respectively. In addition, the expanded uncertainty was calculated for the analysis of each serum both by OFF-IDMS and ON-IDMS with emphasis on the most predominant uncertainty sources in each case. This work comparing OFF- and ON-IDMS from a metrological perspective could be considered as a case study providing pro evidence for the use of ON-IDMS, either for speciation analysis of biomolecules or for the total element determination in biological fluids, due to its simplicity (no sample preparation required at all), versatility and accuracy. -87 -

XXXVIII CSI 2013

Lecture Abstracts

(L15) FROM 2D TOWARDS 3D ELEMENTAL IMAGING BY LASER ABLATION ICP-MS - A STUDY OF ARCHAEOLOGICAL GLASS Vid S. Šelih1, Johannes T. van Elteren1, Martin Šala1, Andrei Izmer2, Frank Vanhaecke2, Emilio F. Orsega3, Serena Panighello3 and Norman H. Tennent4 1

Analytical Chemistry Laboratory, National Institute of Chemistry, Hajdrihova 19, SI-1000 Ljubljana, Slovenia, 2 Department of Analytical Chemistry, Ghent University, Krijgslaan 281-S12, B-9000 Ghent, Belgium 3 Department of Molecular Sciences and Nanosystems, University Ca'Foscari Venezia, Calle Larga S. Marta 2137, IT-30123 Venice, Italy 4 Faculty of Humanities, University of Amsterdam, Hobbemastraat 22, Amsterdam 1071 ZC The Netherlands e-mail: [email protected] Archaeological glass has been a subject of many studies that try to reveal ancient glass manufacturing techniques, sources of materials used during production (sands, fluxes, colourizers, opacifiers, etc.) and provenance studies as well as studies that focus on mechanisms of degradation of glass artefacts during time. Various techniques of elemental analysis, such as e.g. SEM-EDS, EMPA, TEM, micro-XRF, SIMS, LA-ICP-MS have been used for such studies and they mainly focus on bulk or localized microanalysis of the sample. However useful the bulk or localized analyses are, even more information can be retrieved from surface (2D) and depth (3D) elemental distributions. Laser ablation ICP-MS is particularly suitable for such studies, as it is very versatile with a very large dynamic range, low detection limits and the potential for imaging on scales from hundreds of μm2 to tens of mm2. We developed a two-dimensional LA-ICP-MS imaging procedure that succesfully extracts the sample's surface elemental features. For this purpose the laser beam is scanned across the surface of the sample along parallel lines and the data obtained are manipulated so that a “map” of the element distributions is obtained. Aided by sum-normalization calibration approaches1 such element distributions can be converted to quantitative 2D elemental images. In this way maps for 54 elements (oxides) in archaeological glass2 were obtained (Figure 1). To further study processes such as weathering and degradation of surface layers of archaeological glass, 2D surface distributions are not enough and a novel three-dimensional LA-ICP-MS analysis approach was very developed recently3. This approach is a combination of rastering and depth profiling, and allows for direct 3D mapping of “hard” materials such as glass but it might also be used for similar (or even "soft") materials. The 3D mapping procedure (see Figure 2) features slow laser drilling on a virtual grid on the surface of the sample and ultrafast ICP-MS acquisition to resolve individual ablation pulses. Acquired data is then manipulated in such way that 3D quantitative elemental (volume) images are created. These can be visualized as 3D volume images or time-lapse movies. We successfully tested this approach to investigate mechanisms behind the degradation of a medieval, weathered glass artifact using colocalization analysis of selected cross-sectional 2D elemental images constructed in arbitrary planes of the acquired 3D volume images.

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XXXVIII CSI 2013

Lecture Abstracts

(L16) DIRECT SOLID QUANTITATIVE ANALYSIS OF BATTERY COMPONENTS USING LAICP-MS AND DEVELOPMENT OF CUSTOM MADE SOLID STANDARD MATERIALS ANALYSIS OF BATTERY MATERIALS Björn Hoffmann, Martin Winter, Sascha Nowak* *

([email protected]) University of Münster, MEET Battery Research Centre, Corrensstraße 46, 48149 Germany Laser ablation is a method that allows direct sampling of solids. This is done by evaporating small spots of the sample with a high powered pulsed laser in an argon-helium-atmosphere. The aerosol is transported into an inductively coupled plasma and subsequently analyzed in a mass spectrometer. This approach retains spatial information, within certain limitations and can be used to record three dimensional concentration profiles. Lithium-ion batteries still experience a loss in performance over time. Although the technology is state of the art in portable consumer electronics, widespread application in automobiles requires improvement beyond the current capabilities. Understanding deterioration processes and mechanisms requires the examination of aged cells. As electrochemical cells do not age homogeneously and electrochemistry in general is heavily dependent on surface properties, bulk analysis is not suitable for investigating these phenomena. LA-ICP-MS promises to be a suitable tool to study these issues. Our initial studies show that battery materials are challenging samples that require thorough optimization of the ablation conditions. Due to analysis of the undiluted and undissolved solid sample, laser ablation offers detection limits comparable to liquid analysis with easier sample preparation and most importantly offers spatial information on analyte concentrations.

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XXXVIII CSI 2013

Lecture Abstracts

(L17) DIRECT ELEMENTAL ANALYSIS OF NANODIAMONDS WITH ICP-OES Dmitry S. Volkov, Mikhail A. Proskurnin, and Mikhail V. Korobov Lomonosov Moscow State University, Chemistry Department, 119991, 1-build. 3, Leninskie gori, MSU, Moscow, Russia e-mail: [email protected] Detonation nanodiamonds (DNDs) gain much attention for biomedical and clinical applications [1], and high-technology purposes [2-7] due to their unique properties. However, many DND properties, which are relevant for such uses (aggregate size, surface groups, optical and colloidal properties, etc.), depend on their production and purification technology. In particular, it is very important to know, reliably and precisely, the DND impurity composition — content of metals and nonmetal elements first — because some chemical elements may be hazardous even in trace quantities, especially if we deal with nanomaterials. In addition, they also change the DND properties, e.g. thermal and oxidative resistance [8, 9]. Thus, the replicability of DND technology is a topical problem in the industry [10]. The development of reliable chemical analytical control is the obvious first step to render traceable DND properties and to improve and advance the required technologies. This usually means sensitive and selective multielement analysis because the impurities in DNDs have various nature and quantity level — metal-oxide nanoparticles, carbides, silicon dioxide, insoluble salts as well as cations and anions adsorbed at DND surface [11-13]. They appear due to the interactions in the detonation reaction chamber (Fe and Cr) or from the explosion initiation (Cu, Pb, and Hg) [12], or adsorbed [14] on already formed DNDs from liquids (acids and water) used for their isolation from the detonation-chamber charge [13, 15]. To the best of our knowledge, the problem of quantitative multielement analysis of DNDs was not sufficiently investigated. In our opinion, analysis of NDs can be reliably solved using the state-of-the-art method of atomic spectroscopy — optical-emission analysis with inductively coupled plasma (ICP-OES). This method is de facto standard for various environmental, high-technology, clinical and pharmaceutical analysis. In this paper, we will discuss the analytical possibilities of ICP-OES for accurate and precise quantifications of various elements in DNDs. We developed a technique for quantitative multielement analysis of DND impurities by ICP-OES using a slurry nebulization technique. We found out that the most of analysed DNDs contain relatively high amounts of Fe, Na, Si; Cu, B, Ni, Al (>100 ppm), while Pb, Zn, K, Mn, B, Cr, Mg, Mo, Sn, W, Ba, Sb, Co, Sr are in low but significant amounts. Moreover, we measured generalised indicator property — the ash mass after combustion — and found that all incombustible impurities comprise 1–3% of the total DND mass. In commercially available «deeply purified» DND samples, we detected much lower impurities of Сu, Ni, Al and slightly lower amounts of Fe, while other elements were almost at the same average level as in not so thoroughly purified DND species. This means that the purification process is possible, but needs improvement. We have found that DNDs from different manufacturers contain very different impurities and even for a single product type, they change from lot to lot. This means that DND purity needs to be monitored, and additional purification might be made if necessary Acknowledgements. This work was supported by the RFBR, grants nos. 12-03-00653-а and 12-0331569-mol_a and the MST of Russian Federation, contract no. 16.740.11.0471. -90 -

XXXVIII CSI 2013

Lecture Abstracts

(L18) EXPERIMENTAL SPECTROSCOPIC AND QUANTUM CHEMICAL STUDIES OF THE REACTIVITY OF ALKYLRESORCINOLS IN REDOX PROCESSES Alexander A. Kamnev1, Roman L. Dykman1, Alexei G. Shchelochkov1, Krisztina Kovács2, Ernő Kuzmann2 and Alexei N. Pankratov3 1

Laboratory of Biochemistry, Institute of Biochemistry and Physiology of Plants and Microorganisms, Russian Academy of Sciences, 410049 Saratov, Russia 2 Laboratory of Nuclear Chemistry, Institute of Chemistry, Eötvös Loránd University, P.O.Box 32, H-1512, Budapest, Hungary 3 Division of Analytical Chemistry and Chemical Ecology, Institute of Chemistry, N.G. Chernyshevskii Saratov State University, 410012 Saratov, Russia e-mail: [email protected]; [email protected] The physical chemistry and reactivity of extracellular signalling molecules, which are used by microbial consortia as a “chemical language”, is of importance for understanding and predicting abiotic impacts of the environmental conditions on microbial communication [1]. Any possible chemical transformations of such molecular signals (e.g., hydrolysis, complexation or oxidation reactions) would result in their exclusion from the signalling pathways, which is equivalent to a “message non-delivery”. In our earlier studies, it was shown using a variety of spectroscopic techniques that indolic phytohormones of the auxin series (e.g. indole-3-acetic acid synthesized by many soil bacteria and excreted into the environment), involved in plant-microbe interactions and signalling, can be gradually oxidised in moderately acidic media in the presence of iron(III) [2, 3]. In this work, chemical reactivity under similar conditions (simulating acidic soil environment) was studied for alkylresorcinols (ARs; 1,3-dihydroxybenzenes with alkyl substituents in positions 4 or 5), chemical analogues of extracellular microbial autoinducers with adaptogenic functions [4, 5]. The kinetics of iron(III) reduction by ARs with different molecular structures and the ironcontaining products formed both in the solutions and in the dried solids were studied using freezequench 57Fe Mössbauer spectroscopy. Soluble products in the course of ARs oxidation were monitored using UV spectrophotometry [4, 5] and analysed using GC-MS and FTIR spectroscopy. The results obtained have shown that the AR redox-reaction rate strongly depends on the length and position of the alkyl substituent in the aromatic ring. Thus, at pH~3, 4-n-hexylresorcinol is much more rapidly (within minutes) oxidised than 5-methylresorcinol under similar conditions. The results of GC-MS and FTIR spectroscopic analyses of 4-n-hexylresorcinol oxidation products have shown that the first step of AR oxidation in the presence of iron(III) in weakly acidic aqueous media involves an additional hydroxylation of the benzene ring in the position C6. This abiotic oxidation pathway is similar to enzymatic oxidation of ARs reported in the literature. The observed chemical transformations show possible routes of mutual influence of FeIII in acidic soils and organic biomolecules of microbial origin, including extracellular molecular signals. These routes are of importance both for soil microbial ecology and for biogeochemistry of iron. In order to obtain theoretical evaluations of the ARs reactivities in redox processes, quantum chemical computations at the B3LYP/6-311++G(3d,3p) level were carried out to elucidate the steric and electronic structures of resorcinol as well as its 4-n-hexyl- and 5-methyl-substituted analogues. -91 -

XXXVIII CSI 2013

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The results have shown that 4-n-hexylresorcinol has the highest propensity for oxidation as compared with 5-methylresorcinol, while resorcinol has the lowest propensity. This trend is in line with our experimental data showing that 4-n-hexylresorcinol is much more rapidly oxidised at pH~3 in the presence of iron(III) than 5-methylresorcinol, while non-alkylated resorcinol is not prone to oxidation under similar conditions (see [1] and references therein). Regioselectivity of the hydroxylation process in the positions C4 and/or C6 of the benzene ring for resorcinol and its alkylated analogues has been shown to correlate with the calculated spin density values at the atoms in the corresponding cation radicals. This implies a homolytic mechanism of the hydroxylation process. Acknowledgements. This work was supported in part by NATO Grant ESP.NR.NRCLG 982857 and under the Agreement on Scientific Cooperation between the Russian and Hungarian Academies of Sciences for 2011–2013 (Project # 28). 1. Kamnev A.A., Kovács K., Kuzmann E., Vértes A. (2009) J. Mol. Struct. 924, 131-137. 2. Kovács K., Sharma V.K., Kamnev A.A., Kuzmann E., Homonnay Z., Vértes A. (2008) Struct. Chem. 19, 109-114. 3. Kovács K., Kamnev A.A., Mink J., Nemeth Cs., Kuzmann E., Megyes T., Grosz T., Medzihradszky-Schweiger H., Vértes A. (2006) Struct. Chem. 17, 105-120. 4. Kamnev A.A., Kovács K., Dykman R.L., Kuzmann E., Vértes A. (2010) Bull. Russ. Acad. Sci. Phys. 74, 394-398. 5. Kamnev A.A., Dykman R.L., Kovács K., Kuzmann E. (2013) Bull. Russ. Acad. Sci. Phys. 77 (6), in press (DOI: 10.7868/S0367676513060161).

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XXXVIII CSI 2013

Lecture Abstracts

(L19) VIBRATIONAL SPECTRAL ANALYSIS OF THE ISOTOPIC SPECIES OF HYDROGEN SULPHIDE, HYDROGEN SELENIDE AND WATER USING THE U(4) ALGEBRAIC MODEL Nirmal Kumar Sarkar Department of Physics, Karimganj College, Karimganj – 788710, India Email : [email protected] With the development of more powerful experimental techniques, molecular spectroscopy is now going through an exciting time of renewed interest. Tunable, stable and powerful lasers are now available to create highly excited levels with unprecedented resolution. Further more, new detection techniques are constantly being developed with sensitivities far exceeding the limits of detectors used just a few years back. To maintain resonance with the rapid development of sophisticated experimental approaches, theoretical physics has also been constantly tested to provide a collection of satisfactory models that can account for the experimental observations. It should be noted that molecular spectroscopy is undergoing a radical change not simply due to the development of more powerful experimental techniques. Also, one should realize that as a consequence of new (and quite often unexpected) experimental results, unprecedented efforts towards constructing alternative theoretical models have taken place in recent years. A comprehensive theoretical treatment for most aspects of molecular spectroscopy necessarily has to rely on a Hamiltonian formulation. The typical theoretical procedure used to study a given molecule consists of (i) separating the electronic and nuclear motions (assuming the Born-Oppenheimer approximation ) and (ii) solving the Schrödinger equation in the potential surface for the rovibrating nuclei. For large molecule (larger than a diatomic), the potential energy surface is a very complex function, composed of a discouragingly large number of coordinates. To this problem, a standard approach involves approximating the potential energy surface by convenient analytical functions. Various approaches have been used so far in the study of molecular spectra. Out of these, two important approaches are – ( i ) Dunham expansion[1] and ( ii ) potential approach[2]. A simple analysis of molecular rovibrational spectra is provided by the Dunham expansion. This is an expansion of the energy levels in terms of vibration-rotation quantum numbers. This expansion, however, does not contain any information about the wave functions of individual states. Thus, matrix elements of operators cannot be directly calculated. In the Dunham expansion, one needs a large number of parameters to account for a large polyatomic molecule. Further, these parameters have to be adjusted by a fitting procedure over a conveniently large experimental database, which is not always available. This is another serious drawback for this approach. Compared to the Dunham expansion, a better analysis is provided by the potential approach in the study of molecular spectra. Energy levels are obtained by solving the Schrödinger equation with an inter atomic potential. The potential is expanded in terms of inter atomic variables. The solution of the Schrödinger equation here provides wave functions from which matrix elements of various operators can be calculated. In this approach, all manipulations are either differentiations or integrations. Though the potential approach is better compared to the Dunham expansion, one should note that this approach also encounters difficulties as soon as we consider highly excited levels. Once more, a large number of parameters are needed here to achieve meaningful results for a large polyatomic molecule. Since the last part of the 20th century, an algebraic approach[3-4] has been used in the study of molecular spectra. The algebraic approach attracted a wider scientific community in recent years for

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XXXVIII CSI 2013

Lecture Abstracts

the analysis and interpretation of experimental rovibrational spectra of small and medium-sized molecules. This approach is based on the idea of dynamical symmetry and is expressed through the language of Lie algebras. This approach can account for any specific mechanism relevant for the correct characterization of the molecular dynamics and spectroscopy. Applying algebraic techniques, in this approach, one obtains an effective Hamiltonian operator that conveniently describes the rovibrational degrees of freedom of the physical system. Unlike the more familiar differential operators of the potential approach, the Hamiltonian used in the algebraic approach is algebraic and so are all the operations in the method. The technical advantage of the algebraic approach is the comparative ease of algebraic operations. Equally important is the results, obtained by comparison with experiment. For this approach, another important advantage is that there are general forms of algebraic Hamiltonians and that entire classes of molecules can be described by a common Hamiltonian where only the ( typically, linear ) parameters are different for the different molecules. Furthermore, in algebraic approach, we can have a good accuracy in the study of vibrational spectra of a molecule, by using only a fewer parameters than in the traditional approaches. Till today, the algebraic models have been applied successfully in the study of vibrational spectra of linear triatomic, linear tetratomic and some other small and medium-sized molecules[5-10]. A limited number of successful attempts[5,9-10] has been reported so far in the application of algebraic models to study the vibrational spectra of bent XY2 and bent XYZ molecules. For algebraic models, a large sector of bent triatomic molecules has been remained unattended till today. In this study, a successful application of U(4) algebraic model has been reported in the vibrational spectral analysis of the isotopic species of hydrogen sulphide, hydrogen selenide and water. The inclusion of intermode couplings in algebraic models has been stated to give a deep insight into detailed spectroscopy of the molecules. With a detail spectral analysis, in this study it has been shown that the isotopic species of hydrogen sulphide, hydrogen selenide and water can be approximated very well using the U(4) algebraic model.

References [1] [2] [3] [4]

J. L. Dunham, Phys. Rev. 1932, 41, 721-731. G. Herzberg, Spectra of Diatomic Molecules, Van Nostrand, Toronto, (1950). R. D. Levine and C. E. Wulfman, Chem.Phys.Lett. 1979, 60, 372-376. F. Iachello, Chem. Phys. Lett. 1981, 78, 581-585.

[5] F. Iachello, R. D. Levine, Algebraic Theory of Molecules, Oxford University Press, Oxford, 1995. [6] Nirmal Kumar Sarkar, Joydeep Choudhury and Ramendu Bhattacharjee, Mol. Phys. 2006, 104, 3051-3055; Nirmal Kumar Sarkar, Joydeep Choudhury, Srinivasa Rao Karumuri and Ramendu Bhattacharjee, Mol.Phys. 2008, 106, 693-702. [7] Nirmal Kumar Sarkar, Joydeep Choudhury, Srinivasa Rao Karumuri and Ramendu Bhattacharjee, Eur. Phys. J. D. 2009, 53, 163-171. [8] Srinivasa Rao Karumuri, Nirmal Kumar Sarkar, Joydeep Choudhury and Ramendu Bhattacharjee, J. Mol. Spectrosc. 2009, 255, 183-188. [9] Nirmal Kumar Sarkar, Joydeep Choudhury, Srinivasa Rao Karumuri and Ramendu Bhattacharjee, Vib. Spectrosc. 2011, 56, 99-104. [10]Nirmal Kumar Sarkar, Joydeep Choudhury, Ramendu Bhattacharjee, Vib. Spectrosc., 2012, 60, 63-67.

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XXXVIII CSI 2013

Lecture Abstracts

(L20) THEORETICAL INVESTIGATION OF THE CW ABSORPTION, RESONANCE RAMAN AND REMPI SPECTROSCOPY OF THE S1 AND S2 STATES OF CIS-1,3,5-HEXATRIENE AND TRANS-1,3,5-HEXATRIENE Clemens Woywod1 1

Centre for Theoretical and Computational Chemistry, Chemistry Department, University of Tromsø, N-9037 Tromsø

The 21Ag and 11Bu states of trans-1, 3, 5-hexatriene (THT) are vibronically interacting to first order via modes of bu symmetry. Likewise, vibrations transforming according to the b1 irreducible representation are linearly coupling the 21A1 and 11B1 states of cis-1, 3, 5-hexatriene (CHT). We have developed vibronic coupling Hamiltonians for a description of the photoinduced excited state dynamics of both isomers based on ab initio electronic structure information [1,3,5,6]. Solution of the vibronic Schr¨odinger equation for each system allows for the simulation of continuous wave ultraviolet photoabsorption and resonance Raman spectra [2, 4]. In addition, the observed resonance enhanced multiphoton ionization (REMPI) spectrum of the 21A1 state of CHT has been modeled. The results of the calculations provide evidence for strong S1–S2 vibronic coupling in both molecules and an explanation for the elusiveness of the 21Ag state of THT to observation. [1] C. Woywod, W. C. Livingood and J. H. Frederick, J. Chem. Phys. 112, 613 (2000). [2] C. Woywod, W. C. Livingood and J. H. Frederick, J. Chem. Phys. 112, 626 (2000). [3] C. Woywod, W. C. Livingood and J. H. Frederick, J. Chem. Phys. 114, 1631 (2001). [4] C. Woywod, W. C. Livingood and J. H. Frederick, J. Chem. Phys. 114, 1645 (2001). [5] C. Woywod, J. A. Snyder and J. H. Frederick, J. Phys. Chem. A. 105, 2903 (2001). [6] C. Woywod, Chem. Phys. 311, 321 (2005).

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XXXVIII CSI 2013

Lecture Abstracts

(L21) BASIS SET EXTRAPOLATION FOR HIGH RESOLUTION SPECTROSCOPY Kiran Sankar Maiti Department of Chemistry and Molecularbiology, University of Gothenburg, PO Box 462, SE-40530 Gothenburg, Sweden e-mail: [email protected] Recent development on experimental method of coherent multi–dimensional infrared spectroscopy provides a powerful new tool to study structure and dynamics of proteins and other biomolecules with a temporal resolution down to the sub–picosecond regime. The observed multidimensional spectra contain structural and dynamical information in terms of diagonal and cross–peak shapes, locations, and intensities and their respective temporal evolution. Extensive theoretical modeling is required to invert this data to obtain insight into the molecular dynamics. The important spectral features are due to anharmonicities in the vibrational Hamiltonian and nonlinearities in the dipole operator of the molecule. The accuracy of the anharmonic spectra depend upon the accurate potential energy surface (PES) calculation through the internal degrees of freedom. The recent development of high level quantum chemical ab initio method reached to spectroscopic accuracy for small molecules. The highly accurate ab initio calculation requires the basis functions to be as large as possible. As the basis function increases, the computational expense grows much faster than the rate at which the accuracy is improved, which makes the method unaffordable for the highly accurate PES calculation. On the other hand, spectroscopic accuracy can not be achieved by the smaller basis sets. In such a situation extrapolation of the energy to the basis set limit may speed up the PES calculation if there is a general extrapolation scheme. It is well known that Hartree-Fock (HF) energy converges very quickly and essentially reaches the basis set limit with the small basis set. Therefore spectroscopic accuracy only depends upon the accurate calculation of the correlation energy, which is known to converge very slowly. Two point extrapolation of the correlation energy, proposed by Halkier et al. reached to the spectroscopic accuracy but this method suggests to extrapolate from two larger basis sets, which is not feasible for large molecules. Inclusion of fifth order term from Schwartz’s formula provides an efficient route to extrapolate the correlation energy from small basis sets and reduces the computational expenses by two to three order of magnitude to reach the basis set limit correlation energy.

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XXXVIII CSI 2013

Lecture Abstracts

(L22) EXPLORING STRUCTURE AND ULTRAFAST DYNAMICS OF PROTEIN AND PEPTIDE USING TWO COLOR 2DIR SPECTROSCOPY Susmita Roy and Kiran Sankar Maiti Department of Chemistry and Molecularbiology, University of Gothenburg, PO Box 462, SE-40530 Gothenburg, Sweden e-mail: [email protected] A significant technological development on laser science and spectroscopy is going on during last couple of decads. Specially generation and control over the femtosecond infrared pulse, permits to visualize the time-dependent structural changes of fundamental physical processes in complex material and biological system. One of these development is two-dimensional infrared (2DIR) vibrational echo spectroscopy which has essentially sufficient time resolution to observe the structure and dynamics of proteins and peptides. Mainly three sequence of ultrafast pulses with phase match conditions are employed experimentally. Depending upon the sequence and data collection, the technique varies and named differently, but the 2DIR spectra looks same. The structural information is typically present in terms of the position, strength, and shape of the offdiagonal cross-peaks in the 2D spectrum. These are directly related to the anharmonic vibrational structure of the molecule.

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XXXVIII CSI 2013

Lecture Abstracts

(L23) FAT DETERMINATION OF INTACT FOOD SAMPLES WITH TIME-DOMAIN NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY AND CHEMOMETRICS Fabiola Manhas Verbi Pereira and Luiz Alberto Colnago Embrapa Instrumentation, St Quinze de Novembro, 1452, 13561-260 São Carlos/São Paulo state, Brazil e-mail: [email protected]

The analytical technique time-domain nuclear magnetic resonance (TD-NMR) is a potential alternative to distinguish between fat and water molecules, mainly in food products. The high specificity of this technique for total fat or oil content is based on signal from protons, in our study hydrogen protons, that is recorded as relaxation decays. For instance, the decays acquired using the sequence of pulses Carr-Purcell-Meiboom-Gill (CPMG) comprise analytical information from oil and water of samples. The differences within signals are directly related to the fat/water composition and 1H transverse relaxation time (T2) is usually applied to differentiate both components, because this physical property depend on molecular mobility. The sequence known as Continuous WaveFree Precession (CWFP) is able to measure longitudinal relaxation time (T1) and T2 in a single and fast experiment. The main objective of this study is to develop accurate models for prediction of the fat content in mayonnaise and beef cattle samples. This method was previously applied to measure moisture on frozen-thawing meat and to classify plums according to sugar content. The direct application is to help the consumers to better choice the food product according to their needing and diet. The tested mayonnaise samples were purchased at the local markets (São Carlos, São Paulo State, Brazil). Twenty one samples were from the same lot and, 10 remaining samples from another lot were used to test the prediction ability of the models. All samples were taken of three worldrenowned manufacturers. The number of samples varying in fat according to the label product was: 3 of 10.0 g 100 g-1, 19 of 15.0-22.5 g 100 g-1 and 9 of 30.8-55.8 g 100 g-1. The volume of the packing was between 107 and 109 cm3, corresponding to net weight up 400 to 500 g. Sixty-one Bonsmara heifers were separated into five groups according to genetic (breeding composition) and feed system (grain and grass feed). After harvest and chilling, a portion of each left side strip loin (Longissimus dorsi muscle) was collected and vacuum packaged. The through-package signal acquisition of intact mayonnaises were recorded using NMR spectrometer (Spinlock Magnetic Resonance Solution, Cordoba, Argentina) with a permanent Halbach magnet of 0.23 T (9 MHz for 1H), 10 cm bore, 50 cm of analytical magnet and 120 cm of pre-polarizer magnet. The applied sequence of pulses for CPMG was π/2 and π pulses of 9.2 and 18.08 µs, respectively; echo times τ = 200 µs and 2500 echoes. After thawing, each raw beef sample was separated into three cylindrical slices using a cylinder cutter with a diameter of 2 cm. For beef cattle measurements, a benchtop SLK 100 TDNMR spectrometer (Spinlock Magnetic Resonance Solution, Cordoba, Argentina) equipped with a 0.23 T permanent magnet (9 MHz for 1H) and a 13 x 30 mm probe head was applied to collect CPMG and CWFP decay signals. The CPMG sequence was executed using π/2 and π pulses of 6.28 and 12.56 µs, respectively, and echo times of τ = 300 µs with a total of 1500 echoes. The dead time was approximately 50 µs. The CWFP [6] sequence also used π/2 and π pulses of 6.28 and 10.6 µs, echo times of τ = 141.56 µs and 1501 echoes. The frequency offset was 5 KHz. Each signal for both sequences was the result of an average of four scans. The room temperature was held constant at 23 °C for every measurement. Three replicates for each sample were carried out for the extraction of lipids using the Bligh and Dyer method. Firstly, the signals of TD-NMR CPMG were investigated using the principal component analysis (PCA). -98 -

XXXVIII CSI 2013

Lecture Abstracts

The univariate model for fat prediction was performed using the transverse relaxation time (T2) values exponentially fitted to a function available on Origin 8.1 (OriginLab, Northampton, MA, USA). The chemometric technique partial least squares (PLS) was used to compute the multivariate model. PCA and PLS are available at Pirouette 4.0 rev. 2 software (Infometrix, Bothell, USA). The exploratory analysis of mayonnaise data using PCA shows the tendency of samples to spread along a first principal component (PC1) according to the fat range with 99.5% of total explained variance for the PC1 and PC2, as shown in Figure 1a. On right side of the plot of Figure 1a, the scores represent the samples with low values of total lipids (g 100 g-1) up 10.0 (dark circles) and on opposite side the scores with dark triangles symbols are the highest ones up 30.8 to 55.8 g 100 g-1. No outliers were observed in this data. The loadings plot related to independent variables was represented in Figure 1b. The best pre-processing applied to the signals was mean-centering. In this case, the auto-scaling of the independent variables (X matrix) was not adequate, because the spectral nature of data. The profiles of the signals represent more or less short decays according to fat content on samples under analysis.

A very good linear fitting was verified between the reference values and those predicted by PLS with values of 0.93 and 0.97 for training and validation data sets. The total fat content of 10 remaining samples was also successfully predicted by PLS with high linear correlation coefficient of 0.93. For PLS model, the highest values of r prove better fat predictability than univariate model. The results from PLS model shown indicates a potential of TD-NMR for industrially applicable in food analysis considering the high linearity and, regarding the signals were obtained from entire content of packing of mayonnaise. Otherwise, the bulk material was used for lipids extraction. For beef cattle, the potential of these multivariate models was also confirmed by the low values for RMSEP, between 1.16 (CPMG) and 1.55 (CWFP). Thus, the multivariate models can help predict the studied properties by measuring of fat content using TD-NMR. The correlation coefficients (r) between the values of reference methods and those predicted by the PLS models for CPMG is very promising with r value of -0.91. Otherwise, CWFP signals have higher correlation for fat content (r = 0.99) than CPMG. The main advantage verified here is the no-invasive measurement of fat content performed for intact packing of food products. The high linear correlation coefficients between the reference values from Bligh and Byer lipids extraction and those predicted by PLS model evidences the accuracy of multivariate model against the univariate fitting with the discrete T2 values.

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XXXVIII CSI 2013

Lecture Abstracts

(L24) DIODE LASER ABSORPTION SPECTROMETRY AS A TOOL FOR CONTACTLESS DIAGNOSTIC OF A HOT ZONE M. A. Bolshov, Yu. A. Kuritsyn, V. V. Liger, and V. R. Mironenko Institute for Spectroscopy RAS, 5 Fizicheskaya str., 142190, Moscow, Troitsk, Russia [email protected] Temperature is the critical parameter of any combustion process. In particular, temperature of the combustion zone in mixing flows of oxidant and fuel characterize the efficiency of a jet and fuel consumption. Absorption spectrometry with tunable diode lasers (TDLAS) is a powerful tool for contactless measurements of gas concentration and temperature in hot zones. The technique is based on the registration of the experimental transient absorption spectra of water molecules and fitting of the experimental spectra by the simulated ones constructed using the spectroscopic data bases. Wavelength scale, frequency, temperature, pressure, base line and the concentration of water molecules were the parameters of the fitting. Specific technique of transient data processing and algorithm of fitting will be discussed. The advantages and limitations of the developed technique will be discussed in the talk with the emphasis on the problems of the experimental spectra fitting and different fitting algorithms. The efficiency of the developed technique was exemplified by the measurement of the temperature and water vapor concentration in the hot zone of plasma-assisted combustion in air-fuel supersonic flow. The combustion is ignited and sustained by the pulsed electric discharge in experimental aerodynamic tube, characterized by rather strong fluctuations, vibrations and different optical and electrical noises. The air flow parameters were: Mach = 2, total pressure 150-300 torr. Air was used as the oxidant, hydrogen or ethylene were used as the fuel. The mean temperature of the hot tail of the combustion zone varied within (800-1200)K for hydrogen and (700-1000)K for ethylene, the water concentration varied within 10-20 Torr interval. The high signal-to-noise ratio enabled to obtain the temporal profile of both parameters with the resolution of ~ 1 ms. Precision of the temperature evaluation was estimated to ~ 40 K.

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XXXVIII CSI 2013

Lecture Abstracts

(L25) LIQUID CHROMATOGRAPHY MASS-SPECTROMETRY AS A TOOL FOR DETECTION OF CHEMICALS CONNECTED WITH CHEMICAL WARFARE AGENTS IN THE ENVIRONMENTAL AND BIO SAMPLES Igor A. Rodin Chemistry Department Moscow State University 119991 Leninsky Gory 1-3 Moscow Russia e-mail: [email protected] The development, production, stockpiling and use of chemical weapons are prohibited under the Chemical Weapons Convention [1]. In cases of alleged use of chemical warfare (CW) agents, environmental samples may be collected and analyzed for agents and their degradation products presented as a supporting evidence of a CW attack. Biomedical samples, e.g. blood and urine, may be analyzed for biological markers of poisoning as evidence that individuals have been exposed to a CW agent. Biomedical sample analysis also has applications in exposure monitoring, e.g. in individuals engaged in demilitarization activities, and for the diagnosis of poisoning prior to the administration of medical countermeasures. Common technique for organic toxicants is a gas chromatography-mass spectrometry. In general, chemical warfare agents are rather volatile and easy to degrade. Once exposed to the environment chemical warfare readily degrade by rapid hydrolysis or oxidation to the corresponding degradation chemicals which never exist in nature. These chemicals are highly polar and unsuitable to direct separation by gas chromatography. Liquid chromatography is a good alternative to separation for low volatile and highly polar compounds, and mass-spectrometry detection provides excellent sensitivity and selectivity. Several novel analytical methods for chemicals connected with various types of chemical warfare agents detection (nerve agents and vesicants) were developed using liquid chromatography massspectrometry. Development, validation and using in OPCW Proficiency Tests of techniques for sulfur mustard metabolites detection [3], nerve agents metabolites detection (alkylmethylphosphonic acids and dyalkyltaurines) [4-5] and lewisite metabolites detection [6] will be reported. References Convention on the Prohibition of the Development. Production. Stockpiling and Use of Chemical Weapons and on their Destruction. Technical Secretariat for the Organization for the Prohibition of Chemical Weapons. The Hague. 1997. Rodin, I. A., Braun, A. V., Savelieva, E. I., Rybalchenko, I. V., Ananieva, I. A., & Shpigun, O. A. (2011). Rapid method for the detection of metabolite of sulfur mustard 1,1'-sulfonylbis[2-S-(Nacetylcysteinyl)ethane] in plasma and urine by liquid chromatography-negative electrospray-tandem mass spectrometry. Journal of Liquid Chromatography and Related Technologies, 34(16), 1676. Rodin, I. A., Braun, A. V., Anan'eva, I. A., Shpigun, O. A., Savel'eva, E. I., Rybal'chenko, I. V., (2011). Detection of nerve agent markers by liquid chromatography - mass spectrometry. Journal of Analytical Chemistry, 66(14), 1417. I. Rodin, A. Stavrianidi, R. Smirnov, A. Braun, O. Shpigun, I. Rybalchenko (2013) New Techniques for Nerve Agent Oxidation Products Determination in Environmental Water by HPLC-MS and CE with Direct UV Detection. Environmental Forensics, 2(14). In press. Rodin, I., Braun, A., Stavrianidi, A., Shpigun, O., & Rybalchenko, I. (2011). Lewisite metabolites detection in urine by liquid chromatography-tandem mass spectrometry. Journal of Chromatography B: Analytical Technologies in the Biomedical and Life Sciences, 879(32), 3788. (L26)

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XXXVIII CSI 2013

Lecture Abstracts

COLLISION-INDUCED DISSOCIATION OF HYDROXYLATED POLYCYCLIC AROMATIC HYDROCARBONS IN AN ION TRAP TANDEM MASS SPECTROMETER Xue Li1,2 and Renato Zenobi2 1 2

Institute of Environmental Pollution and Health, Shanghai University, Shanghai 200444, PR China Department of Chemistry and Applied Biosciences, ETH Zurich, CH-8093 Zurich, Switzerland

e-mail: [email protected] Hydroxylated polycyclic aromatic hydrocarbons (OH-PAHs) are important biomarkers of carcinogenic PAHs and widely used for assessing health risks due to exposure to PAHs. Tandem mass spectrometry (MS/MS) based methods have advantages in both sensitivity and selectivity for the detection of OH-PAHs; however, MS/MS fragmentation efficiency still needs to improve due to the stable fused-ring aromatic structure of OH-PAHs. 100 Intensity

Rel. Int. (%)

6000

NCE = 60%@AQ = 0.45

239

267

4000

2000

3-Hydroxybenzo[a]pyrene

267 CO (28 Da)

50

0 180

200

220

240

260

m/z

Instrument Default Value

0 0.0

0.1

0.2

0.3

0.4

0.5

0.6

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AQ

Fig.1. Relative intensity variation of 3-OHBaP fragment ion ([M–H–CO]–) as a function of AQ In this study, eight OH-PAHs (with 2 to 5 rings) were selected as target compounds, including 1-/2naphthol (1-/2-OHNap), 3-/4-/9-hydroxyphenanthrene (3-/4-/9-OHPhe), 1-hydroxypyrene (1OHPyr), 6-hydroxychrysene (6-OHChr) and 3-hydroxybenzo[a]pyrene (3-OHBaP). Collisioninduced dissociation (CID) MS/MS analyses were performed using a LCQ Deca XP ion trap mass spectrometer (Thermo, San Jose, CA, US). The effects of CID parameters, such as the activation Q (AQ) and normalized collision energy (NCE) on fragmentation efficiency of all eight OH-PAHs were systematically investigated. By optimizing NCE and AQ in the CID experiments, the fragment ion [M–H–CO]– generated from the parent ion [M–H]– was monitored. Compared with previous results, 3-OHBaP was efficiently fragmented (Fig.1), and the MS/MS fragmentation efficiencies for 1-OHNap, 3-/4-/9-Phe and 6OHChr were clearly improved, too. AQ was found to be the critical parameter for fragmenting OHPAHs in the LCQ ion trap tandem mass spectrometer. A possible explanation is that as AQ is raised above a threshold value, parent ions of each OH-PAHs can be efficiently trapped even at increased NCE, and thus ion internal energy of the parent ion can be greatly increased, resulting in effective fragmentation (Fig. 1). (L27)

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XXXVIII CSI 2013

Lecture Abstracts

ELECTROSPRAY IONIZATION MASS SPECTROMETRY ASSISTED BY INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRY AS A TOOL TO STUDY THE SE/S SUBSTITUTION IN METHIONINE AND CYSTEINE IN SE-ENRICHED YEAST Katarzyna Bierła, Juliusz Bianga, Laurent Ouerdane and Joanna Szpunar CNRS/UPPA, Laboratoire de Chimie Analytique Bio-inorganique et Environnement (LCABIE), UMR5254, Hélioparc, 2, av. Pr. Angot, 64053 Pau, France e-mail: [email protected] Selenium-enriched yeast produced by growing Saccharomyces cerevisiae in the presence of selenite is a popular food supplement and an established ingredient of Se-enriched feed premixes and finished feed product. The latest patents issued indicate possible emerging uses of the Se-yeast and its extracts for cultivating mammalian cell cultures and altering cell functions for therapeutic applications. The development of suitable methods for speciation analysis is necessary to understand the Se-involving biochemical processes during Se-rich yeast production, the optimization of the Seincorporation during the yeast growth and the characterization of the final products in terms of the selenium chemical forms present which is requested by regulatory agencies. Till now most of the methodological developments concerning analysis of Se-rich yeast have been focused on the quantitative determination of selenomethionine (SeMet) leading to several round robin exercises culminated at the issue of a certified reference material (SELM-1). The improvement of analytical methods allowed the SeMet content above a certain value to be accepted as an indispensable parameter of the quality control of marketed products. The other mainstream of analytical chemistry developments included the identification of the myriad of selenium metabolites allowing the quasi-complete characterisation of the water soluble part of the Se metabolome. Nevertheless, none of these approaches allowed to balance an account of selenium species. We developed a proteomics approach (based on 2D gel electrophoresis followed by capillary HPLC with ICP MS and electrospray Orbitrap MS/MS parallel detection) allowing an investigation of the replacement and the degree of the Se/S substitution in methionine and cysteine and quantification of Se-compounds in Se-rich yeast. Mass spectrometry enabled to demonstrate for the first time a considerable incorporation of selenocysteine (SeCys) in proteins of the yeast proteome despite the absence of the UGA codon. The SeMet/Met and SeCys/Cys ratios were determined in a large number of peptides (57 and 26, respectively) issued from the tryptic digestion of 19 Se-containing proteins located in the gel by laser ablation - ICP MS imaging. The average Se/S substitution in methionine was 42.9 ± 35.0 and was protein dependent with ratios ranging from 5 to 160 for individual peptides. The substitution of sulphur in cysteine (14.1 ± 4.8 %) in the cysteine containing peptides was relatively similar (ratios from 9 to 23). Taking into account that the cysteine/methionine average ratio (2:1) in the yeast protein fraction, the study allowed the conclusion that 10-15% of selenium present in Se-enriched yeast is in the form of selenocysteine making up the mass balance of selenium species.

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XXXVIII CSI 2013

Lecture Abstracts

(L28) IDENTIFICATION OF ORIGINAL SOURCES OF VERMILION IN ANTIQUITY USING SULFUR ISOTOPE RATIO ANALYSIS Takeshi Minami1 , Bálint Péterdi2, and Miguel Angel Cau3 1

School of Science & Engineering, Kinki University 3-4-1 Kowakae, Higashi-osaka, Osaka 5778502 Japan 2 Geological and Geophysical Collections, Geological and Geophysical Institute of Hungary, Stefánia út 14, Budapest 1143, Hungary 3 Institució Catalana de Recerca i Estudis Avançats (ICREA)/director of Equip de Recerca Arqueològica i Arqueomètrica, Universitat de Barcelona (ERAAUB), Department de Prehistòria, Història Antiga i Arqueologia, Montalegre, 6-8, 08001 Barcelona, Spain e-mail: [email protected] Vermilion is a vivid red colour pigment used for decorating in ancient times worldwide. The chemical identification for vermilion is mercuric sulfide, and it was purified from cinnabar ore. A fine vermilion increases the vividness of the red colour. Cinnabar ores might have been collected from the outcrop of mines, and it is believed that a large amount of vermilion was necessary for decorating. Therefore, it is thought that there were not so many mines where a large amount of vermilion could have been collected in ancient times. We observed that the ratio of sulfur isotope of cinnabar ore varies according to the main mines of Europe. The samples were taken from the collections of the Geological and Geophysical Institute of Hungary. The ratio of sulfur isotope is measured by using Elemental Analyzer (Euro EA HEKAtech GmbH, Germany) and IsoPrism High Performance Stable Isotope Ratio MS (GV Instrument Ltd, Germany). As shown in Table 1, the sulfur isotope ratio of cinnabar ore from Almaden mine was very different from the value of other European mine ores. Then, we measured the ratio of sulfur isotope of vermilion used in Roman paintings collected from two Spanish Roman cities, Clunia (Burgos) and Baetulo (Badalona, Catalonia), in order to examine whether it was possible to determine the original source. The results of the analysis and the calculation of the ratio of sulfur isotope for the four samples collected from Clunia gave a value of +9.85 ± 0.94 ‰ and the ratio for the three samples from Badalona was +13.11 ± 2.67 ‰. From these results, vermilion used in Clunia could have been originally collected Table 1. Sulfur isotope ratio of cinnabar ores of from the Almaden mine. However, the value of vermilion European main mines used in Badalona is slightly higher than the value of the ore Mine Country mean SD (n) of the Almaden mine. The possibility of the use of ore from Almaden Spain +8.78 ± 1.20 (9) another mine ─but not the other mines shown in Table 1─ in Monteamiata Italy -0.97 ± 0.51 (2) order to produce the vermilion used in the paintings of Erzberg Austria +0.65 ± 3.47 (3) Badalona cannot be excluded. Idria Slovenia -1.33 ± 0.50 (6) In conclusion, the analysis of sulfur isotope ratio in vermilion Rudnany Slovakia -1.60 ± 0.16 (2) is an effective method to identify the original sources of 34 δ S(‰) vermilion used in ancient times.

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XXXVIII CSI 2013

Lecture Abstracts

(L29) STUDY OF INTERACTIONS BETWEEN REACTIVE GAZ SPECIES AND MICROORGANISMS BY NANO-RESOLUTION MASS SPECTROMETRY IMAGING Jean-Nicolas Audinot1, David Duday1, Franck Clément2, Elodie Lecoq1, Christian Penny1, Thierry Belmonte3, Kinga Kutasi4, Henry-Michel Cauchie1, Patrick Choquet1 1 Centre de Recherche Public Gabriel Lippmann – SAM & EVA, 41 rue du Brill, L-2422 Belvaux, Luxembourg 2 Pau University UPPA – IPREM UMR 5254 – LCABIE, Plasmas & Applications, 2 Avenue du Président Angot, F-64000 Pau, France 3 Nancy University – Institut Jean Lamour UMR CNRS 7198, Chemistry and Physics of Solids and Surfaces, CS 14234, F-54042 NANCY Cedex, France 4 Research Institute for Solid State Physics and Optics - Hungarian Academy of Sciences, POB 49, H-1525 Budapest, Hungary e-mail: [email protected] By working with a plasma reactor under gas flow conditions, it is possible to obtain a reactive gaz which keeps high reactivity on materials surfaces. Nowadays, these plasma reactors are commonly used for decontamination applications by acting on various micro-organisms (bacteria, virus, …). The interaction mechanism of the reactive species with microorganisms and living tissues is currently one of the most active fields of research in the plasma community [1]. Several innovative characterization methods are currently developed in order to study thoroughly the modifications induced by the reactive species (e.g. Reactive Oxygen Species (ROS) on plasmatreated microorganisms. The method used in this work consists of determining the effect of hydrogen, oxygen and nitrogen coming from the plasma on Escherichia coli bacteria. In order to follow the treatment effect on bacteria, we used isotopically labelled 15N2, 18O2 and 2H2 containingAr gas mixtures to produce the plasma. To localize and quantify the amount of reactive species on the bacteria, we used the unique mass spectrometry technique allowing working at the cellular scale: the NanoSIMS50 [2]. This mass spectrometer has been developed for high-resolution imaging (with an optimized lateral resolution down to 50 nm) allowing the investigation of subcellular structures and measurement of isotopic compositions with an excellent limit of detection in the analyzed nanoscale volume [3-4]. Different exposure times (1, 5, 10 and 15 min) were used to treat the biological samples under different experimental plasma conditions. The NanoSIMS50 analyses deliver isotopic images of cellular structures and we measured gas fixation pixel by pixel in different intracellular areas for each individual E. coli. Once the acquisition done, we calculated the values of the isotopic ratio and the percentage of penetration of labelled gas for individual bacteria [5]. For example, an increase in isotopic oxygen incorporated into the structure as a function of the exposure time was observed, until a saturation time. These results were compared with other treatments performed with nitrogen and hydrogen labelled gases (15N, 2H).

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XXXVIII CSI 2013

Lecture Abstracts

(L30) SOLID SAMPLING TECHNIQUES FOR THE DIRECT ELEMENTAL OR ISOTOPIC ANALYSIS OF DRIED MATRIX SPOTS Martín Resano,1 M. Aramendía,2 L. Rello,3 E. García-Ruiz1 1

Department of Analytical Chemistry, University of Zaragoza, Zaragoza, Spain, 50009 Centro Universitario de la Defensa-Academia General Militar de Zaragoza, Carretera de Huesca s/n, 50090, Zaragoza, Spain 3 Department of Clinical Biochemistry, “Miguel Servet” Universitary Hospital, Paseo Isabel La Católica 1-3, 50009, Zaragoza, Spain 2

e-mail: [email protected] The deposition of biological fluids onto clinical filter paper, producing a dried matrix spot (DMS), is a methodology that has become increasingly popular in the years to date and is nowadays deployed in a wide variety of bioanalytical contexts, such as screening for metabolic diseases in newborns, therapeutic drug monitoring, pharmacokinetic or toxicological and forensic studies.1,2 This popularity is a consequence of the significant advantages brought by this methodology, that permits the development of minimally or non-invasive collection approaches, and results in specimens (DMS) that are very stable and can be easily transported and stored. However, there is still a very limited number of works exploring its potential for elemental and/or isotopic analysis. In part, this can be explained considering that the transformation of a liquid sample (e.g., blood or urine) into a solid one (DMS) often implies additional problems for the analyst, such as lower sensitivities or enhanced matrix effects. Fortunately, there are analytical techniques that permit direct analysis of these types of solid samples and are capable of offering an excellent performance. This work discusses the use of solid sampling high-resolution graphite furnace atomic absorption spectrometry (SS HR CS GFAAS) and laser ablation-inductively coupled plasma mass spectrometry (LA-ICPMS) for the direct analysis of dried blood spots and dried urine spots, and its application to a variety of situations, such as i) fast screening of large populations;1 ii) monitoring of chronic patients,2,3 and iii) early detection of disease associated with the metabolism of some metals.4 References 1. M. Resano, L. Rello, E. García-Ruiz and M. A. Belarra, J. Anal. At. Spectrom., 2007, 22, 1250– 1259 2. L. Rello, A. C. Lapeña, M. Aramendía, M. A. Belarra and M. Resano, Spectrochim. Acta Part B, 2013, 81, 11–19. 3. M. Aramendía, L. Rello, F. Vanhaecke and M. Resano, Anal. Chem., 2012, 84, 8682−8690. 4. M. Resano, M. Aramendía, L. Rello, M. L. Calvo, S. Bérail and C. Pécheyran, J. Anal. At. Spectrom., 2013, 28, 98–106

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XXXVIII CSI 2013

Lecture Abstracts

(L31) LOW RESOLUTION CONTINUUM SOURCE ELECTROTHERMAL ATOMIC ABSORPTION SPECTROMETRY: CLARIFICATION OF ANALYTICAL POTENTIAL Dmitri Katskov1 and Svetlana Kurilko2 1

Department of Chemistry, Tshwane University of Technology, Private Bag X680, Pretoria 001, South Africa 2 Department of Optical Information Technologies, State Technical University, 20, K. Marx av. Novosibirsk 630073, Russia e-mail: [email protected] The methodology of simultaneous multi-element electrothermal atomic absorption spectrometry (SMET AAS) [1-3] is based on pulse vaporization of the sample in a graphite tube atomizer, CCD detection of transitory radiation from the continuum source (CS) within broad wavelength range and calculation of absorption at the resonance lines of the elements to be determined. Relatively small number of lines in atomic absorption compared to that in respective emission spectra makes possible to employ low resolution (LR) spectral instrument, which can provide fast data acquisition within wavelength range 200-400 nm where most part of resonance lines is located. Providing simultaneous access to the absorption spectra of various elements LR, however, causes substantial sensitivity loss compared to traditional AAS and non-linearity of calibration curves. In SMET AAS the sensitivity loss is partially compensated by high pulse density of atomic vapor in the fast heated tube atomizer with narrow absorption volume. The calculation algorithm provides background (BG) correction, linearization of function absorption vs. concentration of atomic vapor and integration of the modified signals. Simultaneous determination of individual analytes is performed within 3-5 orders of magnitude concentration range. The methodology has been applied to the analysis of underground water and coal slurry [2, 3]. In this work the investigation of analytical potential of SMET AAS continued with focus on instrumental and software improvement as well as on methodology of multi-element calibration. The D2 and Xe arc lamps for 190-350 and 220-410 nm ranges were employed combined with Ocean Optics HR4000 CCD spectrometer (3600 pixels) and fast heated tube atomizer (25 and 2.5 mm in length and internal diameter, respectively). High CS intensity permitted increasing of number of spectra collected during 1 s atomization time, from 80 to 200. Together with the increased sensitivity on account of longer tube this helped to reach limits of detection equal or for some elements better than it is claimed for ICP instruments. The calculation algorithm permits BG correction of sharp molecular bands using reference spectra obtained independently. The calculation results are presented directly in the concentration units using permanent calibration obtained for single element solutions or can be justified by the measurements with multi-element standard addition. Instant observation of 3-d or temporary integrated spectra helps to select conditions for chemical modification of the sample or determination of non-metals using molecular bands. References: D.A.Katskov, G.E.Kanye, S.Afr.J.Chem. 63 (2010) 45-57 G.Jim, D.Katskov, S.Afr.J.Chem. 64 (2011)71-78 D.Katskov, Trends in Applied Spectroscopy, 9 (2013) 17-40

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Lecture Abstracts

(L32) TRACE DETERMINATION OF METALS BY IN-ATOMIZER HYDRIDE TRAPPING AAS: METHOD DEVELOPMENT, VALIDATION AND ANALYTICAL APPLICATIONS Libor Průša1,2, Stanislav Musil1, Miloslav Vobecký1, Jiří Dědina1 and Jan Kratzer1 1

Institute of Analytical Chemistry of the ASCR, v.v.i., Veveří 97, Brno, CZ 602 00, Czech Republic Charles University in Prague, Faculty of Science, Department of Analytical Chemistry, Albertov 8, Prague 2, CZ 128 43 Czech Republic

2

e-mail: [email protected] Hydride generation coupled to atomic absorption detector (HG-AAS) is due to its simplicity, selectivity and sensitivity a powerful and favorite analytical technique. Analyte conversion to the gaseous hydride has two advantages – firstly, the analyte is separated from the matrix and secondly, analyte can be preconcentrated from the gaseous phase. Employing the preconcentration step, the HG-AAS limit of detection (LOD) can be lowered to meet the requirements of the ultratrace analysis being often inevitably requested for hydride forming elements either by law regulations or by the customers. Providing that the preconcentration step is simple, fast and efficient, this inexpensive approach based on hydride trapping-AAS can substitute or even surpass conventional approaches to elemental and speciation analysis based on the liquid phase sampling inductively coupled plasma mass spectrometry (ICP-MS), which generally serves as a trademark of unparalleled sensitivity. The most common approach to hydride preconcentration is in-situ trapping in graphite furnaces. However, also quartz and metal preconcentration devices have been designed and successfully employed for ultratrace determination of hydride forming elements with detection by AAS. A compact trap-and-atomizer device based on a quartz multiatomizer has been constructed in our laboratory recently. It was shown to be a powerful tool for ultratrace determination of hydride forming elements (As, Sb, Bi, Se, Pb and Sn) since it allows rapid and efficient in-atomizer preconcentration of the analyte prior to its detection by AAS. Oxygen rich atmosphere is used in the collection step of the preconcentration procedure to remove hydrogen evolved during the chemical hydride generation of the analyte to reach efficient trapping. On the contrary, hydrogen rich atmosphere is used in the volatilization step to efficiently release trapped species. The optimum preconcentration conditions for individual hydride forming elements as well as the corresponding preconcentration efficiencies are summarized in Tab. 1. Optimization of generation, preconcentration and atomization conditions will be discussed using tin as a model analyte. Complete analyte collection followed by quantitative release of trapped tin species is reached under the optimum preconcentration conditions, i.e. collection temperature of 500 °C and volatilization temperature of 800 °C. Hydrogen flow rate of 50 ml.min-1 was found to be optimum with respect to sensitivity and peak shape (FWHM 0.7 s).

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Tab. 1 Optimum preconcentration conditions and corresponding preconcentration efficiencies of hydride forming elements in the quartz trap-and-atomizer device element

Tcollection, (°C)

Tvolatilization, (°C)

H2(volatilization) flow rate, (ml min-1)

preconcentration efficiency, (%)

As

80 - 650

650 - 800

100

 50

Sb

400 - 1000

900 - 1050

75

100

Bi

80 - 1000

800 - 1100

100

100

Se

80 - 300

550 - 650

50

 70

Pb

100 - 300

700 - 900

100

100

Sn

200 - 600

750 - 900

50

100

Analytical figures of merit reached by the proposed method for ultratrace determination of Sn by stannane generation in-atomizer trapping AAS will be presented. Whereas LOD for the on-line atomization mode (no preconcentration, 2 ml sample) reached 0.14 ng.ml-1 Sn, LOD for 30 s preconcentration (2 ml sample) was 0.05 ng ml-1 Sn. Preconcentration period can be further increased without any change in the preconcentration efficiency indicating sufficient stability of the trapped Sn form (no losses). Preconcentration period of 2 min (sample consumption 8 ml) was chosen as a compromise between sample throughput and sensitivity (LOD 0.03 ng ml-1 Sn). Interferences of other hydride forming elements on Sn determination were investigated employing analyte to interferent ratios up to 1:1000. Both the on-line atomization (no preconcentration) as well as the preconcentration modes have been found free of significant interferences of other hydride forming elements (As, Sb, Bi and Se). Analyses of real samples (tinned food) will be discussed. Radiotracer technique is a very effective, reliable and powerful tool to verify the newly developed analytical procedure independently of the detector used during the development. This fact will be demonstrated employing lead as model analyte. The use of radiotracers enables not only to quantify the efficiency of single steps (generation, collection, volatilization) of the newly developed procedure but also to visualize the spatial distribution of the analyte in the apparatus. Lead preconcentration on quartz surface after plumbane generation was studied by means of laboratory prepared 212Pb radioactive indicator. Trapping capacity, preconcentration efficiency as well as Bi interference on Pb preconcentration were characterized by radiometry and autoradiography. The mechanism of Bi interference was understood thanks to the use of the radioactive indicator - it appears in the volatilization step of the preconcentration procedure. This work was supported by the Czech Science Foundation (grant No. P206/11/P002), Institute of Analytical Chemistry of the ASCR, v.v.i. (project no. RVO: 68081715) and the Ministry of Education, Youth and Sports of the Czech Republic (project MSM 0021620857).

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Lecture Abstracts

(L33) OPTIMIZATION STUDY ON DETERMINATION OF INORGANIC ARSENIC SPECIES IN HOT CHILLI PEPPER AND TOMATO VARIETIES BY USING MICROWAVE ASSISTED DIGESTION FOLLOWED BY FLOW INJECTION-HYDRIDE GENERATION ATOMIC ABSORPTION SPECTROMETRY Nittaya Thaharn1, Suchila Techawongstien2 and Saksit Chanthai1* 1

Department of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science, Khon Kaen University, Khon Kaen, 40002 Thailand. 2 Department of Plant Science and Agricultural resources, Faculty of Agriculture, Khon Kaen University, Khon Kaen, 40002 Thailand. *e-mail: [email protected] An analytical procedure for inorganic arsenic (As) species in hot chilli pepper and tomato fruits at red-ripe stage using microwave assisted digestion (MAD) followed by flow injection - hydride generation atomic absorption spectrometry (FI-HGAAS) was presented. The optimum conditions of both acid digestion method and arsenic hydride (AsH3) determination were studied in details. The plant sample (0.5 g) was digested with 5 mL of concentrate nitric acid by MAD programmed at 900 W for 25-35 min. Regarding on speciation analysis, arsenite, As(III), in the acid digests could only be analyzed by FI-HGAAS using 1.0% (v/v) HCl as a carrier solution and 0.5% (w/v) NaBH4 in 0.04% (w/v) NaOH as a reducing agent, while total As content was determined after pre-reduction of arsenate, As(V), to be As(III) with 2% (w/v) thiourea prior to measurement by the instrument. The concentration of As(V) was then calculated by the difference. Detection limits for As(III) and As(V) were 0.004 and 0.006 μg L-1, respectively. Relative standard deviation (RSD) of the data was less than 5.32% (n = 10). Recovery study (98-103%) of the real samples spiked with 10 µg L-1 As was satisfactorily obtained. The proposed method was applied for the trace determination of As in six varieties of hot chilli pepper (0.55-0.88 µg As(III) g-1 & 0.22-0.93 µg As(V) g-1) and seven varieties of tomato (0.36-0.64 µg As(III) g-1 & As(V): 0.22-0.60 µg As(V) g-1) samples. Keywords: Arsenic speciation, Chilli, Tomato, Microwave assisted digestion, FI-HGAAS

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XXXVIII CSI 2013

Lecture Abstracts

(L34) PRECONCENTRATION OF MERCURY FROM NATURAL WATERS BY AMALGAMATION OF HG2+ ON COPPER POWDER AND HG0 ON GOLD NANOPARTICLES Nikolay Panichev, Khakhathi Mandiwana and Merimee. Kalumba Department of Chemistry, Tshwane University of Technology, P.O. Box 56208, Arcadia 0007, Pretoria, South Africa e-mail: [email protected] Determination of total amount of mercury (Hg) in natural waters is usually carried out after chemical restoration of Hg+2 ions to elemental mercury Hg0, using cold vapour generation technique with atomic absorption detection (CV-AAS). The limit of detection (LOD) of Hg determination in natural waters using CV-AAS is approximately 0.2 µg L-1. At present, to reduce the value of LOD of Hg determination in natural waters is only possible by analytical methods in which a step of preconcentration is involved. The most promising method of preconcentration could be the sorption of Hg0 on golden nanoparticles. For this, all Hg+2 ions in water samples must be reduced to elemental mercury. This step of chemical pretreatment is connected with additional time of analysis and could be the reason of either losses of Hg or contamination of samples. To avoid the problem of samples chemical pretreatment, we proposed the method of determination of Hg in water samples by preconcentration of Hg+2 on copper particles and Hg0 on golden nanoparticles impregnated into membrane filters. The reaction between different chemical forms of mercury with Cu and Au are the following: Hg2+ + Cu → Hg + Cu2+ Hg + Cu → CuHg AM Hg + Au → AuHg AM

(1) (2) (3)

The addition of golden nanoparticles to membrane filters for Hg0 collection was connected with their high efficiency for amalgamations, which in combination with high efficiency of Hg+2 collection by copper powder created the possibility of total Hg (Hg +2 + Hg0) determination. Cu powder Cu Hg 20000

Intensity

15000

10000

5000

0

20

40

60

80

2

 

Fig.1 SEM image of copper powder on membrane filter (A) and pattern XRD of copper powder with accumulated Hg0 (B)  

The measurements of Hg were carried out by thermal desorption of Hg from filters, using a RA 915+ mercury analyzer (Lumex, Russia). The determination of Hg by thermal desorption does not

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involve any additional chemical reagents and sharply reduces risk of samples contaminations. The LOD calculated using the calibration graph function (y=332x + 2; R2 = 0.9983) and corresponding standard deviation (3.2 %) for the calibration line was found to be 0.02 ng (absolute mass). It should be noted that the LOD in concentration units is inversely proportional to the sample volume processed. In our study, the relative LOD (0.2 ng L–1) was calculated for 0.1 L of water sample. The validation of method was done by analysis of several CRM’s and by the recovery test. For example, the result of Hg determination in CRM TORT-2 (National Research Council of Canada), 0.28 ± 0.02 µg g-1, which was obtained after its chemical decomposition in HNO3 + H2O2 using microwave, Mars-5 were in a good agreement with certified value 0.27 ± 0.06 µg g-1. The results of recovery test, which was conducted with samples of tap water collected at in Pretoria city, were between 94-104 % for Hg concentrations 0.5 and 1.0 ng L-1. The greatest advantage of this method is the possibility of samples collection on the sport, without transportation of large amounts of water for the analysis in laboratories due to high efficiency of simultaneous collection of mercury ions Hg+2 and elemental mercury Hg0 from aqueous phase on membrane filters.    

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XXXVIII CSI 2013

Lecture Abstracts

(L35) SAMPLING OF LIQUIDS IN ATOMIC EMISSION SPECTROMETRY USING A HELIUM ATMOSPHERIC PRESSURE GLOW DISCHARGE José A.C. Broekaert, Katharina K. Moß and Klaus-Georg Reinsberg Department of Chemistry, University of Hamburg, Martin-Luther-King-Platz 6, D-20146 Hamburg, Germany e-mail: [email protected] Atmospheric pressure glow discharges (APGD) during the last years have been recognized as powerful radiation and ion sources for atomic emission and mass spectrometry, respectively. One of the many possible systems is the He operated dc APGD with hollow electrodes, as it has been developed and optimized with respect to its geometry and working conditions by Gielniak et al. [1]: Initially for this source the excitation and rotational temperatures and electron number densities were determined. Further, this source has been found useful to excite dry element vapours, as in the case of Hg vapour released in the Hg cold vapour technique, but also for the excitation of gas chromatography effluents, as shown for halogenated hydrocarbons [2]. The source in this contribution has been studied to elutriate its possibilities to take up wet aerosols for spectral analysis purposes. At a current of 40 mA and a He flow of 500 mL.min-1 the source was found to be able to accept aerosols generated with a conventional pneumatic nebulizer positioned in a double pass spray chamber according to Scott as well as with a custom built drop on demand system based on printer cartridges [3]. In the case of pneumatic nebulization ca. 170 µL.min-1 was consumed at an efficiency of some %. The current-voltage characteristics were found to be normal both in the case of dry as well as with wet aerosols. However, the burning voltage in the case of a change from dry to wet aerosols was found to considerably increase. Indeed, in the case of pneumatic nebulization the burning voltage at 40 mA was found to increase from 630 to 840 V but therefor in the case of the drop on demand nebulizer only from 630 to 750 V. Further, the influence of the water load on the rotational temperatures measured on OH bands and on the excitation temperatures measured with the aid of Fe atomic lines was studied. In the case of dry He for this purpose ferrocene vapour was lead into the plasma and in the case of wet aerosols aqueous solutions of Fe were used. Whereas the rotational temperatures were found to be at the 1500 K level and the excitation temperatures at 4500 K both for a dry plasma, the introduction of the sample liquids was found to decrease the rotational temperatures by 500 K. The excitation temperatures were found to decrease by 400 K for pneumatic nebulization and 240 K for the drop on demand system. The electron number densities as determined from Stark broadening of the Hß line are of the order of 1 x 1014 cm-3 and they were found to be mainly unaffected by the introduction of moisture into the plasma. As all influences of the introduction of wet aerosols discussed above were found to be moderate, the analytical figures of merit of the He APGD in the case of its use as radiation source for atomic emission spectrometry using both ways of sample liquid introduction were studied. For these experiments a 0.55 m Czerny-Turner monochromator with a 2400 lines.mm-1 grating (Triax550, Horiba Jobin-Yvon) equipped with a iDus 420-OE CCD camera (Andor Technology Ltd., Belfast, UK) was used. It was found that in the spectra almost only atomic lines and hardly any ion lines were found. The detection limits for the case of pneumatic nebulization for some elements were: Cd 228.802 nm: 19; Cu 324.754 nm: 140; Mg 285.213 nm: 110; Mn 279.482 nm: 130 and Na 588.995 nm: 10 µg.L-1. For Na in the case of the drop on demand nebulizer a detection limit of the same range of concentration was found. The calibration curves with both liquid sampling systems were found to be linear over the range of 1 – 100 mg.L-1 . With OES using the He dc APGD a concentration of Na in tap water of 18.9 + 0.3 mg.L-1was found with the drop on demand system. In -113 -

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the case of the pneumatic nebulization system the analysis result was: 20.8 + 0.9 mg.L-1 Both values were in the range of the concentration determined with ICP-OES (20.2 + 0.4 mg.L-1). The results show that the He APGD developed and optimized within the frame of this work for the case of the introduction of minute flows of aqueous solutions, as it is e.g. the case in elementspecific detection in liquid chromatography, might be useful. [1] B. Gielniak, T. Fiedler and J.A.C. Broekaert, Spectrochim. Acta, Part B 2011, 66: 21-27. [2] Unpublished work. [3] J.O. Orlandini v. Niessen, J.N. Schaper, J.H. Petersen and N.H. Bings, J. Anal. At. Spectrom. 2011, 26: 1781-1789.

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XXXVIII CSI 2013

Lecture Abstracts

(L36) GD TOFMS WITH PULSED COMBINED HOLLOW CATHODE FOR DIRECT ANALYSIS OF DIELECTRIC SAMPLES Alexander Ganeev1,2, Anna Guball, Ilja Ivanov1, Sergey Potapov2 and Volker Hoffmann3 1

Faculty of Chemistry, St. Petersburg State University, Universitetsky pr., 26, St. Petergof, St. Petersburg, 198504, Russia 2 Lumass Ltd., Obukhovskoy Oborony pr. 70, bld.2, St. Petersburg, 192029, Russia 3 Institute for Complex Materials, Leibniz Institute for Solid State and Materials Research Dresden, Helmholtzstrasse 20, 01069 Dresden, Germany e-mail: [email protected] Now GD MS is used both for bulk analysis and for depth profiling. One of the important applications of GD MS is the direct determination of the elements (including radioactive) in pressed dielectric powders (first of all oxides), nuclear fuel, spent nuclear fuel, different glasses and besides semiconductors with large band gap. But the analysis of non-conductors with the traditionally used Grimm cell is seriously more difficult than that of conductors. Using the DC mode it is impossible to perform the direct analysis of such non-conducting samples without a secondary (or hollow) cathode. The use of RF power allows the analysis of dielectric samples, but one cannot avoid problems with overheating of the sample and capacitive loss of voltage and consequently of the sensitivity. The first problem is easily solved by pulsing the RF power supply, but lower erosion rates and thus longer times for the analysis are caused. The combination of the combined hollow cathode discharge cell and pulsed powering of the discharge was found to overcome these limitations. From the one hand pulsed glow discharges help to get a significant increase of the analytical signal, do not lead to an overheating of the sample and besides they are easy to couple with a fast mass analyzer and have more independent parameters to tune for optimization. Moreover using the pulsed mode helps to reduce the accumulation of surface charge. At the same time by the use of the combined hollow cathode one can additionally get a considerable increase in sensitivity due to the so called “hollow cathode effect”. A number of non-conducting samples including sapphire, polycor (Al2O3), GaN, SiC, Si, pressed oxides of rare elements, iron and uranium were used for investigations. GD OES and GD TOFMS techniques were used in the experiments. The Pulsed GD hollow cathode (PGD HC) source was shown to give considerably higher signal intensities comparing with the RF Grimm source. It is worth mentioning that the use of the hollow cathode effect does not give a considerable advantage at equal power. The only benefit was found at thick dielectric samples since for the HC system no decrease of signal with sample thickness was observed. A principle difference between sputtering processes in HC cell and Grimm cell was found to take place. The mechanism of sputtering of nonconductors in direct current mode was investigated and established to be connected with the formation of a thin conductive surface layer. Thus it is possible to sputter non-conducting samples even in DC mode and thus the signal intensity practically does not depend on sample thickness in contrast to the RF discharge in a Grimm type cell. Considering the nature of this layer both, cathode material deposition and the formation of the “enriched” surface layer produced when the component with high sputtering rate leaves the surface faster than the component with lower sputtering rate were found to take place. As for the disadvantages of the HC system it should be noted that due to the introduction of the additional component this system is more complicated to operate and optimize and is less stable than the Grimm source. Sputtering processes were found to depend strongly on cathode material. Aluminum, copper, and tantalum cathodes were considered and compared. The present work includes the results of the application of PGD HC TOFMS system for the analysis of various non-conducting sample. Possibilities and limitations of the system are discussed. -115 -

XXXVIII CSI 2013

Lecture Abstracts

(L37) SELECTIVE EXCITATION IN ANALYTICAL GLOW DISCHARGES – ITS RELEVANCE IN GD-OES ANALYSIS Edward B. M. Steers, London Metropolitan University, 166-220 Holloway Road, London, N7 8DB, UK e-mail: [email protected]

All analytical glow discharges are relatively low power sources, running in low pressure plasma gases (Grimm type sources: ~15 W, 5 hPa, VG9000 type sources: ~5 W, 1 hPa). Such sources are not in local thermodynamic equilibrium, and line intensities and ion signals depend on the excitation and ionization processes populating the relevant levels. For energy levels produced by electron excitation, the intensity will depend on the optical excitation function for that particular level and the electron energy distribution function (EEDF) so that changes in the EEDF produced by the plasma gas composition will affect the intensity of the various spectral lines differently. However, the main selective processes for ionisaton and excitation are Penning excitation (PE), Penning ionisation (PI), both resulting from collisions with metastable atoms of the plasma gas, and asymmetric charge transfer (ACT), caused by collisions with plasma gas ions. PE: Ao + Bm  A* + Bo + ΔE PI: Ao + Bm  Ao+ + Bo + e + ΔE or Ao + Bm  A+* + Bo + e + ΔE, ACT: Ao + Bo+  A+* + Bo + ΔE, Ao, Bo are ground state atoms, e.g. A from the sputtered sample, and B from the plasma gas * denotes an excited state Bm is a metastable atom, Ao+ a ground state ion and ΔE is the kinetic energy released in the collision In all cases, ΔE must be positive, or small if negative. For PE and ACT, conservation of energy and momentum mean that ΔE must be small even when positive – these are resonant processes. For PI, the release of an electron allows the conservation laws to be satisfied for larger values of ΔE. Thus all the selective excitation processes depend on the arrangement of the energy levels of the colliding atoms and ions, and vary greatly from element to element. Moreover, the presence of foreign gases in the plasma gas can cause major changes in the number density of plasma gas ions and metastable atoms and so affect the intensities of the spectral lines. The most significant process affecting the intensities of spectral lines is probably ACT – not only must there be ionic states with appropriate energy to be excited, but spin must also be conserved, at least for the strongest interactions. Since the change from ionised to atomic ground state in a noble gas involves a spin change of ½, the element to be excited must have ionic states of appropriate energy differing in spin by ½ from the spin of the atomic ground state or possibly of low lying metastable atomic states – i.e the multiplicity must differ by 1. This latter condition is satisfied, e.g. for copper, iron and manganese for Ar-ACT, but not for chromium. ACT in particular can be seriously affected by small amounts of hydrogen or oxygen in the plasma gas – this may come from gas trapped in the sample or may arise from a constituent of the sample, e.g. an oxide or hydride. For example, the presence of hydrogen in argon causes a dramatic fall in + + the number density of Ar ions and their replacement by ArH ions. Oxygen also reduces the + number of Ar ions but to a lesser extent. In both cases the intensity of lines excited by Ar-ACT is

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reduced. On the other hand, both hydrogen and oxygen can excite ionic levels having a total excitation energy (i.e. ionisation energy + excitation energy) close to but less than 13.6 eV. We have carried out extensive experimental work, deliberately introducing hydrogen or oxygen into the plasma gas at low levels ~ 0.1% v/v, corresponding to the amount that may arise e.g. from a hydride layer and at higher levels so that the effect may be more clearly seen. All the results to be presented have been obtained using a “Grimm-type” source with “standard excitation conditions”, i.e. constant voltage (700 V) and current (20 mA). The pressure used therefore had to be changed, depending on the cathode (sample) material and the plasma gas. Further, the addition of small amounts of molecular gases (H2, O2 or N2) required a change in pressure to maintain standard conditions. In the majority of cases, the spectra were recorded using the Imperial College high resolution vis-vuv Fourier transform spectrometer. Examples of selective excitation will be presented for various elements, including the effect of impurities, e.g. hydrogen, and the analytical implications discussed. For example, Figs 1 & 2 show effects produced by hydrogen with a manganese cathode

Ar + 0.15% H2

Line Intensity (AU)

4.0 –

250

275 Fig. 1. A section of the manganese spectrum excited in argon and in an argon/hydrogen plasma

Intensity Ratio Ar+H2 / Ar

Pure Ar

Line Intensity (AU)

5.0 –

257.610 12.245 eV

272.210 15.697 eV

259.372 12.213 eV

271.003 15.427 eV

1.8 1.6 1.4 1.2 1.0 0.8 0.6 0.4 0.2 0.0 0

0.1

0.2

0.3

0.4

0.5

Hydrogen concentration,  %

Fig. 2 Intensities of some Mn II lines with various argon/ hydrogen mixtures, normalised to intensity with pure argon. di /h d l

Mn II lines with total excitation energy ~ 15.8 eV are normally strongly excited by Ar-ACT and fall dramatically in intensity when hydrogen is introduced.

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Lecture Abstracts

(L38) MOLECULAR EMISSION IN GD-OES REVISITED – STRATEGIES FOR BACKGROUND CORRECTION Arne Bengtson1 and Mats Randelius1 1

Swerea KIMAB, Isafjordsgatan 28A, SE-164 07 Kista, Sweden

e-mail: [email protected] Previous work has shown the existence of molecular emission in Glow Discharge Optical Emission Spectroscopy (GD-OES). The most prominent emission bands originate from the diatomic radicals CO, OH, NH and CH, but emission from C2 and a few metal oxides has also been observed. The molecular emission is always present in the very beginning of the discharge, but when sputtering organic coatings, oxides etc. the emission often persist throughout the layer. From the analytical point of view, the molecular emission is a problem in compositional depth profile analysis (CDP) since it is a source of spectral background at several of the atomic emission lines used for elemental analysis. Although this problem has been well known for several years, there is not yet a well developed technique to perform background correction for molecular emission. In principle a conventional “line interference correction” algorithm is applicable, but there is no easy way to determine the correction factors. In most CDP work with GD-OES, the molecular emission problem is simply ignored, which undoubtedly gives rise to “false” depth profiles of certain elements. In this work, the temporal behaviour of emission lines from CO, OH, NH and CH is studied. A Leco GDS 850 spectrometer fitted with channels for these molecules was used. Since the spectrometer is a conventional multichannel instrument with PMT detectors, only the emission from single vibrational – rotational lines within broad “emission bands” from each molecule is detected. In addition, simultaneous observations of complete low – resolution spectra of the molecular bands were made with miniature CCD spectrometers, coupled directly to the glow discharge. The temporal profiles of the molecular emission signals were compared with profiles of several atomic emission lines, located within the spectral width of the corresponding molecular band structure. It was shown that while the expected correlation between the molecular channels and the spectral background of the atomic lines is obvious, the temporal behaviour can be different when comparing initial signals (< 2 s) with the long-term signals through e.g. polymer coatings. This indicates that the relative intensities of the different parts of a molecular band are affected by the discharge conditions, which inevitably takes a finite time to stabilise after ignition of the discharge. Possible strategies to deal with this problem by implementing “dynamic” background correction for molecular emission will be discussed.

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(L39) CHEMICAL CHARACTERIZATION OF DEKATI® LOW PRESSURE IMPACTOR (DLPI) WALL DEPOSITS Thibaut Durand, Yves Morele, Denis Bemer, and Davy Rousset Institut National de Recherche et de Sécurité, Rue du Morvan CS60027, 54519 Vandoeuvre-lèsNancy, France e-mail: [email protected] Cascasde impactors are widely used to assess aerodynamic particle size distribution of airborne particles. It is possible from each impaction stage to determine mass concentration and chemical composition of particles according to size fractions. Geometry of these impactors however induces inner deposit phenomena, which can be due to particle bounce on impacting support, or to diffusion phenomena for fine particles, or because of the particles charges for specific impactors (for instance in the electrical low pressure impactor). Previous studies have highlighted wall depositions for several impactors but these have never been properly studied on low pressure impactors which are dedicated for ultrafine particles characterization and monitoring. In this study, characterization of wall deposits was carried out with the Dekati® Low Pressure Impactor (DLPI), which separates airborne particles into 13 size fractions from < 30 nm up to > 10 μm (filter stage configuration). In the DLPI, many surfaces could be subjected to particles collection, in addition to impaction filter. Airborne particles were generated by a metal coating process, an electric arc gun with zinc wires. This process is widely used for coating and generates large quantities of ultrafine particles. The aerosol produced was bi-modal (80 nm and 5µm) and thus covered the whole DLPI collection range. In front of the gun spray, aerosol was driven through a tunnel at a constant flow rate. The sampling point was situated few meters down the tunnel from the emission point so that the aerosol stabilized. This sampling point was connected to a 10 fold diluter with 4 outputs among which two was connected to the DLPI and to a 47 mm filter holder (PVC filters) as a reference in mass concentration. The diluter was used because of the high particle concentration (~300 mg.m-3). This concentration would imply too short sampling duration without dilution. For the first generation, an additional Electrical Low Pressure Impactor (ELPI) was connected with the DLPI and the filter to assess the difference in collection efficiency for two similar impactors. No wall characterization was performed for the ELPI. Two different amounts of zinc were investigated (N=3) to check the influence of the particle concentration on the deposition phenomena for two collection duration (5 and 20 minutes). For each generation, gravimetric and chemical analyses were performed. Before each generation, the DLPI was entirely cleaned, by cleaning each part in an ultrapure water sonicated bath, then by isopropyl alcohol wiping. To quantify wall deposits, 37 mm mixed cellulose ester (MCE) membranes were wetted with ultrapure water to wipe inner surface of the impactor. One MCE membrane was used for each collection plate and one for each jet-plate. Each MCE was first cut into four parts in order to wipe each side of a specific piece at least twice. Once used, the four parts of the membrane were stored in clean tube before acid digestion. Blanks were performed before and after each run to verify cleaning procedure, and the wall particles collection efficiencies. Digestion of MCE membranes was performed directly in the storage tube with HClO4:HNO3 (1:6) acid mixture. 25 mm PVC filters were used as collection medium in the DLPI impaction stage. They were previously Triton-X washed, vaseline greased, and weighed before generation. After generation, they were weighted again and then digested with ultrapure nitric acid using a microwave digestion system. Chemical composition from both PVC filters and MCE membranes were determined either by inductively coupled plasma optical emission spectrometry (ICP-OES) or by inductively coupled -119 -

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plasma mass spectrometry (ICP-MS), according to particle loading. Results showed a good repeatability between the different generations regarding the mass collected on the PVC impaction filters. Moreover gravimetric results and chemical analysis match well. Wall deposits were more scattered among generations although a similar whole trend could be noticed. Considering the relative amount of Zn on walls per stage, three main deposition sites could be distinguished. The first one was in a small size range, around the fourth and fifth collection plate (~200 nm), the second one in the intermediate size range (~1 µm), and the third one in a large range, on the thirteenth stage (~10 µm). These maximums were not related to the mode of the aerosol. Amounts of zinc were higher on jet-plate parts than onto corresponding collection plates, which is consistent regarding the surface wiped. No significant differences regarding the relative amount of wall deposits were observed between 5 and 20 minutes sampling duration. For the whole DLPI column, in average, about 13 % of the total mass collected was found on surfaces rather than onto the PVC impaction filters. These wall losses could be considered as negligible, but locally for some stages, wall losses could rise up to 30%, which could lead to an underestimation of a specific size fraction of the airborne particles. Results from the ELPI experiments showed a large difference between ELPI and DLPI: ELPI collected 75 and 59 % of particles less than DLPI did respectively, when comparing chemistry and gravimetric results. This cannot be explained only because of the charge of particles. More investigation should be done to explain the phenomenon. In conclusion, characterization of DLPI wall deposits using a zinc aerosol containing ultrafine particles mainly showed that: Wall deposits were not specifically related to aerosol modes Collection times were not influent on the relative quantity deposited on walls Main wall deposits were found on jet-plate nozzles

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(L40) CHEMICAL CHARACTERIZATION AND OXIDATIVE POTENTIAL OF PM2.5 COLLECTED IN OFFICE BUILDINGS IN GREECE AND THE NETHERLANDS: A COOPERATIVE STUDY Tamás Szigeti1, Philomena M. Bluyssen2*, Henricus J.M. Cornelissen2, Chrissi Dunster3, Krystallia K. Kalimeri4, Frank J. Kelly3, Yvonne de Kluizenaar2, Franco Lucarelli5, Ioannis Sakellaris4, Dikaia E. Saraga4, John Bartzis4, Gyula Záray1, Victor G. Mihucz1 1

Department of Analytical Chemistry, Eötvös Loránd University, 1117 Budapest, Hungary TNO, PO Box 49, 2600 AA Delft, The Netherlands 2* Current address: Department of Architectural Engineering and Technology, Delft University of Technology, Delft, 2628 BL, The Netherlands 3 MRC-HPA Centre for Environment and Health, King’s College London, SE1 9NH London, UK 4 Department of Mechanical Engineering, University of Western Macedonia, 50100 Kozani, Greece 5 Department of Physics and Astronomy, University of Florence/INFN, 50019 Sesto Fiorentino, Italy 2

e-mail: [email protected] Indoor air quality has a high importance in the everyday life of people of the 21st century, as people spend a large proportion of their time indoors. One of the objectives of the European collaborative project called OFFICAIR is the characterization of indoor and outdoor PM2.5 (particles with an aerodynamic diameter smaller than 2.5 μm) in and around modern office buildings. PM2.5 sampling was performed in 1 office in 5 different buildings in Greece and 1 office in 2 buildings in The Netherlands with low-volume aerosol samplers operating for about 100 hours (from Monday morning to Friday afternoon) onto 47 mm quartz fibre filters (Whatman QM-A) in summer 2012 and in the same offices in winter 2012/2013. All sampling locations were < 15 km far from sea). Thus, in Greece the 5 office buildings were in Athens and its metropolitan area, while in The Netherlands, one sampling location was by the sea and the other in Delft (about 15 km far from the sea). Outdoor sampling was also undertaken close to the air intake of the of HVAC system (4 buildings out of the 7) or at ground floor (3 out of the 7). Filters had been conditioned at 20  1 °C and 50  5% relative humidity. Field blanks were also employed. In summer, indoor PM2.5 mass concentration values ranged between 5.2 μg m-3 and 16.8 μg m-3 whereas outdoor concentrations were always higher, ranging between 10.6 μg m-3 and 31.2 μg m-3. In winter, indoor PM2.5 mass concentration values ranged between 5.0 μg m-3 and 18.5 μg m3 and the outdoor concentration ranged between, 6.1 μg m-3 and 33.6 μg m-3. Indoor / outdoor (I/O) mass concentration ratios varied between 0.42 and 0.86. This outcome is in good agreement with literature data: 0.37-0.88 (Horemans et al., 2008). However, the summer and winter I/O ratios differed for each monitored building. Every one third part of the filters were subjected to microwave-assisted digestion using closed Teflon vessels with quartz inlets filled with 5 mL of aqua regia and immersed in a mixture of 10 mL hydrogen peroxide and deionized water (1: 4 v/v). After the samples were evaporated close to dryness, they were dissolved into 5 mL of 5 % w/v HNO3 and subjected to inductively coupled plasma mass spectrometric (ICP-MS) analysis. Another third part of the samples were sonicated in 5 mL of deionized water for 150 min. Then, the acidified samples also underwent to ICP-MS analysis. The anion and cation content of the filter samples subjected to water sonication were further diluted

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five times and determined by ion chromatography equipped with suppressor columns for the determination of anions. Major ion sources of the samples were: SO42- , NH4+, Ca2+, Na+ and NO3ions. Chloride, K+ and Mg2+ can be considered as minor ions in the samples. Generally, the major anion in the samples was sulphate (40.3-67.8 % of the total ions determined) in all samples independently of their provenance for the summer campaign. In the air-conditioned Dutch offices, the nitrate concentration was lower in summer than outdoor by 4-10 times when the outdoor temperature was lower than the indoor value. The contribution of sea-salt-sulphate to the PM2.5 mass was higher in the Netherlands than in Greece. Contribution of ions to PM2.5 mass varied between 25% and 63%. Seventeen elements (Al, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Rb, Mo, Cd, Sn, Sb, Pt, Pd) could be determined in the filter samples independently of the provenance and sampling site in the pg m-3- ng m-3 concentration range. The traffic density was reflected in the trace element concentration: the traffic-related element concentration was higher in the urban areas compared to rural or suburban sampling sites. Iron, Al and Zn were the major trace elements in the samples independently of the site of collection. Considerable differences were observed in the concentration of some elements in the water-soluble fraction of the samples compared to the aqua regia extractable part. For example, Fe concentration in the water-soluble part was 4%-24% of the aqua regia extractable part. For V, the same percentage varied between 59% and 99%. Some elements (i.e., Cr, Fe, Cu, Rb, Cd, Pb) were accumulated in the indoor environment. Generally, the water soluble metal concentration/aqua regia extractable metal concentration ratios were higher for indoor samples than for the outdoor ones. Samples were also subjected to oxidative potential analysis (Godri et al., 2011). This consisted of a 4-h incubation at 37 °C of 5-mm discs cut from the loaded filters in 0.5 mL of a model respiratory tract lining fluid containing the antioxidants of urate (UA), ascorbate (AA) and glutathione each at 200 µmol dm-3. After centrifugation, the remaining amounts of UA and AA were determined by reversed-phase high performance liquid chromatography with electrochemical detection. Glutathione (GSX, GSSG, GSH) was determined by enzyme-linked 5,5'-dithio-bis(2-nitrobenzoic acid) (DTNB) assay by using a microplate reader. Indoor PM2.5 generally had increased oxidative potential compared with the equivalent outdoor sample and this appeared to be related to the increased concentrations of some trace elements in the indoor PM2.5. This work was supported from the project “OFFICAIR” (On the reduction of health effects from combined exposure to indoor air pollutants in modern offices) funded by the European Union 7th Framework (Agreement 265267) under Theme: ENV.2010.1.2.2-1. The financial support through grant TÁMOP-4.2.2/B-10/1-2010-0030 is also, hereby, acknowledged. Horemans, B., Worobiec, A., Buczynska, A., Van Meel, K. and Van Grieken, R. (2008) J. Environ. Monitor. 10, 867-876. Godri, K.J., Harrison, R.M., Evans, T., Baker, T., Dunster, C., Mudway, I.S., Kelly, F.J. (2011) PLoS ONE 6, e21961. doi:10.1371

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(L41) FTIR (DRIFT) SPECTROSCOPIC ANALYSIS OF ACCUMULATION AND STRUCTURAL FEATURES OF POLY-3-HYDROXYBUTYRATE IN CELLS OF AZOSPIRILLUM BRASILENSE: EFFECTS OF COPPER(II) Anna V. Tugarova1, Alexander A. Kamnev1, Petros A. Tarantilis2, Olga P. Grigoryeva3 and Alexander M. Fainleib3 1

Laboratory of Biochemistry, Institute of Biochemistry and Physiology of Plants and Microorganisms, Russian Academy of Sciences, 410049 Saratov, Russia 2 Laboratory of Chemistry, Department of Science, Agricultural University of Athens, 11855 Athens, Greece 3 Department of Heterochain Polymers and Interpenetrating Polymer Networks, Institute of Macromolecular Chemistry, National Academy of Sciences of Ukraine, Kyiv 02160, Ukraine e-mail: [email protected]; [email protected] Unfavourable environmental factors can induce the accumulation of polyhydroxyalkanoates (PHAs) in many bacteria in the form of intracellular granules serving as energy and carbon reserve materials. In the agriculturally important phytostimulating rhizobacteria of the genus Azospirillum, PHAs are known to be represented by a homopolymer, poly-3-hydroxybutyrate (PHB). This biopolyester, playing a role in bacterial stress endurance, is also of industrial and biotechnological significance as an environmentally friendly biodegradable plastic. For the last decade, we have been studying metabolic responses of Azospirillum brasilense, one of the most widely studied species, to various stresses using Fourier transform infrared (FTIR) spectroscopy. Using this technique in the diffuse reflectance mode (DRIFT), which is sensitive to fine structural modifications of major cellular biomacromolecules, PHB accumulation was analysed in cells of A. brasilense (strain Sp7). Stress conditions included bound nitrogen limitation (high C:N ratio inducing PHB accumulation) and, as an additional stress factor, the presence of 0.1 mM Cu2+ in the medium. It has been found that Cu2+ induced a 1.6-fold increase in PHB accumulation (up to 40 wt.% of dry biomass) at an earlier phase of growth (after 2 days). By the 9th day, in both cases PHB content reached ca. 50 wt.%. Analysis of DRIFT spectra has shown that prolonged stressed conditions induced a shift in some main PHB-related vibrational bands reflecting the accumulation of PHB of lower crystallinity. A more amorphous PHB fraction is known to be more rapidly enzymatically hydrolysed (i.e., more readily ‘digestible’ by starving cells). In the presence of Cu2+, this effect was already noticeable after 2 days of PHB accumulation, reflecting cellular response to the double stress. PHB samples extracted with CHCl3 from biomasses after 9 days of growth (with and without Cu2+) were also comparatively studied as dried films using FTIR spectroscopy, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Some differences in the PHB structure, lower thermostability of the PHB sample obtained from Cu2+-stressed cells and its lower degree of crystallinity (partly remaining after extraction and film formation) were detected. The results obtained show the possibility to regulate PHB accumulation and its structural features by varying the nature, severity, duration and combination of stress factors. This work was supported in part by a research grant from The Siberian Health International LLC (Novosibirsk, Russia; Call for Projects, 2012).

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(L42) A NEW HYBRID FLUOROMETER-SPECTROPHOTOMETER FOR WATER QUALITY ANALYSIS OF OIL, CHROMOPHORIC DISSOLVED ORGANIC MATTER, CHLOROPHYLL AND -NHX Adam M. Gilmore1 1

HORIBA Instruments Inc., 3880 Park Avenue, Edison, NJ 08820

e-mail: [email protected] This presentation describes a new water quality analysis instrument that can continuously and simultaneously measure the absorbance spectrum and fluorescence excitation-emission matrix (EEM). Key applications include oils and polycyclic aromatic hyrdocarbons, chromophoric dissolved organic matter (CDOM), chlorophyll and –NHx containing compounds as well as oxygen demand parameters. The concentration of CDOM compounds in the humic and fulvic acid classes are globally regulated for drinking water treatment because they represent disinfection by-product precursors (DBPPs) that can generate toxic disinfection by-products during halogen disinfection treatments for microorganisms such as Giardia spp. CDOM thus plays an important role in the new Stage 2 USEPA regulations for drinking water sterilization. The instrument allows for continuous and rapid (seconds to minutes) monitoring of the DBPPs to facilitate accurate prediction of the trihalomethane formation potential (THMFP) and dissolved organic carbon (DOC) concentrations. Conventional tests for THMFP and DOC require long and tedious protocols that are prone to errors and prevent rapid responses to the natural dynamics of CDOM concentrations. Further, conventional total organic carbon meters and online ultraviolet absorbance methods have proven to indicate THFMP with poor correlative capacity due to lack of specific information on key DBPPs. The fluorescence data corrections for the spectral response, sample concentration-dependent absorption and for both the excitation beam and fluorescence signals are certified by standard reference materials and protocols that are either NIST and or ISO traceable. The data collection and processing is fully automated through to a component ID and concentration table by means of a selection of validated multivariate tools including principal components analysis (PCA), parallel factor analysis (PARAFAC) and classical least squares (CLS). Notably the wavelength range of the instrument is also compatible with USEPA approved absorbance and fluorescence methods for monitoring chlorophyll concentrations as these relate algae that produce odor and taste compounds as well as toxins associated with algal blooms. The absorbance data further can be used to quantify concentrations of N –NH2 and N–NH3 compounds simultaneously to the fluorescence EEM information. The system also has proven potential to quantify oxygen demand parameters as well as identify and quantify a wide range of pollutants.

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(L43) OCCURRENCE OF POLYCHLORINATED BIPHENYLS (PCBS) AND POLYBROMINATED DIPHENYLETHERS (PBDES) IN DIFFERENT FISH SPECIES FROM ILHA GRANDE BAY, SOUTHEASTERN BRAZIL Ricardo Lavandier1, Natalia Quinete2, Rachel Ann Hauser-Davis1, Patrick Simões Dias3, Satie Taniguchi3, Rosalinda Montone3 and Isabel Moreira1 1 Department of Chemistry, Pontifícia Universidade Católica do Rio de Janeiro (PUC-Rio), Rua Marquês de São Vicente, 225, Gávea – Rio de Janeiro, RJ 22453-900, Brazil 2 Environmental Analysis Research Laboratory, Southeast Environmental Research Center (SERC), Florida International University, Biscayne Bay Campus, Marine Sciences Building, 3000 NE 151st, North Miami, FL 33181, USA 3 Institute of Oceanography, São Paulo University (USP), Praça do Oceanográfico 191, Butantã, São Paulo, SP 05508-900, Brazil e-mail: [email protected]

Polybrominated Diphenyls Ethers (PBDEs) and Polychlorinated biphenyls (PCBs) are environmental contaminants that have been the aim of several recent investigations. They have similar physicochemical properties and may present up to 209 different congeners. These compounds bioaccumulate throughout the food web. Both are endocrine disrupters and can cause reproductive alterations, as well as neurotoxic and carcinogenic effects. Humans are subject to a high risk of contamination by these compounds. PBDEs and PCBs have been increasingly studied in the northern hemisphere, but few studies have been conducted in the southern hemisphere. In the present study, PBDEs and PCBs levels were determined in three different fish species from the Ilha Grande Bay, located in the state of Rio de Janeiro, Brazil. This area is considered a reference area, since previous investigations have indicated no sources of contamination regarding organochlorine pesticides and metals. The analyzed fish species were Mugil liza - mullet (n=15), Micropogonias furnieri - croaker (n=25) and Trichiurus lepturus - scabbardfish (n=21), the latter in two different seasons (dry and wet). Fish were sexed, individually measured (±1.0 mm), weighed (±0.01 g) and dissected to obtain muscle and liver samples. Samples were immediately frozen at -80 ºC, freezedried and stored until analysis. Sample extraction consisted of four different steps: saponification, extraction, clean-up and chromatographic analysis by GC-MS. Lipid content was also determined. The GC–MS analyses was conducted in an electron capture negative ionization mode (GC/MSECNI) and operated in selected ion monitoring (SIM) mode. PCB-53 was used as an internal standard. The carrier gas was helium with a constant flow of 1.1 mL min-1 and 1 μL of sample extract was injected in the splitless mode. The conditions for PCBs determination were the following: the column oven was programmed for an initial temperature of 75 ºC for 3 min and a rate of increase of 15 ºC min-1 from 75 to 150 ºC, then at a rate of 2 ºC min-1 the temperature was raised to 260 ºC. Finally, the temperature was increased at a rate of 20 ºC min-1–300 ºC and was held for 10 min. The conditions for PBDE determination were the following: the column oven was programmed for an initial temperature of 70 ºC for 1 min and a rate of 12 ºC min-1 from 75 to 154 ºC, then at a rate of 2 ºC min-1 the temperature was raised to 210 ºC. Finally, the temperature was increased at a rate of 3 ºC min-1–300 ºC and was held for 5 min. PBDEs levels were very low, with values below the limit of quantification. PCBs concentrations ranged from 2.29 to 27.60 ng g-1 ww in muscle and from 3.41 to 34.22 ng g-1 ww in liver of the three investigated fish species. Values for the daily intake of fish by the human population around the Ilha Grande area were calculated and levels of PCBs were above the maximum allowed under Brazilian law, the FDA/EPA norms and the Italian legislation, therefore raising great concern regarding PCB contamination of fish products consumed in the area. Correlations were established between the concentration of PCBs and biometric variables of the fish individuals, such as length and fat content, and a statistical variation due seasonality was also observed only for croaker, with higher PCBs concentrations during the wet season. -125 -

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(L44) APPLICATION OF MULTI-REFLECTION, HIGH RESOLUTION TIME-OF-FLIGHTMASS SPECTROMETRY AS DETECTOR FOR ONE- AND TWO-DIMENSIONAL GAS CHROMATOGRAPHY: CHARACTERIZATION OF COMPLEX MIXTURES Ralf Zimmermanna, Thomas Grögera, Marie Schäffera, Benedikt Wegglera, Jürgen Wendtb, Martin Sklorza, Theo Schwemera Joint Mass Spectrometry Centre of University of Rostock, Chair of Analytical Chemistry, Rostock/Germany and Helmholtz Zentrum München,CMA, Neuherberg/Germany Contact: [email protected] LECO Instrumente GmbH/Mönchengladbach/Germany Complex samples e.g of petrochemical origin require highly selective analytical methods for comprehensive analysis. Gas chromatography-mass spectrometry (GC-MS) and comprehensive twodimensional gas chromatography-time-of-flight mass spectrometry (GCxGC-TOFMS) are current standard approaches for resolving the “petrochemical complexity”. On the other hand, ultra-high mass resolution mass spectrometry became prominent in elucidating the complexity of petrochemical samples (e.g. by direct infusion FTICR- or Orbitrap-MS measurements) by determination of elemental compositions via exact mass measurement. This approach, however, usually has limitations in generality (AP ionization selectivities/matrix effects) and discrimination of isomeric compounds. By coupling of high resolution (gas-) chromatography and high massresolution mass spectrometry, the knowledge e.g. on the “chemical space” of SVOC in petroleum fractions can be increased. A novel TOFMS-system with a multi-reflection-time-of-flight technology using periodic ion focusing lenses (HRT, LECO Inc, St. Joseph, USA), allows the detection of gas chromatographic transients at high mass-resolution (R = 50.000) with good mass accuracy (< 1 ppm) and at a very fast acquisition rate (200 Hz) without compromising the detection sensitivity. As the HRT-TOFMS is capable to follow accurately very fast changing chromatographic transients it is particularly well suited for coupling to comprehensive two-dimensional gas chromatography (GCxGC, GC: Agilent Inc., USA, Modulator: Zoex Inc., USA). The HRT-TOFMS (electron ionization, 70 eV) was applied e.g. to the analysis of petrochemical samples (one- and two-dimensional comprehensive gas chromatography), including a B5 biodiesel (~ 5 % fatty acid methyl esters (FAME) content). The high-resolution mass spectra can be used for target compound identification/verifications in the case of one dimensional gas chromatography. For comprehensive two-dimensional gas chromatography the high resolution MS mode was used to improve the selectivity of a no-targeted compounds-class identification scheme, called “scripting” [1]. The scripting approach uses on the one hand two-dimensional retention-time information (i.e. specific “areas” in the GCxGC - 2D-retention time-space, which can be translated into a physical-chemical parameter-space characterizing e.g. polarity and volatility of compounds) and on the other hand substance-class specific EI-fragmentation pattern rules for classification of peaks to substance classes. The high mass resolution enables an improved scripting approach, using the exact massvalues of specific fragments to suppress the any accidental contribution of matrix (fragment-)peaks with different elemental composition. Note that this interfering “matrix”-peak contribution is usually quite large in complex samples. It is demonstrated that the “exact mass filtering” in combination with the high chromatographic resolution of GCxGC can have significant impact on a better understanding of complex molecular mixtures. Finally the approach is also compared to another GCHRMS technique using FT-ICR. [1] W. Welthagen, J. Schnelle-Kreis, R.Zimmermann; J. Chromatography A 1019 (2003) 233-249

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(L45) NEW IMAGING CAPABILITIES USING LA-ICPTOF MASS SPECTROMETRY H.A.O. Wang,1,3 C. Giesen,2 D. Grolimund,3 B. Bodenmiller,2 D. Günther1 1

Trace Element and Micro Analysis Group, ETH Zurich, 8093 Zurich Institute of Molecular Life Sciences, University of Zürich, 8057 Zürich 3 microXAS Beamline Project, Swiss Light Source, PSI, 5232 Villigen PSI 2

e-mail: [email protected] This work demonstrates an advanced multiplexing imaging setup based on Laser Ablation (LA) coupled to a sector field-ICP-MS and a commercial Mass Cytometer. The current measurements successfully demonstrate sub-cellular (~1 μm) spatial resolution imaging of biological tissue thin sections. One of the key improvements is attributed to a laser ablation cell.1 This novel LA cell has a short washout time and enhances the signal to noise ratio of the LA transient signal. It enables complete separation of single shot signals generated by high frequency (>20 Hz) laser ablation and furthermore acquisition of analytes in the sample aerosol produced by 1 μm laser single shot. As shown in a case study, multiplexing biomarkers with metal-tagged antibodies were imaged in thin sections of breast cancer tissue. The resulted high spatial resolution high sensitivity biomarker images were acquired simultaneously by the mass cytometer (CyTOF®). Finally, the experimental setup helps biologists investigate various breast cancer sub-types, and better understand cancer metastasis mechanisms. The presented imaging setup will open new research opportunities for pathologists and pharmacologists and some of the potential applications will be discussed. 1 Wang, H.A.O. et al. Fast Chemical Imaging at High Spatial Resolution by Laser Ablation Inductively Coupled Plasma Mass Spectrometry. Submitted to Analytical Chemistry (2013).

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(L46) FURTHER DEVELOPMENTS OF AN ENERGY- AND POSITION-SENSITIVE XRF IMAGING SYSTEM BASED ON A THCOBRA DETECTOR A.L.M. Silva1, M.L. Carvalho2, J.M.F. dos Santos3, J.F.C.A. Veloso1 1

I3N – Physics Department of University of Aveiro, 3810-193 Aveiro, Portugal Atomic Physics Centre, University of Lisbon, 1649-003 Lisboa, Portugal 3 GIAN—Physics Department of University of Coimbra, 3004-516, Coimbra, Portugal 2

e-mail: [email protected] New developments of a full-field and large area energy dispersive X-ray fluorescence (XRF) imaging system for elemental analysis, are presented. The system offers an alternative instrument for today's X-ray fluorescence imaging needs in different fields of science. The system presents moderate both energy and spatial resolution which are sufficient for many applications which require the combination of these two detector modes and large detection area. The XRF imaging system is based on a new Micropattern Gaseous Detector called 2D-THCOBRA. The 2D-THCOBRA is a combination of the THGEM with the 2D-MHSP, benefiting from the robustness and low cost of the first structure and from the position discrimination, together with the two charge multiplication stages of the second structure The micropatterned structure uses a simple position readout based on resistive lines and has an active area of about 10x10 cm2 allowing large area of analysis. The sample is excited by a broad X-ray beam and the resulting X-ray fluorescence photons are detected, through a pin-hole lens, by the full-field energy dispersive detector, the 2D-THCOBRA. The single-photon counting detector allows for energy resolved X-ray imaging (22% FWHM for 5.9 keV X-rays) with a spatial resolution of about 0.5 mm (FWHM), and a counting rate capability of up to 0.5 MHz limited by the present electronic readout configuration. Results will be presented and discussed concerning the XRF system performance and the different analyzed samples. Acknowledgements: This work was partially supported by projects CERN/FP/123604/2011 and PTDC/FIS/110925/2009 through COMPETE, FEDER and FCT (Lisbon) programs. A.L.M. Silva, was supported by a doctoral grant from FCT (Lisbon) with the reference SFRH/BD/61862/2009.

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(L47) PHARMACEUTICAL IMAGES HARVESTING AND COMPARISON Tomáš Pekárek1, Martina Mudrová2, Tomáš Chvojka1 and Aleš Procházka2 1

Development Dept., Zenitva, k.s., CZ-10237 Prague 10, Czech Republic Department of Computing and Control Engineering, Institute of Cemical Technology Prague, CZ16628 Prague 6, Czech Republic 2

e-mail: [email protected] Infrared and Raman mapping and imaging can result in very valuable information, not only in the generic pharmaceutical development for originator’s manufacturing procedure estimation, but also for counterfeit detection, as many counterfeits have different particles’ size and/or their distribution. Obtained images are currently usually evaluated and compared manually. In order to make the comparison and evaluation more objective, reliable and person independent, a new approach employing the in-house build software was developed. Firstly, it is necessary to extract as much information as possible from the initial map (Fig. 1) obtained by IR or Raman mapping or imaging of pharmaceutical tablet cross-section. Such crucial information is the individual components’ area, number and size of individual components and the neighborhood of individual components.

Fig. 1. IR map – different colors represent individual components of a pharmaceutical tablet. Once the data mentioned above are known, two or more maps can be simple compared in selected parameters (Fig. 2) to see how (dis)similar are the maps, which parameter contributes the most to the map differentiation, etc. Up to five parameters can be easily displayed: three axes, mark size, mark color. As there is a large amount of observed properties, Principal Component Analysis can be used for dimension reduction (Fig. 3). The influence of each parameter to the map differentiation can be investigated, as well. Using such method it is possible to make the generic backward-engineering easier and cheaper and to detect counterfeits in case of originators’ litigation.

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Lecture Abstracts

Selected Properties - Comp. No.2 8

30 Component Occurence

Mark Size ~ Particle Size (8-con.)

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Fig. 2. Comparison of different maps in selected parameters: Properties of the investigated component are marked (Component’s occurrence, its neighborhood with other two selected components and average particle size).

(a) Original Data

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Fig. 3. Example of reduction of a number of observed parameters by means of PCA: Six selected properties (a) were transformed into four new parameters (b). Result obtained is presented in (c).

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XXXVIII CSI 2013

Lecture Abstracts

(L48) NOVEL MULTISPECTRAL IMAGING APPROACHES FOR RECOVERING OF DEGRADED ARCHAEOLOGICAL WALL PAINTINGS S. Legnaioli1, G. Lorenzetti1, G.H. Cavalcanti2, E. Grifoni3, L. Marras3, A. Tonazzini4, E. Salerno4, P. Pallecchi5, G. Giachi5 and V. Palleschi1,6 1 Institute of Chemistry of Organometallic Compounds Research Area of National Research Council Via G. Moruzzi, 1 – 56124 Pisa (ITALY) 2 Instituto de Fìsica, Universidade Federal Fluminense Av. Gal. Milton Tavares de Souza, s/nº - Campus da Praia Vermelha - CEP 24210-346 - Niterói – Rio de Janeiro (BRAZIL) 3 Art-Test s.a.s. Via del Martello, 14 - 56121 Pisa (ITALY) 4 Institute of Sciences and Technology of Information Research Area of National Research Council Via G. Moruzzi, 1 – 56124 Pisa (ITALY) 5 Soprintendenza per i Beni Archeologici della Toscana Via della Pergola, 65 - 50121 Firenze (ITALY) 6 Department of Civilizations and Forms of Knowledge University of Pisa Via G. Galvani, 1 – 56126 Pisa (ITALY) e-mail: [email protected] New approaches in the application of multispectral imaging to the recovery of archeological wall paintings are presented, based on blind deconvolution techniques and on a novel method of image treatment (Chromatic Derivative Imaging – ChromaDI) which offers a way of visualizing in color the information coming from more than three spectral bands. The methods are applied to the recovery of some wall paintings from the Tomb of the Monkey, an Etruscan tomb in the necropolis of Poggio Renzo, near the city of Chiusi (Siena), dated around 480-470 BC. It is shown that a number of otherwise invisible details emerge from the multispectral image set, which can be enhanced and evidenced using the techniques described.

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XXXVIII CSI 2013

Lecture Abstracts

(L49) LA-ICPMS IMAGING AND NUCLEAR FORENSICS: PU ISOTOPE RATIOS IN SEDIMENTS FROM MAYAK PA, RUSSIA Simone Cagno1,2, Kevin Hellemans2, Ole Christian Lind1, Lindis Skipperud1, Koen Janssens2, Brit Salbu1 1

CERAD, Department of Plant and Environmental Science, Norwegian University of Life Sciences, P.O. Box 5003, N-1432 Ås, Norway 2 Department of Chemistry, University of Antwerp, Groenenborgerlaan 171, B-2020 Antwerpen, Belgium e-mail: [email protected] Laser Ablation – Inductively Coupled Plasma Mass Spectrometry (LA-ICPMS) was initially intended as the combination of a well-established trace-ultra trace analytical technique (ICPMS), plus a tool for representative solid sampling, i.e. the laser ablation system. The development of fast washout ablation cells has recently allowed great advances in 2D and 3D isotope mapping [1]. In this paper we focus on the application of LA-ICPMS on reservoir sediments originating from the MAYAK Production Association, Ural region, Russia. There, weapon production took place from 1948, and reprocessing of civil sources took place from mid 1980s. Both sources generated d vast radioactive contamination at the site, downstream the river and in the surrounding region [2]. The samples of investigation originate from the 1996 joint Russian-Norwegian monitoring campaign. At that time, the activity concentrations of plutonium isotopes (239,240Pu) were determined using by alpha spectrometry (AS). Sediments were ashed and radiochemical separations were performed prior to electrodeposition of Pu on steel planchettes [3]. In alpha spectrometry, 239Pu and 240Pu cannot be distinguished due to similar alpha energies. However, the 240Pu/239Pu ratio is a highly useful tool for source identification, i.e. to distinguish civil sources (high ratio, e.g. reprocessing), global fallout (intermediate ratios) and weapon grade material (low ratio). Large archives of electrodeposited alpha sources, usually planchettes, are stored worldwide. With the development of new techniques such as LA-ICPMS, these samples could be subject to further measurements, allowing information on individual Pu isotopes. The MAYAK samples have therefore been reanalysed with the aim of demonstrating the feasibility of LA-ICPMS mapping of Pu isotopes, allowing the comparison of the LA-ICPMS results with those previously obtained by AS and AMS on the same samples [4-5]. The LA-ICPMS analyses were performed at the University of Antwerp, with a NWR193 ArF excimer laser, combined with an Agilent 7700X and a Varian 820 ICPMS. The results show minimal or no presence of other elements in the electrodeposited samples, thus confirming high efficiency of the separation procedure. The Pu electrodeposition was fairly inhomogeneously distributed on the steel surface, however, LA-ICP-MS allowed the measurements of individual Pu isotopes, and the obtained 240Pu/239Pu ratios demonstrated the presence of global fallout Pu as well as weapon grade Pu. Based on a series of planchettes from the Mayak reservoir 10, the 240Pu/239Pu ratios in the deep sediments were low, reflecting the Pu weapon production activities of MAYAK PA in the 1940-50s. [1] Van Elteren JT et al. (2013) J Anal Atom Spectrom DOI: 10.1039/C3JA30362D [2] Christensen, GC et al. (1997) Sci Total Environm 202: 237-248 [3] Ketterer ME et al. (2004) J Anal Atom Spectrom 19:241–245 [4] Skipperud L et al. (2005) Health Physics 89: 255-266 [5] Oughton DH et al. (2000) Environ. Sci. Technol. 34: 1938–1945

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XXXVIII CSI 2013

Lecture Abstracts

(L50) PHYSICOCHEMICAL INVESTIGATION OF THE WALL PAINTINGS OF PETROS PAULOS CHURCH, ETHIOPIA Kidane Fanta Gebremariam, Norwegian University of Science and Technology, Trondheim, Norway

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Lecture Abstracts

(L51) COMPARISON BETWEEN SR-XRF AND ICP-AES Jun Kawai Kyoto University, Department of Materials Science and Engineering, Sakyo-ku, Kyoto 606-8501, Japan e-mail: [email protected] Sensitivity of elemental analysis between SR-XRF (synchrotron radiation X-ray fluorescence) and ICP-AES (inductively coupled plasma atomic emission spectrometry) is compared using data submitted to court for the arsenic poisoning case in Japan. The key evidence was that Sn, Sb, and Bi were found as impurity elements in the arsenic stored at kitchen of a saleswoman (she used it as pesticide), and paper cup near the poisoned curry pot. It was generally accepted that the Sn, Sb, and Bi were trace impurities and thus were possible to be detected only by the SR-XRF method. However when I compared SR-XRF and ICP-AES results, the concentration of Sn, and Sb were 20 ppm levels, and Bi 50 ppm level. Additionally ICP-AES could detect Ca, Fe, Zn, Se, and Pb. Ca (>10000 ppm) was not detected by SR-XRF; Fe (30 ppm) and Zn (200 ppm) were too weak in SRXRF spectra; Se (100 ppm) was overlapped by major element As (74 wt%) in XRF; Pb (200 ppm) was high blank intensity because of the shielding material of the synchrotron beamline. SR-XRF found Mo as a key element of murder (ICP-AES did not analyse Mo), and thus finally the saleswoman was sentenced to death due to the SR-XRF analysis. However, if I include Fe, Zn, and Ba for identification, the saleswoman’s arsenic was significantly different from that found in the paper cup. The saleswoman is now in the death row and this issue is now discussed in Japanese journalism.

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XXXVIII CSI 2013

Lecture Abstracts

(L52) SPECTROSCOPIC ANALYSIS OF BONES FOR FORENSIC STUDIES A. D’Ulivo1, L. Pardini2, M. Borrini3, L. Marchesini3, M. Tofanelli1, F. Bartoli4, E. Pitzalis1, M.C. Mascherpa1, S. Legnaioli1, G. Lorenzetti1, G.H. Cavalcanti5 and V.Palleschi1 1

Institute of Chemistry of Organometallic Compounds, CNR Area della Ricerca del CNR di Pisa Via G. Moruzzi, 1 – 56124 PISA (Italy) 2 Institut für Physik und IRIS Adlershof Humboldt-Universität zu Berlin Zum Großen Windkanal 6, 12489 Berlin (Germany) 3 Italian Accademy of Forensic Sciences Viale Regina Margherita 9/D - 42124 REGGIO EMILIA (Italy) 4 Department of Biology Via A. Volta, 4 - 56126 PISA (Italy) 5 Instituto de Fìsica, Universidade Federal Fluminense Av. Gal. Milton Tavares de Souza, Campus da Praia Vermelha - CEP 24210-346 - Niterói – RIO DE JANEIRO (Brazil)

s/nº

e-mail: [email protected] The elemental analysis of human bones can give information about the dietary habits of the deceased, especially in the last years of their lives, which can be useful for forensic studies. The most important requirement that must be satisfied for this kind of analysis is that the concentrations of analyzed elements is the same as ante mortem. In this work, a set of bones was analyzed using Laser-Induced Breakdown Spectroscopy (LIBS) and validated using Inductively Coupled Plasma – Optical Emission Spectroscopy (ICP-OES), in order to compare those two techniques and to investigate the effect of possible alterations in the elemental concentrations' proportion resulting from the treatment usually applied for preparing the bones for traditional forensic analysis. The possibility that elemental concentrations’ changes would occur after accidental or intentional burning of the bones was also studied.

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XXXVIII CSI 2013

Lecture Abstracts

(L53) PRINTABLE SURFACE ENHANCED RAMAN SCATTERING STRIPS WITH IN-SITU GROWTH OF GOLD NANOPARTICLES Wei Ju, Liao and Surojit Chattopadhyay* Institute of Biophotonics, National Yang-Ming University, Taiwan (ROC) * Corresponding author: e-mail: [email protected] Surface enhanced Raman scattering (SERS) is being developed to challenge existing conventional technologies used for biomolecular sensing. SERS strips are printed on paper with in-situ growth of gold nanoparticles (AuNPs) on printed patterns. Plasmons generated in these AuNPs when irradiated with suitable light increase the scattering cross-section for Raman spectroscopy of selected analytes. Components of human sweat were used as a bio-ink to reduce HAuCl4 forming the AuNPs on paper. These AuNPs on the strip’s surface enhances the local electric field to increase the Raman signal. SERS strips are capable of absorbing analyte molecules readily and firmly. Development of this inexpensive SERS strips for detection of toxic chemical will be important for health applications. We demonstrate detection of Rhodamine 6G, a standard Raman analyte, at μM levels, on these strips to show its efficacy in sensor applications.

Figure 1. (A) UV-Vis absorption spectrum on the AuNP printed pattern (Black) and bare paper (RED) showing the surface plasmon absorption of AuNPs at 530 nm only for the black curve. Inset shows a camera image of the SERS strip with printed patterns of AuNPs (purple). (B) Raman spectra of R6G (M) on the AuNP pattern (black) and bare paper (Red), showing strong signals originating from the AuNP patterns.

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XXXVIII CSI 2013

Lecture Abstracts

(L54) SPECIATION AND COBALT TOXICITY ON HUMAN LUNG CELLS: AN INTERDISCIPLINARY STUDY Carole Bresson, 1 Carine Darolles, 2 Asuncion Carmona, 3, 4 Céline Gautier, Stéphane Roudeau, 3, 4 Richard Ortega, 3, 4 Eric Ansoborlo, 6 Véronique Malard. 2

5

Nicole Sage,

2

1

CEA, DEN, DPC, SEARS, Laboratoire de développement Analytique Nucléaire, Isotopique et Elémentaire, F-91191 Gif-sur-Yvette, France. 2 CEA, DSV, IBEB, Lab Biochim System Perturb, Bagnols-sur-Cèze, F-30207, France. 3 Univ. Bordeaux, CENBG, UMR 5797, F-33170 Gradignan, France. 4 CNRS, IN2P3, CENBG, UMR 5797, F-33170 Gradignan, France. 5 CEA, DEN, DPC, SEARS, Laboratoire d’Analyse en Soutien aux Exploitants, F-91191 Gif-sur-Yvette, France. 6 CEA, DEN, DRCP, CETAMA, Marcoule F-30207, Bagnols-sur-Cèze, France.

e-mail: [email protected] Understanding the toxicity mechanisms of radionuclides towards living organisms in case of contamination is crucial, in order to develop strategies for prevention, diagnosis and design efficient and selective decorporants. Cobalt is used in industrial and nuclear sectors and occupational risks of exposure, particularly by inhalation, are known. In this framework, we investigated the impact of a soluble cobalt compound, CoCl2.6H2O, on the BEAS-2B lung epithelial cell line, as well as its impact on metal homeostasis. Cobalt speciation study in various culture media was performed by modeling and experimentally, highlighting the influence of the culture medium composition on the precipitation level of cobalt. The cytotoxic effects of cobalt on the cells were also assessed. Upon in vitro exposure of BEAS-2B cells to cobalt, intracellular accumulation of cobalt and zinc was shown using in situ microchemical analysis based on ion micro-beam techniques and analysis after cell lysis by inductively coupled plasma mass spectrometry (ICP-MS). Microchemical imaging revealed that cobalt was rather homogeneously distributed in the nucleus and in the cytoplasm whereas zinc was more abundant in the nucleus. Combined in vitro exposure of the cells to zinc and cobalt induced a clear synergistic increase in toxicity and a substantial increase in intracellular zinc amount. A decrease in ZnT1 expression, involved in zinc efflux, seems to be the origin of this significant increase. This work highlights the considerable contribution of analytical techniques to the understanding of complex toxicity mechanisms at the cellular and molecular level.

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XXXVIII CSI 2013

Lecture Abstracts

(L55) FAST AND NON-DESTRUCTIVE QUANTIFICATION OF DAPIVIRINE IN HIV PREVENTIVE INTRAVAGINAL RINGS BY RAMAN SPECTROSCOPY Lotte B. Lyndgaard1), Rolf Spångenberg2), Ann-Charlotte Jägervall2) Christopher Gilmour3) and Frans van den Berg1) 1

Department of Food Science, Faculty of Science, University of Copenhagen, DK-1958 Frederiksberg, Denmark 2 Qpharma, Malmø, Sweden 3 International Partnership for Microbicides (IPM), Silver Spring, MD, USA e-mail: [email protected] An intravaginal ring (IVR) is a polymeric delivery device designed to provide controlled release of drugs to the vagina over an extended period of time. The international partnership for microbicides (IPM) is investigating the use of the active pharmaceutical ingredient (API) Dapivirine in a silicone matrix vaginal ring delivery system, with the potential to reduce female vaginal HIV infection rates. Several phase I and II studies have proved the ring as a safe viable drug method. The ring is intended as a 28 day use device for women as a complementary prevention technology to safer sex practices. The ring formulation will be used continuously by HIV-uninfected women for the prevention of male to female vaginal transmission of HIV-1 infection. The objective of the study was to test Raman spectroscopy as a fast alternative to the current standard reference method (High-performance liquid chromatography) for quantifying Dapivirine in IVRs. By Raman spectroscopy IVRs can be measured directly, without any tedious and time consuming sample preparation, and non-destructively. The Raman signal of Dapivirine is strong, but the silicone-based polymer matrix also has a high signal which interferes with the quantification. Measurements on rotating rings using a wide area illumination probe with a spot size of 6 mm allowed that almost the entire ring were sampled. Both reference rings containing 50-150% of the nominal concentrations of Dapivirine and rings from six different production batches were evaluated. Raman spectra were baseline corrected using asymmetric least squares smoothing. We demonstrate how a calibration model for Dapivirine concentration can be conducted and used for the prediction of concentrations in rings collected from the production. The task turned out to not be a straight forward partial least squares (PLS) regression on the Raman signals, predominantly due to batch-to-batch variations in the silicone sample matrix. Different data analytical approaches proved to be more of less effective and will be discussed: spectroscopic knowledge based quantification using the ratios of selected band heights, band fitting using Cauchy-Lorentz functions, interval based normalization, orthogonalization according to silicone elastomer and estimation of interference using multivariate curve resolution (MCR).

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XXXVIII CSI 2013

Lecture Abstracts

(L56) TITANIUM MEASUREMENT IN BIOFLUIDS BY ICP-OES (SIMULTANEOUS INDUCTIVELY COUPLED PLASMA OPTICAL EMISSION) AND HE-CC KED QUADRUPOLE ICP-MS Balázs Berlinger2, Dr. Lee Blum1, Nathaniel Rieders1 and János Fucskó1 1 NMS Labs, 3701 Welsh Road, Willow Grove, PA 19090 2 National Institute of Occupational Health, Gydas vei 8., N-0363 Oslo, Norway Abstract Titanium measurement in biofluids by ICP-MS – the preferred way for trace metal analysis in biological matrices - involves multiple challenges: interferences from polyatomic species like PO+, SO+ ClC+ , direct isobaric overlap of 48Ca with the major isotope of 48Ti, and typically very low concentration of Ti in urine, serum and blood. While titanium is not known to be particularly toxic, quantification at concentrations of < 20 ng/mL is desirable. These challenges have been acknowledged by many clinical laboratories during the last decade, and sector field ICP-MS appeared to be the most accurate way to measure Ti below the 2 ng/mL typical levels in bio-fluids. Experiment A He-CC KED quadrupole ICP-MS method on Agilent 7700 ICP-MS and a simultaneous ICP-OES method on Thermo iCAP6500Duo ICP-OES were developed to measure and confirm Ti levels in urine, serum and blood at > 2 ng/mL concentrations. Multiple internal standards – Sc, Ga, Y, Rh, In, Zr - were evaluated and compared. While good tuning conditions would suppress polyatomic interference from S and below the 1 ng/mL Ti BEC level in urine, serum and blood samples, an interference correction method for PO+ and SO+ interferences using S and P calibration with the He-CC KED ICP-MS and subsequent measurement of P and S in biofluids was developed and used to obtain more accurate data. The interference correction provided good spike recovery down to and below 10 ng/mL Ti concentrations. The urine, serum and blood blank and spike levels measured by He-KED ICP-MS and simultaneous ICP-OES were also compared to sector field ICP-MS data, at the National Institute of Occupational Health in Norway, for more accurate quantitative determination of interferences of major components, like P, S, Cl, C, Li, Be, alkali and alkaline earth metals. Summary Both the He-KED-quadrupole ICP-MS method and the simultaneous ICP-OES method are adequate for measurement of >5-10 ng/mL Ti concentration in biofluids. Thus, a higher cost sector field ICPMS instrument may not be needed for routine analysis if appropriate interference correction is used for the quadrupole ICP-MS method. The ICP-OES method is particularly promising for urine measurement, due to the higher available sample volume, lower dilution ratio required and the lack of polyatomic interferences causing elevated BEC by ICP-MS.

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XXXVIII CSI 2013

Lecture Abstracts

(L57) DISTRIBUTION AND SOURCE OF METALS IN CONTAMINATED SEDIMENTS FROM RIVERS IN COAL FIELDS Rob McCrindle1, Stanley Moyo1, Ntebogeng Mokgalaka1 and Jan G Myburgh2 1

Department of Chemistry, Tshwane University of Technology, Pvt. Bag X680, Pretoria 0001, Republic of South Africa. 2 Department of Paraclinical Sciences, Faculty of Veterinary Science, University of Pretoria, P Bag X04, Onderstepoort, 0110, South Africa E-mail: mccrindleri@ tut.ac.za

A sequential extraction procedure was applied to identify the species of Cd, Co, Cr, Pb, Ti, V and Fe-Mn-oxides present in sediments from the Olifants, Klein Olifants and Wilge Rivers, South Africa. The three rivers pass through the most active coal fields in the country. A four step sequential extraction procedure partitioned the metals into CH3COOH exchangeable/extractable; NH2OH HCI carbonate extractable and easily reducible; H2O2-HNO3 organic extractable/oxidisable and HF, HNO3 residual/acid soluble. Most of the elements were found to exist in the residual fraction, characterized by stable compounds in the sediments. The non-residual fractions, total of the first three fractions, were analyzed since they are more bioavailable than the residual amount. Correlation analysis and two multivariate analysis techniques (factor and cluster analysis) were applied to understand the associations between the non-residual phase of the trace metals and Fe-and Mn-oxides within the sediments, since Fe-and Mn-oxides play a critical role in the adsorption of trace metals within aquatic environment.

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XXXVIII CSI 2013

Lecture Abstracts

(L58) INTERPRETATION OF THE PLASTIC LIFE CYCLE USING FTIR-ATR AND ICP-OES SPECTROMETRY Van Oyen, Albert1 and Oppermann, Uwe2 1 2

CARAT GmbH, Harderhook, D-46395 Bocholt, Germany Shimadzu Europa GmbH, Albert- Hahn- Str. 6-10, D-47269 Duisburg, Germany

e-mail: [email protected]

The worldwide production of plastics in 2008 was 245 million tons and has reached an all-time high [1]. It is estimated that in the European Union (incl. 27 member states) around 25 Mt of plastic waste was generated in 2008; 12.1 Mt (48.7%) was landfilled while 12.8 Mt (51.3%) went to recovery [2], and only 5.3 Mt (21.3%) was recycled [3]. On the waste management side, collection and sorting of waste from electric and electronic equipment (WEEE) and plastics provide the greatest job opportunities, with a total of 40 and 15.6 jobs respectively being created per 1 000 tons of material processed. Plastic recycling alone has the potential to create 162 018 jobs in the EU if the recycling rate increases up to a level of 70% by 2020 [4]. Plastic is mostly used in packaging as a low-cost one-way product that is most often not reusable or not foreseen for reuse. The plastics converting market is dominated by plastic packaging (40.1%) followed by the building and construction sector (20.4%). The plastics industry expects a long-term growth of around 4% globally, well ahead of expected global GDP growth [5]. Europe is still a net exporter of plastic products with a value of 13 billion Euro in 2009, but Chinese production has reached similar levels since 2008 [6]. There are hundreds different kinds of plastic [7]. Most of these plastics aren’t mixable, this means that the plastic varieties have to be separated before the recycling process cab start. Furthermore the additives are playing an important role in the quality of the recyclates, especially the presence of heavy metals and flame retardants. Another problem is degradation. Plastics are not inert but degrade under influence of UV-radiation, heat and other external influences. From a thermodynamic point of view plastics are meta-stable, which means that after extra energy exposure (e.g. heat), the plastic will degrade in unknown rest products. FTIR spectrometry is a useful tool for determination and identification the kind of plastic. Experimental work has been done using the Shimadzu IRPrestige-21 FTIR spectrometer in combination with commercial libraries, which are available on the market, containing usually the spectra of most used plastics. For identifying the kind of plastic from pre-consumer waste this method is quick and accurate. Identifying post-consumer plastic is more difficult because the plastic could have several signs of degradation. This becomes visible only by some extra peaks in the spectrum. Furthermore the heavy metal concentration in plastics is of interest, as it is nowadays restricted by RoHS and the European packaging directive. This requires precise analytical systems such as X-ray fluorescence, ICP-OES-, and atomic absorption spectrometers. For the quantitative determination of hazardous substances such as cadmium and lead the EDX-720P energy dispersive x-ray fluorescence spectrometer and -141 -

XXXVIII CSI 2013

Lecture Abstracts

ICPE-9000 simultaneous ICP-OES spectrometer have been used. Experimental data for post consumer recyclate samples will be presented – advantages and limitations will be discussed. References [1] BIOIS, Plastic waste in the environment, Final Report EU Commission 2010 http://ec.europa.eu/environment/waste/studies/pdf/plastics.pdf [2] Member State's statistics do generally only report on plastic packaging. The actual amount of plastic waste can be assumed to be higher. See: FORWAST, 2010, Policy recommendations, p. 43. (http://forwast.brgm.fr/Documents/Deliverables/Forwast_D63.pdf). [3] (BIOIS) Plastic waste in the Environment, loc. cit., p. 73. [4] Friends of the Earth, Report of September 2010, more jobs, less waste, p. 16, p. 31 [5] Plastic Europe, plastics – the facts, 2012 p.5. [6] Plastic Europe, plastics – the facts, 2012 p.12. [7] Wikipedia: plastics http://en.wikipedia.org/wiki/Plastic

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XXXVIII CSI 2013

Lecture Abstracts

(L59) ADVANCED TECHNIQUES FOR ENVIRONMENTAL ANALYSIS USING ICP-MS Jianfeng Cui, Daniel Kutscher, Shona McSheehy Ducos, Lothar Rottmann, Tomoko Vincent, Julian Wills Thermo Scientific, Bremen, Germany e-mail: [email protected]

Environmental monitoring has become a key strategy in determining how industrial activities and pollution affect our water supplies and ecosystems. Policies for example, such as the Water Framework Directive and Cleaner Air for Europe (CAFÉ) provide the framework for standards and objectives for pollutants that can damage health and the environment. Additionally, research activities investigate other activities or analytes that could have detrimental effects. Analytically meeting the requirements in legislation and research can be challenging due to sampling, sample handling, matrix effects and the ever decreasing levels of analytes that need to be measured. ICP-MS is a highly sensitive, accurate and rapid technique that efficiently meets the demands of environmental analysis. This paper outlines some approaches for ICP-MS analysis that offer flexibility for the analysis of challenging samples and environmental compartments. Trace elemental speciation is a growing field that offers information about the chemical forms of analytes in the environment and thus information on pathways and cycling of elements. The IC-ICP-MS approach presented for speciation is based on a completely metal free flow path that enables contamination free speciation in natural waters, fauna and flora. For handling of high matrix samples, an autodilution system is presented that enables prescriptive and intelligent dilution of samples as well as on-line preparation of calibration standards. Challenges in air monitoring are overcome using a Gas Exchange Device (GED). The GED substitutes atmospheric gases from air samples with argon for direct introduction of particulate matter in the air or direct analysis of toxic gases in air after an on-line chemical reaction.

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XXXVIII CSI 2013

Lecture Abstracts

(L60) QUANTITATIVE ANALYSIS OF HEAVY ELEMENTS AND SEMI-QUANTITATIVE EVALUATION OF HEAVY MINERAL COMPOSITIONS OF STREAM SEDIMENTS IN JAPAN FOR CONSTRUCTION OF A FORENSIC SOIL DATABASE USING SYNCHROTRON RADIATION X-RAY ANALYSES Izumi Nakai1, Shunsuke Furuya1,Willy Shun Kai Bong 1, Yoshinari Abe1, Keiichi Osaka2, Takuya Matsumoto2, Masayoshi Itou 2, Atsuyuki Ohta3, and Toshio Ninomiya2 a. Department of Applied Chemistry, Tokyo University of Science, Shinjuku,Tokyo 162-8601 b. Japan Synchrotron Radiation Research Institute(JASRI), SPring-8,Kouto,Hyo-go 679-5198 c. Institute of Geology and Geoinformation, National Institute of Advanced Industrial Science and Technology (AIST), Higashi, Tsukuba, Ibaraki 305-8567, Japan e-mail: [email protected] Soil materials are routinely encountered in a crime scene and used as evidence by police and forensic staff, and thus the forensic analysis of soils has a long history. However, characterization of soil materials requires high level of training and expertise. We have therefore started to construct a nationwide forensic soil sediment database for Japan, which can be used by non-expert forensic staff. The database is based on the heavy mineral and trace heavy element compositions of stream sediments collected at 3,024 points across Japan. Heavy element compositions of the samples were determined by high-energy synchrotron X-ray fluorescence analysis (HE-SR-XRF) utilising 116keV X-rays from Wiggler source (Fig.1). Heavy mineral compositions were determined by high-resolution synchrotron X-ray powder diffraction (SR-XRD) utilizing a Deby-Scherrer camera with a radius of 286.5mm (Fig. 2). After optimization of the measurement conditions, the measurements were carried out at SPring-8, JASRI in Japan. The automated sampling systems allow the measurements of 130 powder diffraction patterns and 100 XRF spectra per day using sediment samples of 2 milligrams, which enabled us to construct a database of a large number of samples. The concentrations of heavy elements such as rare earth elements, Cs, and W from 1 ppm to 500 ppm levels in a soil sediment can be determined by the calibration curve method using HE-SRXRF. A heavy element concentration map superimposed on a geographical map of Japan was successfully prepared from these analytical data. The powder diffraction data were recorded on IP. The heavy mineral compositions were quantitatively evaluated using the peak intensity of characteristic X-ray diffraction peaks of the component minerals. The obtained data have been expressed by heavy mineral map. This study demonstrates that XRF and XRD data collected from the sediments of Shizuoka Prefecture closely reflect the geological and geographical signature of the sediment samples, which can be used for the provenance determination of soil evidence from a crime scene. This will become the first forensic database constructed by SR X-ray analyses.

Fig.1 HE-SR-XRF system at BL08W

Fig.2 SR-XRD system at BL19B2

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XXXVIII CSI 2013

Lecture Abstracts

(L61) EFFECT OF METAL STRESS ON PIGMENTS IN COPPER-HYPERACCUMULATING LICHENS Hiromitsu Nakajima and Kiminori Itoh Graduate School of Environment and Information Sciences, Yokohama National University, Tokiwadai 79-7, Hodogayaku, Yokohama 240-8501, Japan e-mail: [email protected] To understand the ecology and physiology of metal-accumulating lichens growing in Cu-polluted sites, we investigated lichens near temple and shrine buildings with Cu roofs in Japan and found that Stereocaulon japonicum (Fig. 1) and Cladonia humilis (Fig. 2) grow in Cu-polluted sites. Metal concentrations in the lichen samples collected at some of these sites were determined by inductively coupled plasma mass spectroscopy (ICP-MS). UV-vis absorption spectra of pigments extracted from the lichen samples were measured, and the pigment concentrations were estimated from the spectral data using equations from the literature. We found that S. japonicum and C. humilis are Cuhyperaccumulating lichens. Differences in pigment concentrations and their absorption spectra were observed between the Cu-polluted and control samples of the 2 lichens. However, no correlation was found between Cu and pigment concentrations. We observed a positive correlation between Al and Fe concentrations and unexpectedly found high negative correlations between Al and pigment concentrations. This suggests that Al stress reduces pigment concentrations.

Fig. 1. Stereocaulon japonicum on rockwall.

Fig. 2. Cladonia humilis on soil.

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XXXVIII CSI 2013

Lecture Abstracts

(L62) HIGH SENSITIVITY AND EXTENDED SCAN SPEED FOR DEDICATED ISOTOPE RATIO DETERMINATIONS René Chemnitzer1 and Meike Hamester1 1

Bruker Daltonics, Fahrenheitstrasse 4, 28359 Bremen, Germany

e-mail: [email protected] Scientific disciplines like Food Chemistry, Geochemistry, environmental sciences and Paleontology are not only interested in the total concentration of an element but also in the isotope ratio of either two or more isotopes of the same element or isotopes of different elements. Researchers are interested in isotope ratios of elements such as Selenium, Strontium/Rubidium, Lead and Uranium. ICP-MS is a powerful technique for the determination of trace elements in various matrices. Beyond that ICP-MS is able to determine isotope ratios with high accuracy and precision. The sensitivity of an ICP-MS is an indispensable performance characteristic and will enable the instrument to achieve highest isotope ratio precisions even at low, down to single digit ppt levels. On the other hand high sensitivity is important for single collector instrumentation to enable short integration times without sacrificing precision due to counting statistical limitations. An additional challenge is the isotope ratio measurement of spectrally interfered isotopes. Effective interference management with high sensitivity in interference mode is required to ensure precision and accuracy of spectrally interfered isotope ratios. The presentation will illustrate the layout of a high sensitive ICP-MS instrumentation (Bruker Daltonics). With a 90° reflecting ion optic and an optimized ion extraction the instrument is capable to obtain sensitivities of > 106 cps/ppb - without plasma shielding, and > 105 cps/ppb in collision mode for spectrally interfered isotopes. The key parameters to improve the precision for isotope ratio analysis with ICP-QMS are discussed. Geochemical applications using Laserablation-ICP-MS as well as the isotope ratio analysis of liquid samples will be presented.

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XXXVIII CSI 2013

Lecture Abstracts

(L63) DETERMINATION OF HEAVY METALS AT ULTRALOW CONCENTRATION LEVELS IN PRISTINE POLAR SNOW AND ICE Claude F. BOUTRON Honoray Professor at University Joseph Fourier of Grenoble ( Laboratory of Glaciology and Geophysics of the Environment ) , 13 rue Messidor , 05000 Gap , France . E-mail : [email protected] Dated snow and ice layers deposited in Antarctica and Greenland are unique archives of the changing occurrence of heavy metals in the atmosphere . Ancient ice allows to assess past natural levels of these metals and their changes during the successive glacial - interglacial periods . More recent ice and snow allow to evaluate man - induced changes during the Greek-Roman Antiquity and from the Industrial Revolution to present . Deciphering these frozen archives is unfortunately extremely difficult especially because of the extreme purity of polar snow and ice . As an illustration , Pb concentration in Antarctic ice dated 130 000 years ago is about 0.4 picogram per gram , while Ir concentration in Greenland ice dated 5000 years ago is about 0.3 femtogram per gram . Such extremely low concentrations make it mandatory to carefully control contamination problems from field sampling to laboratory analysis , and use highly sensitive analytical techniques . Surface and shallow depth samples can be collected cleanly from the walls of snow pits hand dug by operators wearing clean room clothing far away from local contamination sources such as scientific stations , using sampling tools extensively cleaned with ultrapure water and acids . Deep ice ( depths up to several kilometers ) can only be obtained as ice cores whose outside is heavily contaminated during drilling operations , especially because of the use of wall-retaining fluids which are necessary to counterbalance the enormous pressure encountered at great depths . The core sections must then be decontaminated by chiselling successive veneer layers of ice from the contaminated outside to the pristine inner part of the core . The efficiency of the decontamination procedure has to be assessed by determining changes in concentrations from the outside to the center of each core section . A clear plateau of concentrations in the central part of the core section will indicate that concentrations measured in the center of the core do represent the original concentrations in the ice . Special clean laboratories flushed with air filtered through high efficiency particle air filters have to be used for the analysis of these very valuable samples . Ultrapure water and acids are required , together with the use of sophisticated cleaning procedures . It is also essential to perform extensive blank determinations in order to accurately determine the amount of each heavy metal added to the samples during each successive step of the analytical procedure , especially by processing artificial ice cores made by freezing ultrapure water whose composition is known beforehand . The analytical techniques used for the determination of heavy metals in these very valuable samples include Isotope Dilution with Thermal Ionization Mass spectrometry ( IDMS ) , Laser Excited Atomic Fluorescence Spectrometry ( LEAFS ) and Inductively Coupled Plasma Sector Field Mass Spectrometry ( ICP - SFMS ) . As an illustration , some examples of the data obtained so far will be presented . Especially , Pb and Pb isotopes data obtained for Greenland ice dated from the Greek-Roman Antiquity , which show evidence of an early large scale pollution of the atmosphere of the Northern Hemisphere 2000 years ago at the time of the flourishing of the Roman Republic and Empire . Also , past natural changes of various heavy metals in Antarctic ice during the past 600 000 years , with pronounced natural variations during the successive interglacial and glacial periods . -147 -

XXXVIII CSI 2013

Lecture Abstracts

(L64) CHARACTERIZATION OF DECOMPOSITION PRODUCTS IN ENERGY STORAGE MATERIALS BY CHROMATOGRAPHIC METHODS Sascha Nowak*, Lydia Terborg and Martin Winter *

([email protected]) University of Münster, MEET Battery Research Centre, Corrensstraße 46, 48149 Germany The electrolyte system in lithium ion batteries consists of organic carbonates and a conducting salt. For most commercial available batteries lithium hexafluorophosphate (LiPF6) is established as the conducting salt. Based on the high hygroscopicity of LiPF6, such systems are always contaminated with a certain amount of water that causes decomposition of the conducting salt to LiF and PF5, which subsequently may release hydrofluoric acid (HF). The decomposition products, especially HF and PF5, have a negative influence on the performance of the lithium ion batteries, such as the deterioration of the SEI and can further act as catalysts for the decomposition of the electrolyte. Due to the fact, that the reaction mechanism of the hydrolysis of LiPF6 in the system is still not fully understood, this work focuses on the decomposition of the conducting salt and additionally its interaction with the organic carbonates. Therefore, the decomposition products were analyzed by ion chromatography coupled with inductively coupled plasma optical emission spectrometry (IC/ICP-OES) and verified by ion chromatography coupled with electrospray ionisation mass spectrometry (IC/ESI-MS). Furthermore, the interaction of the decomposition products of the conducting salt with the organic carbonates was investigated by means of GC-MS and Headspace-GC-MS.

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XXXVIII CSI 2013

Lecture Abstracts

(L65) LOCK-IN THERMOGRAPHY – A NOVEL IN-SITU MEASURMENT METHODE TO SUPPORT SURFACE SPECTROSCOPY FOR LITHIUM-ION CELLS Mathias Reichert, Christian Wendt, Chrisitan Herkt-Bruns, Falko Schappacher, Stefano Passerini and Martin Winter University of Muenster, MEET Battery Research Centre, Corrensstraße 46, 48149 Muenster, Germany e-mail: [email protected] Surface spectroscopy methods and imaging techniques like SEM, EDX, XPS and Raman are important tools to investigate aging and failure mechanism in lithium-ion cells. Usually the cell is dismantled in a contamination free environment and samples were taken from the electrolyte, the electrodes and the separator. This proceeding is called “post-mortem analysis”. One drawback of this procedure is the decisions were to take the sample, because in most cases it is not possible to spot interesting areas by optical survey, so samples were taken randomly or by a fix pattern. To identify areas of interest for the post-mortem analysis of lithium-ion cells we are introducing the highly sensitive Lock-In (IR-) Thermography as a new non-destructive and non-contacting (in-situ) measurement method. This method is already known and used in the semiconductor technology to detect failures, like short circuits and oxide-pinholes in integrated circuits.

Fig. 1: Left: Adapted Lock-In Thermography measurement setup. Right: Detailed amplitude picture with the active part marked as (A) and the inactive electrode site marked as (B). Electrode size: 5 x 5 cm. The principle of lock-in thermography consists of introducing periodically modulated current into an object and monitoring only the periodic surface temperature modulation phase-referred to the modulated heat supply. The information of each pixel of the IR image is processed as if it were fed into a lock-in amplifier. Measurement Setup – We adapted and optimized this method for the use in lithium-ion battery research. Our measurement setup is described in Fig. 1. The measurements were carried out with an InSb IR camera. The sample was a standard pouch cell design with a lithium-nickel-manganese-cobalt-dioxide (NMC) / cathode and a graphite anode in a full cell arrangement. The pouch cell surface was blackened with beamless graphite paint (Graphit 33 from Kontakt Chemie). The lock-in measurement was carried out with an electric excitation frequency of 1 Hz between 4.2 V and 2.8 V; 300 single experiments were carried out during a five minute measurement time.

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Lecture Abstracts

separator Fig. 2: Left: 3D-SEM picture taken from a sample from inactive area (B) of the between anode and cathode. Centre: SEM picture taken from a sample from active area (A) of the graphite anode. Right: SEM picture taken from a sample from inactive area (B) of the graphite anode.

Results – The received amplitude image from the lock-in thermography measurement is shown in (Fig. 1 / Left). The amplitude image correlate with the temperature change in the cell, were the bright spots represent the highest temperature rise (max. 1.2 mK) and the dark blue areas no temperature increase. The inhomogeneity of the temperature distribution in the active material is clearly visible in the amplitude picture (Fig. 2 / Centre). In the middle of the squared electrode an area with no heat production and therefore also electrochemical inactive is detected. Samples are taken from the active (A) and inactive (B) areas from the electrodes. The samples were analyzed with a scanning electron microscope (SEM). The thermal active site (Fig. 2 / Centre) of the anode has normal graphite composite electrode morphology, were the inactive part (Fig. 2 / Right) is covered with a dense and thick surface film. Parts of this film are found on the anode facing side of the separator, as shown in the 3D-SEM picture (Fig. 2 / Left). This heavy coating can lead to a very high charge-transfer resistance, which can explain the inactivity of area B, as shown in the thermal amplitude picture (Fig. 1 / Left). Conclusion – The lock-in thermography as a novel in-situ measurement method for lithium-ion cells is a good addition to existing analyse methods, by detecting the areas of interest for the sample preparation for various surface spectroscopy methods. It is also a promising tool to investigate the local conductivity, electrolyte wetting, electrode quality and aging / abuse mechanism.

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XXXVIII CSI 2013

Lecture Abstracts

(L66) CHARACTERIZATION OF THE DECOMPOSITION PRODUCTS OF A UTILIZED BATTERY ELECTROLYTE FROM A COMMERCIAL AVAILABLE HYBRID VEHICLE WITH PURPOSEFUL ANALYTICAL METHODS Martin Grützke, Vadim Kraft, Britta Vortmann, Björn Hoffmann, Martin Winter and Sascha Nowak University of Münster, MEET - Battery Research Centre, Corrensstr. 46, 48149 Germany Email: [email protected], [email protected] In consideration of the global warming and delimited fossil fuels, alternative sources of energy and new techniques for mobility are required. One possibility are regenerative energies like wind, water and solar energy. However all this technologies have one main drawback: they are not constantly available. Therefore a temporary storage of the energy is necessary. Furthermore the mobility based on fossil fuels as we know it nowadays could be replaced by electric vehicles or at least reduced by hybrid vehicles fueled by electricity from regenerative energies. The lithium-ion battery is a promising energy storage device to implement this revolution because of its high energy density and high reversibility without a memory effect. Unfortunately also lithium-ion batteries have their disadvantages. The lifetime is limited due to internal decomposition reactions of the electrolyte solvent, the conducting salt, the active materials and other battery parts during the electrochemical cyclization. It is necessary to identify the decomposition products of the different battery parts and to clarify the interactions between them to understand how the cell works and why its lifetime is limited. Not till then it is possible to improve the battery performance and the lifetime. The investigations were focused on the ion conducting liquid, the electrolyte. Usually the electrolyte of commercial available lithium-ion batteries is a solution of different linear and cyclic organic carbonates like for example dimethyl carbonate and ethylene carbonate, the conducting salt LiPF6 and some additives. In this study the decomposition products of a utilized battery electrolyte solution from a commercial available hybrid vehicle were characterized. The whole battery pack was dismounted into single cells. We drilled up one cell and collected the electrolyte which showed a lightly yellow color. The organic carbonates and other volatile compounds were identified and quantified with GC and GC-MS. The electrolyte solution consists of (37.5 ± 2.1) % dimethyl carbonate, (27.5 ± 1.4) % ethyl methyl carbonate, (32.6 ± 0.6) % ethylene carbonate and (2.3 ± 1.0) % cyclohexyl benzene. Furthermore, the decomposition product PO(OMe)3 could be detected with this method. The only cation found with IC (ion chromatography) was Li+ in a concentration of (1.32 ± 0.02) mol/L. PF6- and its degradation and decomposition products were investigated with the anion column of the IC system and a coupled ESI-MS. Beside PF6-, F- and H2PO4-, a series of fluoro- and alkyl phosphates could be identified with MS/MS fragmentation experiments. To complete the squad of decomposition products, further investigations with coupled IC-ICP-OES and IC-ICP-MS systems were carried out.

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XXXVIII CSI 2013

Lecture Abstracts

(L67) ANALYSIS OF THE MANGANESE DISSOLUTION AND DEPOSITION IN LIMN2O4/LI4TI5O12 BASED LITHIUM ION BATTERIES Markus Börner, Sebastian Klamor, Björn Hoffmann, Melanie Schroeder, Martin Winter, Falko Schappacher University of Münster, MEET Battery Research Centre, Corrensstraße 46, 48149 Germany E-Mail: [email protected] Lithium ion batteries have been extensively investigated in the last decade due to the steadily increasing demands for the application in portable electric devices and the use in electric vehicles. Among the various cathode materials, LiMn2O4 (LMO) is one of most promising candidates for the use in commercial lithium ion batteries. Apart from its high potential of 4 V vs. Li/Li+ its benefits are the low costs and the environmental benignity compared to other cathode materials containing for example Cobalt and Nickel. However it suffers from capacity fading during cycling due to the dissolution of Manganese into the electrolyte. Several research groups investigated this fading mechanism and ascribed the dissolution of the active material to different effects. Therefore various theoretical and experimental approaches have been reported to clarify the dependence of the Manganese dissolution on the discharge/charge rate and the temperature. To overcome the issues of these complex theoretical models and experimental setups, the most suitable approach was found to be the use of a Li4Ti5O12 (LTO) anode material. With its potential of 1.5 V vs. Li/Li+ it does not feature the formation of a solid electrolyte interface (SEI) compared to carbonaceous anodes. Thus the Manganese dissolution was investigated by analyzing the deposition of the dissolved Manganese on the LTO anode. The dissolved Manganese ions migrate to the anode and do not form a surface layer but discrete particles as shown in Fig. 1. Scanning electron microscopy (SEM) and Energy-dispersive X-ray spectroscopy (EDX) revealed the particles to consist of Manganese and Oxygen. Further investigations were performed to determine the structure and composition of the Manganese oxide particles. Since single crystal XRD measurements did not yield a diffraction pattern, the particles seem to be either amorphous or show a short range order. The corresponding Raman spectrum features different bands that can be attributed to Manganese oxide vibration modes and besides clearly deviate from the LTO spectrum. Potential Manganese oxide compositions were analyzed by Raman spectroscopy to create a database of Raman spectra to determine the exact composition of the deposited Manganese oxide particles. EDX mappings of larger areas of the sample showed that Manganese oxide particles grow at several spots on the LTO anode. The comparison of the EDX mappings for samples cycled with different discharge/charge rates at 23°C, 35°C and 45°C suggest general tendencies concerning the quantity and size of the particles. Therefore Raman mappings were performed to examine the temperature dependence of the amount of deposited Manganese oxide particles. However, since SEM, EDX and Raman spectroscopy are very surface sensitive, the measurements do not give information about the actual amount of deposited Manganese oxide. Thus flat particles and tower-shaped particles with the same cross section would yield the same result. The analysis of the amount of deposited Manganese was accomplished by Laser Ablation measurements coupled with ICP-MS. These Laser Ablation mapping experiments clarified the discharge/charge rate dependence of the Manganese dissolution at the LMO cathode as well as the deposition behavior at the LTO anode. Moreover the different shapes of the Manganese oxide particles were confirmed by three-dimensional SEM images.

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XXXVIII CSI 2013

Lecture Abstracts

Fig. 1: SEM image of a Manganese oxide particle on a LTO anode.

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XXXVIII CSI 2013

Lecture Abstracts

(L67B) UV-PHOTOCHEMICAL VOLATILE SPECIES GENERATION EMPLOYED AS A DERIVATIZATION TECHNIQUE BETWEEN HPLC SEPARATION AND AAS DETECTION WITHIN SPECIATION ANALYSIS OF MERCURY(II), METHYLMERCURY(I), ETHYLMERCURY(I) AND PHENYLMERCURY(I) Vaclav Cerveny1, Ondrej Linhart1, Jan Kratzer2, Jakub Hranicek1 and Petr Rychlovsky1 1

Charles University in Prague, Faculty of Science, Department of Analytical Chemistry, Albertov 6, CZ-12843 Prague 2, Czech Republic 2 Institute of Analytical Chemistry of the AS CR, v.v.i., detached workplace - Department of Trace Element Analysis, Videnska 1083, CZ-14220 Prague 4, Czech Republic e-mail: [email protected] After some ecological accidents, increased mercury concentration can be found not only in water but also in living organisms, e.g. fishes. Consequently, toxic effects can be caused by drinking of contaminated water or by eating of poisoned food. The information about content of individual mercury species in a sample is important from the point of view of toxicity and can be obtained also by employing a connection of cheap and easy available analytical techniques as it will be explained in this contribution. HPLC on reverse phases on a GEMINI column was chosen for separation of inorganic mercury(II), methylmercury(I), ethylmercury(I) and phenylmercury(I). Separated mercury species needed to be transformed from a liquid phase in the effluent into gaseous phase in which atomic mercury absorption at 254 nm can be measured using atomic absorption spectrometer. A derivatization stepvolatile species generation was needed between these two common analytical techniques. Therefore, a derivatization unit was made in our laboratory by wrapping of Teflon tubing around a mercury fluorescent lamp without inner luminofor layer. This fluorescent lamp was fixed in a cheap kitchen light source. Additionally, other tubing materials like quartz tubing of various wall thicknesses with different transmittance at 254 nm were tested. Mercury volatile species generation (derivatization) occurs in this UV-photochemical generator in media of acetic acid solution. Comparable signals were obtained for all the four compounds selected for this study when gaseous hydrogen was added prior to the atomizer. This addition could be eliminated when using some other additives directly in the generation electrolyte. It was found that some additives like e.g., 2-mercaptoethanol and/or ethanol in the mobile phase caused positive effects like higher signal measured and better resolution of peaks obtained. On the other hand, some (mostly of) other substances tested caused signal depression or changes in individual species content ratio in a sample. Detection limits of proposed method for four selected species are between 25 and 50 ng/ml, quantification limits were found around 0.1 mg/ml and the linear dynamic range finished at 2 mg/ml for inorganic mercury (II) and 2.5 mg/ml for other species. Proposed method was tested also on real samples of two types: tap water with unknown mercury content and fish tissue which contained methylmercury without doubt and for which the total mercury content was determined by Advanced Mercury Analyzer AMA 254. Unfortunately, the extraction of mercury species from these samples was not carried out satisfactory because used extraction agents speeded up species degradation or decreased signals of standards too much when considering for routine use. Many of these tested insufficient extraction ways were assumed from literature. For sure, the total mercury content was determined very sensitively by AMA 254. Unfortunately, this device equipped with combustion cell, amalgamator and two absorption cells can not resolute between individual mercury species and it also does not allow measurements in real time. -154 -

XXXVIII CSI 2013

Lecture Abstracts

Improving of the extraction step will be the aim of future studies. Acknowledgements: The authors thank for financial support to the Ministry of Education, Youth and Sports for project MSM 0021620857, to the Charles University in Prague (projects SVV267215 and UNCE 204025/2012).

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XXXVIII CSI 2013

Lecture Abstracts

(L68) CHEMICAL VAPOR GENERATION FOR TRACE ANALYSIS. RECENT DEVELOPMENTS Alessandro D’Ulivo1, Massimo Onor1, Enea Pagliano2, Emanuela Pitzalis1, Emilia Bramanti1 1 C.N.R., Institute of Chemistry of Organometallic Compounds, U.O.S. of Pisa, Via G. Moruzzi, 1, 56124 Pisa, Italy. 2 National Research Council Canada, Ottawa, Ontario K1A 0R9, Canada e-mail: [email protected] Chemical vapor generation (CVG) coupled with atomic and mass spectrometry is one of the most powerful analytical tools for determination and speciation of trace elements. The most popular applications are those concerning the determination of volatile hydrides and mercury but in the last few years its scope has been expanded to many other elements, such as Cu, Zn, Ag, Au, Ni and several transition and noble metals. This presentation will be focused on some recent developments concerning both fundamental and applicative aspects of CVG for trace analysis. The mechanisms of generation of volatile hydrides and volatile species by using aqueous NaBH4 has reached a reasonable degree of rationalization, which is confirmed by recent experimental evidence which have been achieved on the CVG of arsane, methylarsane and dimethylarsane. Concerning with analytical applications, the scope of CVG has been expanded to determination of ultra trace amounts of simple inorganic anionic species such as chloride, bromide, iodide, cyanide, thiocyanide, sulfide, nitrite and nitrate, by gas chromatography mass spectrometry (GC-MS). In this case the derivatizing reaction is the aqueous phase alkylation with trialkyloxonium salts, R3O+[X] (R = Me, Et; X = BF4), which converts the anionic species to their volatile, stable alkyl derivatives RX (X=Cl, Br, I, CN, SCN), R2S, RO-NO and RO-NO2. More recently, the use of Et3O+ [FeCl4] allowed the CVG of fluoride as a stable, volatile ethyl fluoride derivative, which can be determined by GC-MS at sub-micromolar level. Mechanistic aspect of CVG of anionic species, at trace level, by aqueous phase alkylation with R3O+ salts has not been investigated, but their knowledge is important for the optimization of reaction conditions and for the control of interferences. The first approach is to identify all the possible reactions involved in the generation and in the liquid-vapor phase transfer of the volatile analytical derivative, RX. They can be classified as analytical reactions, competitive reactions and interfering reactions according to the scheme reported below. Analytical reactions R3O+ + X  RX(aq) + R2O RX(aq) ⇌ RX(g) Competitive reactions R3O+ + H2O  ROH + R2O + H+ X + H+ ⇌ HX(aq)

(1) (2)

primary derivatization reaction phase transfer of analytical derivative

(3) (4)

reagent hydrolysis protonation of analytical substrate

HX(aq) ⇌ HX(g) RX + R3O+  R2X+ + R2O

(5) (6)

phase transfer of protonated analyte alkylation of analytical derivative

Interfering reactions X + Mn+ ⇌ MX(n-1)+ R3O+ + Y  RY + R2O R3O+ + L  RL+ + R2O

(7) (8) (9)

metal complex formation alkylation of anionic species other than X alkylation of ligand/donor species

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XXXVIII CSI 2013

Lecture Abstracts

The optimization of experimental conditions should take into account the those experimental parameters which play a role in controlling all the possible reactions above mentioned. The first approach is to consider temperature, time, acidity and amount of reagent as the most critical parameters which play a major role in controlling the analytical reaction system. The choice of chemical additives (buffers, masking agents) represents a critical aspect of this derivatization procedure due to the reactivity of trialkyloxonium salts with other anionic species or ligand/donor species.

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XXXVIII CSI 2013

Lecture Abstracts

(L69) INFLUENCE OF SELENIUM SPECIES IN AQUACULTURE FEEDS ON THE SELENIUM STATUS OF FARMED RAINBOW TROUT FRY Simon Godin1, Stéphanie FONTAGNE-DICHARRY2, Maïté BUENO1, Philippe TACON3, Brice BOUYSSIERE1, Françoise MEDALE2 1

LCABIE, Université de Pau et des Pays de l’Adour, IPREM UMR CNRS 5254, Technopôle Hélioparc Pau Pyrénées. 2, avenue du Président Angot, F- 64053 Pau Cedex 09, France 2 INRA, UR1067 Nutrition, Métabolisme, Aquaculture, F-64310 Saint-Pée-sur-Nivelle, France 3 Lesaffre Feed Additives, F-59700 Marcq-en-Barœul, France e-mail : simon.godin@univ-pau Nowadays, the extensive use of material from marine origin in aquaculture feeds takes a nonnegligible part in threatening marine resources [1]. Thus, the development of a sustainable aquaculture calls for new fish feeds mainly based on plant-ingredients, but also requires that the nutritional value of the final product is kept. Indeed, compounds such as polyunsaturated fatty acids (PUFAs), which are commonly found in fish, are proved to efficiently protect against cardiovascular diseases and breast cancer [2,3]. Also, selenium is a micronutrient essential to animals and has a decisive role in the regulation of the antioxidative capacity of the body. Therefore, there is a growing interest in the supplementation of plant-based diets with selenium, which would offer an alternative to marine-based feeds, and are moreover expected to fulfill the requirements of fish during its growth, especially during the early developmental stages. In this study, a 12-week feeding trial has been conducted with Se supplemented (selenite or Seyeast) and non-supplemented diets from marine or vegetal origin. The determination of major selenium species in two experimental diets has been carried out using anion exchange chromatography - inductively coupled plasma mass spectrometry (LC - ICP MS). Significant increase was observed in the total selenium level of rainbow trout fry depending on the Se diet level. After enzymatic digestion, the selenoaminoacids levels in fry fed with each diet have been investigated at the end of the trial. Growth rate and mortality were also monitored during the feeding trial, and the activity of some antioxidant enzymes was measured. References [1] L. Deutsch, S. Gräslund, C. Folke, M. Troell, M. Huitric, N. Kautsky, L. Lebel, Global Environmental Change 17 (2006) 238 [2] H. Bartsch, J. Nair, R. Wyn Owen, Carcinogenesis 20 (1999), 2209 [3] P. C. Calder, Clinical Science 107 (2004), 1

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XXXVIII CSI 2013

Poster Abstracts

(P1) DETERMINATION OF TRACE SULFUR IN BIODIESEL AND DIESEL STANDARD REFERENCE MATERIALS BY ISOTOPE DILUTION SECTOR FIELD INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRY Renata S. Amais1, Stephen E. Long2, Joaquim A. Nóbrega1 and Steven J. Christopher2* 1

Group of Applied Instrumental Analysis, Department of Chemistry, Federal University of São Carlos, 13565-905, São Carlos, SP, Brazil 2 Chemical Sciences Division, National Institute of Standards and Technology, Charleston, SC, United States * e-mail: [email protected] Sulfur emissions are related to the formation of acid rain and atmospheric pollution, and environmental concerns about sulfur emissions from the combustion of fossil fuels, have resulted in governmental agencies regulating the maximum sulfur content in biodiesel and diesel fuel.1 The US Environmental Protection Agency (EPA) denominated low sulfur diesel with a sulfur content less than 500 mg kg-1 and, more recently in 2010 mandated the use of ultra low sulfur diesel (ULSD) which must have less than 15 mg kg-1 sulfur.2 In addition, biodiesel has been added to diesel as an alternative to reduce S and other pollutant emissions, and the maximum sulfur content allowed in biodiesel can be as low as 10 mg kg-1 such as that established by the Brazilian Government Petroleum, Natural Gas and Biofuels Agency (ANP) and the European Union (EU) Euro V standard. In this work, a method is described for quantification of sulfur at low mass fractions in the order of µg g-1 in biodiesel and diesel fuels using double isotope dilution and sector field inductively coupled plasma mass spectrometry (ID-SF-ICP-MS). A SF-ICP–MS (Element XR, Thermo Scientific, Waltham, MA, USA) was used for all isotope ratio measurements. The sample introduction system comprised a concentric nebulizer and an ESI (Elemental Scientific, Omaha, NE, USA) stable sample introduction spray chamber which combines cyclonic and double-pass Peltier-cooled spray chamber. The radio frequency applied power was 1.35 kW, the monitored isotopes were 32S and 34S, and the number of spectra per sample was 250. All data for samples, blanks and calibration solutions were corrected for experimental mass bias, typically about 1.5 % per amu. The correction factor applied was based on comparing measured 32/34 ratios to an isotopic standard generated from SRM 3154 (Sulfur Standard Solution) having known isotopic abundances. Medium resolution conditions were employed to eliminate isobaric interferences at 32S and 34S related to polyatomic phosphorus and oxygen species. Closed vessel microwave digestion was employed using a diluted nitric acid and hydrogen peroxide decomposition medium to reduce sample dilution volumes. Biodiesel and diesel fuel digestion was performed using a high-pressure microwave oven (Microwave 3000, Anton Paar, Graz, Austria). A volume of 5.0 mL of nitric acid with a concentration of 7 or 14 mol L-1, plus 3.0 mL hydrogen peroxide was added to each vessel containing 0.25 g fuel sample and an accurately weighed aliquot of the spike solution. The heating program consisted of one power ramp step (40 min to 1.4 kW) and a hold step for 30 min at the maximum pressure setting of 80 bar. A conservative 35 W/min ramp rate was used to avoid a rapid increase of pressure. The same analytical process was applied for the procedure blanks. The final volume of all digests was made up to 50 mL with deionized water. The limit of detection (LOD) and the limit of quantification (LOQ) were calculated as three times and ten times the standard deviation of the mean concentration of S determined in 10 procedure blanks, respectively. The analytical method yielded LOD and LOQ values of 0.7 and 2.5 µg g-1 (in the fuel sample), respectively. Digests obtained using 7 and 14 mol L-1 nitric acid presented accurate results in both systems, 10.64 ± 0.13 mg kg-1 and 10.73 ± 0.17 mg kg-1 respectively, by comparing with the certified value 10.81 ± 0.47 mg kg-1. -159 -

XXXVIII CSI 2013

Poster Abstracts

No statistically significant difference at a 95 % confidence level could be observed between the certified value and both results using diluted and concentrated HNO3. Thus, 7 mol L-1 nitric acid was used in all further determinations. As can be seen in Table 2, the measured sulfur values for B100 Biodiesel (Animal-Based) and NIST SRM 2723a Sulfur in Diesel Fuel Oil agree well with certified data and no statistically significant difference at a 95 % confidence level was observed between measured and certified values for control samples confirming method accuracy. In addition, the analysis of the DRM-272b Sulfur in Diesel demonstrates that the proposed method is also feasible to measure high sulfur content in diesel (Table 2). Table 2. Sulfur determination in SRMs using diluted nitric acid at sample preparation step. The values are expressed as mean ± expanded uncertainty (n = 6). Found (µg g-1) Sample Certified value (µg g-1) B100 Biodiesel animal-based (SRM 2773)

7.39 ± 0.39

7.42 ± 0.32

Sulfur in diesel fuel oil (SRM (2723a)

10.91 ± 0.32

10.85 ± 0.30

409.2 ± 8.6

412.7 ± 4.1a

Sulfur in diesel fuel oil (DRM 272b) a n=5

SRM 2723a was used as a control for the candidate SRM 2723b value assignment measurement process. Both the control and the candidate SRM were measured in the same analytical sequence and the same spike solution (9.9110 µg g-1 ± 0.0076 µg g-1 34S, n=4, mean ± standard deviation) was added to each. The individual components of uncertainty for S in each sample were determined according to ISO guidelines.3 The total sulfur measured in the material was 9.05 µg g-1 ± 0.13 µg g-1, and the expanded uncertainty is under 1.5 % relative. It was demonstrated in this work that it is feasible to use diluted nitric acid solution and microwave-assisted digestion, followed by ID-SF-ICP-MS for biodiesel and diesel fuel measurements of sulfur. Accurate results were obtained for SRM control materials and it was possible to make accurate total sulfur measurements in candidate SRM 2723b Sulfur in Diesel Fuel Oil. Acknowledgement The authors would like to thank the Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) for scholarship and fellowship provided (2010/17387-7 and 2012/00920-0). The authors are also grateful to the Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq). References S. F. Boulyga, J. Heilmann, K. G. Heumann. Anal. Bioanal. Chem., 382: 1808. 2005. 2 Environmental Protection Agency. www.epa.gov Access March, 2013. 3 Guide to the Expression of Uncertainty in Measurement”, ISBN 92-67-10188-9, 1st ed. ISO, Geneva, Switzerland, 1993. 1

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(P2) DETERMINATION OF CHROMIUM SPECIES IN THE WORKPLACE AIR M. Stanisławska, B. Janasik; R. Brodzka; W. Wąsowicz Nofer Institute Of Occupational Medicine, Department of Toxicology and Carcinogenesis, Biomonitoring Laboratory, 91-348, Lodz, Poland; e-mail:[email protected] Occupational exposure to welding fumes is a known health hazard. There is substantial evidence that some chromium (Cr) containing substances are toxic for humans; furthermore hexavalent chromium is known to be carcinogenic. IARC has classified chromium VI (CrVI) as carcinogenic to humans (group 1). Exposure to Cr VI has been known to be responsible for the damage to the airways, irritating skin disease, asthma, bronchopulmonary cancer. According to the welding process, stainless steel welders may be exposed to all chemical species of chromium (metallic chromium, chromium III and chromium VI compounds). The toxicity depends on the chemical forms in which the chromium is present. It is necessary to quantify the individual oxidation states of chromium for an accurate assessment of their impact. The objective of this work was to application of high performance liquid chromatography (HPLC) coupled to inductively plasma mass spectrometry (ICP-MS) to measure the chromium species in the workplace air. The study was carried out in two plants in Poland performing welding operations. Stainless steel welders chosen for the study had worked in welding using three processes: manual metal arc (MMA), metal inert gas (MIG) and tungsten inert gas (TIG). Personal samples (one sample per shift) to assess time-weighted average (TWA) concentrations were continuously collected from the welders’ breathing zone. All the samples covered 6-7 hours out of the 8-hr work shift (including breaks). Airborne particulate sampling was performed on glass filters (Whatman GF/A, diameter 37mm), and membrane filters (Sartorius 11304, 0,8 µm, diameter 37 mm). The concentration of welding fumes (total particulate) were determined by weighing the filter and calculated in milligrams per cubic meter. Concentration the total chromium was determination by ICP-MS. The total hexavalent chromium were analyzed by visible absorption spectrophotometry with the diphenyl carbazide (DPC). The water-soluble chromium species were analyzed by HPLC-ICP-MS. The content of water-insoluble chromium (VI) species in a sample was determined from the difference of total chromium (VI) content and content of water-soluble chromium (VI). Detection of chromium species was accomplished with ELAN DRC-e (Perkin Elmer, SCIEX, USA). Methane was used in the Dynamic Reaction Cell (DRC) to reduce potential polyatomic interferences on Cr+ at m/z 52. Separation was accomplished using HPLC Series 200(PerkinElmer, SCIEX, USA). A 3 cm pecosphere column with 3µm C8 packing (Perkin Elmer) was used for separation. The mobile phase consisted of 1mM tetrabutyloammonium hydroxide (TBAH) and 0.6 mM ethylenediaminetetraaceticacid dipotassium salt (EDTA) and 5% methanol. Total chromium concentrations were measured using conventional nebulization into the ICP-MS. Linear regression analysis established the response function from the reagent blank and the series of five standard solutions (0.05; 0.1; 0.5; 0.75 and 1.0 µg/ml). Each species yielded an r>0.999. Time weighted average concentrations of the welding fumes and its elements at the worker’s breathing zone were respectively (mg/m3): dust 0.14–10.7; iron 0.004–2.9; manganese 0.001– 1.12; nickel < 0.001–0.2; chromium < 0.002–0.85 (mainly Cr (III) and insoluble Cr (VI)). The maximum admissible limits for workplace pollutants (TLV®-TWA) were exceeded for -161 -

XXXVIII CSI 2013

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manganese and for insoluble chromium Cr (VI). For Cr (III) the limit was exceeded in individual cases. The concentration of MIG/ total Cr fumes in air was, arithmetic mean 317µg/m3. It is also known that MIG welding generates more particulate matter than TIG welding. The percent contenof iron in welding fumes at workplace of the stainless steel welders was about 30 percent (MIG) and 15 percent (MMA) and 5 percent (TIG). The contribution of manganese in the welding fumes was about 10 percent (MIG) and 5 percent (MMA) and 1 percent (TIG). The nickel was at the level of about 1 – 2 percent (MIG, TIG). The contributions of the chromium compounds in the welding fumes was about 6 percent (MIG) and 1 percent (TIG), while those of hexavalent chromium was below 1 percent including water-soluble chromium(VI). In the MIG process the proportion of total soluble chromium is low; almost 100% of total chromium emitted in MIG process is the water-insoluble chromium compounds. The results from this work demonstrated that HPLC-ICP-DRC-MS technique can serve as a rapid, sensitive, precision system to determined chromium species in the workplace air samples.

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(P3) A NEW APPROACH FOR THE DETERMINATION OF ARSENIC IN THE WORKPLACE AIR. THE POSSIBILITY OF USING LA-ICP-MS TECHNIQUE R. Brodzka, B. Janasik, M. Stanisławska, M. Trzcinka-Ochocka, W. Wąsowicz Nofer Institute of Occupational Medicine, Department of Toxicology and Carcinogenesis, Laboratory of Biological Monitoring, St. Teresy 8, 91-348 Lodz. e-mail: [email protected] Assessment of occupational exposure to trace elements occurring in the workplace is based on the determination of metals concentrations in the air in the breathing zone of the employee. Arsenic, lead, cadmium and chromium are particularly harmful to health. They may pose carcinogenic effects to the human body. Currently, the method most commonly used to assess the exposure in the workplace is based on analyzing individual air samples collected on filters in the breathing zone of the workers (Polish Norm PN-Z-04008-7). Air filter samples are then mineralized in mixtures of acids. The ways of digestion depend mostly on the type of a filter used for air sampling (e.g. membrane filters). Therefore in present paper, a fast, easy and reliable qualitative and quantitative analysis of the content of metals in air samples from the workplace should be developed. The introduction of the LA-ICP-MS (mass spectrometry with inductively coupled plasma combined with laser ablation) technique for determination of air samples offers great opportunities for eliminating pretreatment steps, like mineralization process. Reducing execution time and low cost saving necessary to conduct research of environmental work would be possible. This study was aimed to assess of the applicability of LA-ICP-MS technique (LXS-500, Cetac, USA, ELAN DRC-e, Perkin Elmer, SCIEX) for the determination of metals in air samples in the occupational settings and compare techniques: LA-ICP-MS (quartz filters) and ICP-MS (by extraction from quartz filters and digestion membrane filters). Air samples were collected via the individual dosimetry method in the workers’ breathing zone continuously throughout a 6 – 7-hour period of time in accordance with the sample collecting strategy contained in the Polish Norm PN-Z-04008-7 (PN-Z-04008-7:2002). All analysis were conducted using three methods: LA-ICP-MS in quartz filters, ICP-MS in quartz filters after extraction 10ml 1% HNO3 and LA-ICP-MS in membrane filters after mineralization. The study included 16 air quartz filters collected at work stations in Copper Smelter. Methods for metals determination in quartz filters by LA-ICP-MS and ICP-MS were developed and optimized. Validation parameters: linearity, range, limit of detection, limit of quantification, precision, accuracy, repeatability and recovery for maximum admissible concentration (MAC) levels in Poland were evaluated. After comparing this method with the mineralization method (regarded as a our reference analysis) adapted by NIOSH No. 7303, it can be concluded that the examined LA-ICP-MS method could be used for rapid pre-monitoring of the work environment based on the determination of metals in the workplace air. On the basis of analysis by LA-ICP-MS and validation set of parameters can be considered that analytical methodologies are correct. Results indicate that, LA-ICP-MS can be used in the future to monitoring of work environment. Application of this technique would be more promising when appropriate reference materials are available and technical problems (e.g. heterogeneity of dust covering the surface of the filter or lability of dust on the filter) would be established by appropriate of analytical strategy.

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(P4) DETERMINATION OF MERCURY SPECIES IN FISH USING HPLC-ICP/MS Syr-Song Chen, Che-Lun Hsu, Wei-Min Fu, Cheng-Ming, Chu, Su-Hsiang Tseng, Ya-Min Kao, Lih-Ching Chiueh and Yang-Chih Shih Food and Drug Administration Department of Health No.161-2, Kunyang St, Nangang District, Taipei City 115-61, Taiwan (R.O.C) e-mail: [email protected] A method was developed for determination of inorganic, methy-, ethyl- and propylmercury in seafood. Mercury species were extracted from 1.0 g of edible seafood by adding 5 mL of alkaline solution (20% tetramethyl ammonium hydroxide in H2O) and using focused microwave digestion system. The condition of irradiation temperature of 70℃ and heating time of 8 min could have the optimal extraction efficiency without decomposing methy-, ethyl- and propyl mercury mercury. Mercury species in filtered extract were separated by reverse-phase high performance liquid chromatograph using a Phenomenex Synergi Hydro-RP column with gradient elution by aqueous (0.1% cysteine + 0.1% cysteine-HCl) and organic(methanol) mobile phase at room temperature and were detected by inductively coupled plasma/mass spectrometer at mass-to-charge 202. Optimum conditions allowed sample through out to be controlled by increasing the organic composition of the mobile phase, and the instrumental analysis time was near 10 min per sample. The recoveries of inorganic, methy-, ethyl- and propylmercury were 94.0 - 113.3%, 102.5 107.2%, 85.6 - 87.8% and 98.9 - 110.8%, respectively. The limits of quantitation of mercury species were found 0.01 ppm for inorganic and methylmercury, and 0.005 ppm for ethyl- and propylmercury. The proposed method was finally validated by the analysis of biological certified reference material DORM-3 fish protein. The detected and certified value of methylmercury were 0.329 ± 0.019 mg/kg and 0.355 ± 0.056 mg/kg respectively. It indicated that the method was well available to detect the mercury species in fish. Twelve samples of fish muscle purchased from markets were analyzed. The results showed the levels of methylmercury were in the range of ND 0.924 mg/kg, those of inorganic mercury were ND - 0.011 mg/kg, and ethyl- and propylmercury were not detected. Key words:seafood, mercury species, high performance liquid chromatograph, inductively coupled plasma mass spectrometer

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(P5) DEVELOPMENT OF A QUANTUM DOT-BASED IMMUNOASSAY FOR SCREENING OF TETRACYCLINES IN BOVINE MUSCLE Jenifer García-Fernández, Laura Trapiella-Alfonso, José M. Costa, Rosario Pereiro, Alfredo SanzMedel. Department of Physical and Analytical Chemistry, University of Oviedo, Avd. Julián Clavería 8, 33006 Oviedo, Spain. e-mail: [email protected] The family of tetracyclines, (TC: tetracycline, chlortetracycline, oxytetracycline and doxytetracycline) is a group of antibiotics that have been widely used in human and veterinary medicine. These drugs have also been applied as growth promoters in animal husbandry. However, the presence of TC residues in food has harmful effects in human health, so maximum residue levels have been set, being 100 µg/Kg in bovine muscle1. Although up to date, there are different analytical strategies available for the determination of TC (based on chromatography,  capillary electrophoresis, photoluminescence or immunochemical techniques), nowadays exists a great demand of developing simple, fast and low cost screening methodologies for the discrimination of such contaminants. Immunoassays with its inherent selective recognition and binding of the analyte and simple sample treatment are specially indicated for such determinations. In this communication we present the development of a new screening strategy for tetracyclines based on a quantum dot (QD) fluorescent competitive immunoassay. In this format of assay the antigen (analyte) and the labeled antigen (tracer) compete for the limited binding sites of the immobilized antibody. We will present our work in the following steps: Synthesis and characterization of the label: CdSe/ZnS QDs. Preparation of the TC-BSA conjugate and further bio-conjugation with QDs to obtain the tracer TC-BSA-QDs that gives the analytical signal in the immunoassay. Characterization of the tracer. Development of the immunoassay and the screening curve; here, unspecific absorptions, cross reactivity, and additive studies are evaluated. Application to muscle tissue by extraction of TC from the bovine muscle. The results obtained showed the positive discrimination between non-contaminated and potentially TCs contaminated meat samples. Moreover, the cut-off level for the screening curve turned out to be about two orders of magnitude lower than the permitted legislation levels. Finally, it should be stressed that the strategy proposed in this contribution could be expanded easily to the adventageous analysis of other food contaminants or other food samples of interest. 1

  Commission  Regulation (EU) Nº 37/2010 on pharmacologically active substances and their classification regarding maximum residue limits in food stuffs of animal origin. 

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(P6) ICP-MS-BASED ISOTOPIC MEASUREMENTS OF ATMOSPHERIC LEAD IN POLAR REGIONS Marco Grotti1, Andrea Bazzano1 and Mery Malandrino2 1 2

Department of Chemistry and Industrial Chemistry, University of Genoa, Italy Department of Chemistry, University of Turin, Italy

e-mail: [email protected] The lead isotopic composition of aerosols reaching the polar regions potentially contains valuable information on the source and long-range transport of atmospheric particulate and associated contaminants, which will complement that from meteorological and elemental composition studies. In the frame of the Italian polar research programmes, samples of atmospheric aerosols have been systematically collected in both Norwegian Arctic (Ny Älesund, Svalbard Islands) and Antarctica (Terra Nova Bay, Victoria Land) and analysed for elemental composition and stable lead isotope ratios (206Pb/207Pb, 208Pb/207Pb). Accurate and precise determination of lead isotope ratios in digests of particulate samples has been achieved by inductively coupled plasma mass spectrometry (ICP-MS), using the dynamic reaction cell to improve the precision. The relevant operating parameters have been optimized in a multivariate way, according to the empirical modelling and experimental design concepts. This allowed the full consideration of mutual interactions among the factors and simultaneous minimization of %RSD-values and mass discrimination effects. After determining the detector dead time, the following instrumental parameters have been studied: settling time, the rod offset voltages of both the quadrupole and the reaction cell, the Mathieu stability parameters of the cell’s quadrupole, the cell path and the axial field voltages, dwell time and number of sweeps. Moreover, the use of argon, methane and ammonia as the collision gas was explored and the measured isotope ratio precision compared to that attainable with standard quadrupole-based ICP-MS and theoretical values. The main figures of merit of the optimized method have been determined according to the IUPAC recommendations, with special attention to the limit of quantification at a given precision threshold and robustness. The main results of the method optimization and validation and preliminary data for the analysis of particulate samples will be reported and discussed.

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(P7) SIGNS OF SPATIAL HETEROGENEITIES WITHIN XLPE CABLE INSULATION PROBED BY SOLID STATE 1H-NMR Jobby Paul1, Eddy W. Hansen1, Sissel Jørgensen1, Bjørnar Arstad2 and Aud Bouzga2 1

2

Department of Chemistry, UiO, P. O. Box 1033 Blindern, N-0315 Oslo, Norway SINTEF Materials and Chemistry, P.O. Box 124 Blindern, N-0314 Oslo, Norway  

e-mail: [email protected] A number of cylindrical samples were drilled out from the inner-, middle- and outer regions of a commercial cross-linked polyethylene (XLPE) cable insulation material as illustrated: Inner Middle Outer

r

During ageing in an air circulating oven at 130oC for a period of 2 months samples were taken out regularly from the oven, cooled to 550C, and analyzed by NMR. As can be inferred from

18 days

22 days

26 days

34 days

Inner

Middle

Outer

 

 

Figure 1. The colour of the inner, middle and outer layers of the XLPE cable insulation disc aged in air at 1300C for 18, 22, 26 and 34 days, respectively. Images are taken at room temperature. the sample color in Figure 1, a significant change in some (unspecified) properties of the polymer occurs during ageing. More specifically, 1H-NMR analysis of the Free Induction Decays (FID) during ageing of the outer region of the samples demonstrates the crystalline (C) component and the two amorphous components – the amorphous soft (AS) and the amorphous rigid (Ar) - change during ageing at 1300C, as noted on Figure 2[1].

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Figure 2. Fractional intensity as a function of ageing time within the outer layer of the XLPE cable insulation. C, Ar and As represent the crystalline, the amorphous rigid and the amorphous solid fractions, respectively. The vertical, dotted lines represent the start (tI) and the end (tII) of the fast oxidation time period (period II), as determined for the C-fraction. Of particular interest is the spatial dependence of the spin-lattice relaxation rate R1 =1/T1 which occurs during ageing, as suggested by the results presented in Figure 3.

Figure 3. Spin lattice relaxation rate R1 (=1/T1) as a function of ageing time within the inner-, middle- and outer layers of the XLPE cable insulation. The measurements were all performed at 55oC, after cooling the sample from 130oC to room temperature. Also, NMR spin-spin relaxation time measurements (not shown) together with sample mass measurements are all consistent and suggest that the native cable insulation material is spatially inhomogeneous. These spatial inhomogeneities are believed to originate during the processing of the material. Acknowledgement. A PhD-grant (Jobby Paul) financed through the project "Demanding Polyolefin Applications" (project partners Nexans, Bredero Shaw SINTEF, Norner, NTNU and UiO) is greatly acknowledged. The project is financed by Nexans, Bredero Shaw, Borealis and the Research Council of Norway (179945/I40). [1]. Hansen EW, Roots J. Determination of crystallinity in polyethylene from 1H-NMR FID analysis. Effect of non-curie temperature behaviour. International Journal of Research and Reviews in Applied Sciences. 2010 (5) 207-212.

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(P8) DELTA (13C) DETERMINATION ON BIOFUELS AND BIOPLASTIC APPLYING CAVITY RING-DOWN SPECTROSCOPY Gisele Birman Tonietto1, 2, Jose M. Godoy1, Julianna M. Martins 1, Walquiria R. S. Ribeiro1, Mara A. Silva1 1 2

Pontifícia Universidade Católica do Rio de Janeiro – Chemistry Department Petrobras – Research Center – Cenpes - Chemistry Department

email: [email protected] Cavity ring-down (CRDS) spectroscopy is a direct absorption technique, which can be performed with pulsed or continuous light sources and has a significantly higher sensitivity than obtainable in conventional absorption spectroscopy. The CRDS technique is based upon the measurement of the rate of absorption rather than the magnitude of absorption of a light pulse confined in a closed optical cavity with a high Q factor. The advantage over normal absorption spectroscopy results from, firstly, the intrinsic insensitivity to light source intensity fluctuations and, secondly, the extremely long effective path lengths (many kilometres) that can be realized in stable optical cavities. In the last decade, it has been shown that the CRDS technique is especially powerful in gas-phase spectroscopy for measurements of either strong absorptions of species present in trace amounts or weak absorptions of abundant species. Cavity ring-down spectroscopy (CRDS) is a laser-based absorption spectroscopy technique that is starting to and extensive application as a consequence of the very high sensitivity of the method compared with more traditional absorption spectroscopy techniques. The present study aimed to obtain the 13C/12C isotopic signature in solid and liquid samples using a laser analyzer. An isotopic analysis method using a total organic carbon analyzer coupled to a cavity ring-down spectrometer (iTOC-CRDS) was developed and implemented. The results were compared with those obtained by IRMS. The method performance was evaluated by the parameters of linearity; accuracy, using standard reference materials; precision, using parameters of repeatability and reproducibility and by calculating the associated uncertainties. The analyzed samples were biofuel and bio-plastic. We determined stable carbon isotopic compositions (δ13C) of plastics to discriminate between plant- and petroleum-derived plastics. The δ13C values of plastics derived from C4 plants are significantly higher than those of petroleum-derived plastics. These results suggest that the stable isotope analysis would be useful in discrimination of plant-derived plastics from petroleumderived plastics.

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(P9) THE STRUCTURAL AND MAGNETO-RESONANCE PROPERTIES OF THE POR-INP Suchikova Y.1 1

Berdyansk State Pedagogical University, str. Schmidt 4, Berdyansk, Ukraine

e-mail: [email protected] Low-dimensional semiconductors are a subject of intensive investigations due to their modified optical and electric properties caused by the quantum-dimensional effects being inherent to nanostructures. Among such the semiconductors a special attention is given to the indium phosphite (InP) as the technologically impotent material in manufacturing the lasers, diodes, solar batteries etc. The single-crystal InP plates are used as the substrates in growing different heterostructures in making the effective radiation sources (injection lasers, light-emitting diodes) and high-speed photodetectors for fiber-optics communication lines. Today, the indium phosphite is the most probable material for chips mass-production. The properties of porous InP are interesting since in contrast to the cilicon, for example, the indium phosphite is the direct gap semiconductor that allows one to use such semiconductor for manufacturing the high-performance light-emitting devices. Finally, the InP is sufficiently inert material, oxidize weakly in the open air and does not interact virtually with acids. Due to that one can expect that the porous based layers will be more stable ones and less subjected to the environmental activity than the porous cilicon. In this paper the structural and magneto-resonance properties of the InP samples doped by the sulfur or zinс with n- and p- polarity of conductivity and the charge carries concentration N=2.3*1018 cm-3 are investigated. The InP samples with n- and p- polarity of conductivity with different surface orientation and with charge carries concentration N=2.3*1018 cm-3 were selected by us the subject under test. The crystal lattice of those is similar to the zinc blende structure. The atom coupling in the lattice has mainly the covalent nature with some part (up to 15%) of the ion component. The samples are doped by sulfur (S) or zinc (Zn). The single-crystalls of InP have been produced by Chohralskii method in the Laboratory of «Molecular Technology GmbH» company (Berlin, Germany). The sample thickness is 1mm. The plates were cut out perpendicularly to the axis growth and polished with both sides. Electrochemical etching was performed on the standard set up in the electrolytic cell with a platinum on the cathode. In this case the hydrofluoric and hydrochloric acid solutions with different concentration were employed as the electrolyte. The morphology of the porous samples under test has been investigated by means of the scanning electron microscope JSM-6490. The analysis of sample's morphology has shown that the active cavitation was observed in all the cases virtually. It has been revealed that a steady-state configuration of the porous layer surface is formed at the current density maximization under conditions when the cavitation becomes as dominating electrochemical process leaking at the given value of the polarizing voltage on the single-crystal semiconductor anode. In the row of halogenide-ions the minimum voltage value of beginning the structure formation corresponds always to the fluorine anion. The morphology of porous samples being obtained by employing the hydrofluoric acid demonstrates a grid of mesoor macropores. The formation of such pores is explained frequently by the emergence of defects and dislocations on the crystall surface. Here, the substantial surface over-pickling is observed (Fig.1a). As can be seen from the Figure, the re-etching areas are clearly visible that is evidence of strongly “hard” etching conditions. The porous surface demonstrates the extended morphology with generated massive etching holes. The surface like that has the dangerous effective area as compared with the single-crystal analogue. However, the aforementioned surface is not to be

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sufficiently perfect for the heterostructure substrate employing. Therefore, it seems to be advisable to change the etching regime. HCl-based etching agents allow one to obtain a layer composed basically of the nanopores (Fig. 1b) demonstrates the ordered assembly of pores formed on the substrate from the single-crystal InP under etching conditions in 5% hydrochloric acid solution. In this case the pores inter-grow along the full ingot surface. The pore size is about 40nm that is evidence of that the given structure is the nanostructure. The wall size between the pores is in the limits of 5-10nm. The result like that is technologically important since a quality of the porous films is determined by the nanostructure dimensions, by the range of porosity and by the uniform pores distribution along the sample surface. Here, the smaller pores size and more porosity ratio the porous structure is more perfect. porosity ratio. The range of porosity is about 60% from the total sample are.

Figure 1. Morphology of n-InP (111), electrolyte HF: H2O=1:1, j=80 mА/сm2, t=10min (a); and of the porous n-InP (100) being obtained in the 5% HCl, t=5min (b) The measured EPR spectra are sufficienty broad (200 -300 Gauss). They undergo minor changes in the temperature range from 300К to 77К. Here, g-factor is changed within the limits 1.97-1.98 for different samples. The observable differences in the EPR spectra of single-crystal samples and porous ones are caused by changing in the surface properties as a result of electrochemical treatment of the crystals. Among the most probable reasons can be next factors: the partial disorder of the crystal lattice; the fast phosphorus sublattice etching leads to the stoichiometry shifting towards the excess of indium atoms; due to the nanocrystallites formation the surface becomes more "relief", i.e. the surface loses both the homogeneity and the uniformity; quite possible the formation of additional disturbed bonds which can also effect on the EPR spectra. The results of investigations of the structural and magneto-resonance properties of both the singlecrystals and porous InP samples doped by S and Zn with the charge carries concentration N=2.3*1018 cm-3 have been presented in this paper. As it follows from the ample's morphology the active cavitation was observed for all the samples under test. It has been shown that in order to decrease the electrolyte effect on the porous surface formation it is advisable to change the etching regime (the time and the current density) on a more soft one or to use the more diluted solution of the etching agent. Really, the HCl-based etching agents allow one to obtain a layer composed basically of the nanopores that determines in the final analysis the porous films quality.

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(P11) 57

FE-MÖSSBAUER, XANES AND HR-TEM STUDIES OF ELECTRICALLY CONDUCTIVE BAO-FE2O3-V2O5 GLASES

Satoru Yoshioka1, Shiro Kubuki2, Hitomi Masuda2, Kazuhiko Akiyama2, Kazuhiro Hara1 and Testuaki Nishida3 1

Department of Applied Quantum Physics and Nuclear Engineering, Graduate School of Engineering, Kyushu University, Moto-oka 744, Nishi-ku, Fukuoka 819-0395, JAPAN 2 Department of Chemistry, Graduate School of Science and Engineering, Tokyo Metropolitan University, Minami-Osawa 1-1 Hachi-Oji, Tokyo 192-0397, JAPAN 3 Department of Biological and Environmental Chemistry, Faculty of Humanity-Oriented Science and Engineering, Kinki University, Kayanomori 11-6, Iizuka, Fukuoka 820-8555, JAPAN e-mail: [email protected] Vanadate glass having electrical conductivity () of 10-7-10-5 Scm-1 is classified as a semi-conductor. Kubuki et al. revealed that 20BaO•10Fe2O3•70V2O5 glass showed larger  value of 100 Scm-1 when it was annealed at around the crystallization temperature (Tc) of 500 oC [1]. Vanadate glass could be a fascinating candidate for cathode active material of secondary battery [2]. Structural change occurring in vanadate glass, i.e., a decrease in the local distortion of FeIIIO4 and VO4 tetrahedra was elucidated by 57Fe-Mössbauer study [1,2]. In this study, 57Fe-Mössbauer, X-ray absorption near edge structure (XANES) and high-resolution transmitting electron microscopy (HR-TEM) were carried out, in order to reveal the structural change of xBaO•10Fe2O3•(90-x)V2O5 glass, abbreviated as xBFV glass, caused by isothermal annealing. Elemental mapping obtained from HR-TEM images of 20BFV glass showed that Ba2+, VIV and VV ions were homogeneously dispersed in the glass matrix before and after isothermal annealing at 500 o C for 100 min, as shown in Fig. 1 (left and center). On the other hand, it proved that FeIII was aggregated after annealing at 500 oC for 100 min (Fig. 1, right). From DTA study, activation energy for crystallization (Ea) of 20BFV glass was estimated to be 2.3 eV [1], which is comparable to Fe-O chemical bond energy of 2.6 eV [3]. These results suggest that FeIII primarily migrated during the partial crystallization of 20BFV glass. In order to estimate the dimension of crystallization, JohnsonMehl-Avrami (JMA) equation [4] was applied to the change of quadrupole splitting () in the Mössbauer spectra due to isothermal annealing, i.e.

Ba

V

Fe

Figure 1. Elemental mapping obtained from TEM image of 20BaO•10Fe2O3•70V2O5 glass after annealing at 500 oC for 100 min.

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ln [−ln(1 − x)] = n ln t + ln k 1− x = (− t) / 

(1), (2),

where, x, n, t, k andt are fraction of crystallization, Avrami index, annealing time, rate constant and quadrupole splitting value obtained after isothermal annealing for t min, respectively. As a result of JMA plot with obtained for 20BaO•10Fe2O3•70V2O5 glass annealed at 450 oC, n value was estimated to be 1.5, indicating that the crystallization proceeded three dimensionally. This result is consistent with the result of elemental mapping of Fe (Fig. 1, right). (a) (b) (c) (d) (e) V2O5 VO2

(a) (b) (c)

Fe2O3

(d) (e)

Fe3O4

V2O3

FeO

(A)

(B) Photon energy / eV

Photon energy / eV

Figure 2. (A) V-K and (B) Fe-K edges of XANES profiles of xBaO•10Fe2O3 •(90-x)V2O5 glass with ‘x’ of (a) 40, (b) 35, (c) 30, (d) 25 and (e) 20 after annealing at 500 o C for 100 min. Dashed lines are guide to the eyes. XANES profiles of xBFV glass before annealing compose of a shoulder peak of 5483 eV for V-K edge and two peaks of 7128 and 7135 eV for Fe-K edge. As shown in Fig. 2, V-K edge XANES profiles of xBFVglass after the annealing became similar to that of VO2, having a shoulder peaks at the photon energy of 5483 eV, with an increase of V2O5 content (Fig. 2(A) (a)→(e)). On the other hand, Fe-K edge profiles showed a decrease in the peak intensity of 7135 eV and became similar to that of Fe3O4, having a characteristic peak at the photon energy of 7128 eV (see Fig. 2(B) (a)→(e)). These results indicate that high electrical conductivity of xBFV glass is associated with the mixed valence states of VIV, VV, FeII and FeIII, affected by isothermal annealing. References [1] S. Kubuki, H. Sakka, K. Tsuge, Z. Homonnay, K. Sinkó, E. Kuzmann, H. Yasumitsu and T. Nishida, J. Ceram. Soc. Jpn., 115 [11], 776-779 (2007). [2] T. Nishida, Y. Yoshida, Y. Takahashi, S. Okada and J. Yamaki, J. Radioanal. Nucl. Chem., 275[2], 417-422 (2008). [3] K. H. Sun, J. Am. Ceram. Soc., 30, 277-281 (1947). [4] M. Avrami, J. Chem. Phys., 7, 1103-1112 (1939).

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(P11) MEASUREMENT OF ELEMENTAL CONTENTS IN HEMOLYMPH, MALPIGHIAN TUBULES, GUT AND URINE OF RHODNIUS PROLIXUS INVESTIGATED BY SRTXRF Andrea Mantuano 1, Arissa Pickler 1, Regina C. Barroso 1, Liebert P. Nogueira 1, Carla L. Mota 2, André P. de Almeida 2, Delson Braz 2, Simone C. Cardoso 3, Marcelo S. Gonzalez 4, Eloi S. Garcia 5 and Patricia Azambuja 5 1

Physics Institute/State University of Rio de Janeiro, Rua São Francisco Xavier 524/3007B, Zip code: 20550-900, Rio de Janeiro, RJ, Brazil 2 Nuclear Engineering Program/COPPE/Federal University of Rio de Janeiro, Brazil. 3 Physics Institute/Federal University of Rio de Janeiro, Brazil 4 Departamento de Biologia Geral/Federal Fluminense University, Rio de Janeiro, Brazil 5 Laboratory of Biochemistry and Physiology of Insects/Oswaldo Cruz Foundation, Rio de Janeiro, Brazil e-mail: [email protected]

Rhodnius prolixus is a blood-sucking insect well known by its importance as vector of Trypanosoma cruzi (parasite causative agent of Chagas’ disease) principally in Latin America. The insect feeds on blood infected with trypomastigote forms which transform into epimastigotes and spheromastigotes in stomach. The gut of triatomines is the first environment for the transformation of the Trypanosoma cruzi where the epimastigote multiply increasing the population of parasites. In the rectum, the epimastigotes transform into metacyclic trypomastigotes which are eliminated with the faeces and urine [1]. The establishment of Trypanosoma cruzi infection in the gut of the insect vector may be dependent on, and possibly regulated by, a range of biochemical and physiological factors. Some nutrients contained in the body of Rhodnius prolixus can influence on the parasite development. In this work, special attention is given to the elemental contents in fluid secretion by Malpighian tubules and gut of the uninfected control insects. The Malpighian tubules filter hemolymph and secrete a liquid that is often compared with the primary urine in vertebrates. The transport regulation of Malpighian tubules is certainly one of the key points for insect homeostasis and, certainly, it is also important for Trypanosoma cruzi transmission. We have investigated Cl, Ca and K elemental changes observed in gut, Malpighian tubules, hemolymph and urine of fifth-stage Rhodnius prolixus on different days after feeding rabbit blood. The analytical approach of Synchrotron Radiation Total Reflection X-ray Fluorescence (SR-TXRF) technique was used to investigate trace elements of these parts of the insect. It was facility at the X-ray Fluorescence beamline in Brazilian Synchrotron Light Laboratory LNLS/Brazil. The point to note from the results is that basically, largest part of Ca and K is deposited in the Malpighian tubules, some is retained in the hemolymph and relatively little is eliminated from the body. The results agree in showing that much the greater part of the Ca in the diet is retained in the body. Our results reveal that the concentrations, in µg mL-1, of Cl, K and Ca in the gut, in comparison with hemolymph, urine and Malpighian tubules, are low statistically significative. We concluded that the Cl and K are extremely excreted in the first two days. The accumulation of K and Ca increased (P gills > soft tissues > eggs, indicating higher oxidative stress and metal detoxification in the latter. GSH followed the same trend as MT, further corroborating the higher oxidative stress in eggs. Regarding human consumption, metal concentrations were lower than the maximum permissible levels established by international and Brazilian regulatory agencies, indicating that this species is safe for human consumption concerning this parameter. The presence of metals in Callinectes sp., however, is of great importance considering that this is a key species within the studied ecosystem and, therefore, plays a major role in the transference of pollutants to higher trophic levels. In -178 -

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addition, the presence of significant metals concentrations found in eggs must be considered in this context, since crab eggs are eaten by several other species, such as shorebirds, seabirds, and fish. The increasing oxidative stress levels observed in eggs are also of concern since they may be related to developmental issues in this species.

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(P15) ICP-MS METHODOLOGY FOR BLOOD TRACE ELEMENTS COMPOSITION ANALYSIS FOR PATIENTS WITH DIFFERENT STAGES OF TUMOR O.V. Kovalenko1, I.V. Boltina1, E.O. Pisarev1, G. A.Liubchenko2, L.S. Kyolodna2, N.Ya. Gridina3 , I.V. Kalinitchenko4 1

Medved`s Institute of Ecohygiene and Toxicology, Ministry of Health, Kyiv, Ukraine Taras Shevchenko National University of Kyiv, Ukraine 3 Institute of Neurosurgery, National Academy of Medical Science, Ukraine 4 Bruker, 3500 West Warren Ave, Fremont, CA, USA 2

e-mail: [email protected]

It is known that about 8% of total tumors have genetic origins. The rest (about 92%) could be related to poor habits such as smoking, drinking, unhealthy life style, iatrogenic and environment factors. Deviations in optimal chemical elemental composition of blood could be a reason for or consequence of different health disorders, particularly cancerous tumors. We have been researching trace elements composition deviation between reference group of people - healthy patients and groups of those with a compromised medical history (oncologic pathology) and brain tumors (meningioma of different malignancy grades). Bruker 820 ICP-MS equipped with Ion Mirror optics and CRI mini-Collision Cell technology has been used for the trace element analysis due to its superior sensitivity and excellent interference suppression. One of the requirements for this work was to setup a reliable method for microelements quantitative and qualitative determination based on minimal sample preparation routine due to extra-large number of samples. The ICP-MS results obtained were compared to parallel cytogenetic study of peripheral blood lymphocytes in all chosen groups of patients. Lymphocytes cultivation and chromosome specimen preparation was carried out by a standard semi-micromethod. Samples and materials: Blood samples taken from group (aged 29 -55y.o.) treated for benign and malignant meningioma at Romodanov Institute of Neurosurgery (Ukraine) were analyzed at the ICP-MS trace element laboratory at Medved`s Institute of Ecohygiene and Toxicology.

Results: Benign meningioma patients: increase [times] in concentration for Se-3.2, Fe-1.2 , Cr-6, Ni-4, Al6, and I-3.2 and decrease for Zn-1.7, Mn-4, Sr-1.6, Ca-1.7 compared to the reference group. Malignant meningioma patients: increase [times] in concentration: Se-4.8, Cr-5, Ni-2.7, Al-9.6, Fe-1.7, I- 6.7, Mn-4 and decrease Cu-1.4, Zn-6, Sr-1.8, Ca-1.8 found in blood serum under the conditions of malignant meningioma development.

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(P16) THE ISAS- X-RAY FLUORESCENCE BEAM LINE AT DELTA: POSSIBILITIES AND APPLICATIONS Roland Hergenröder, Alex von Bohlen and Martin Brücher Leibniz-Institut für Analytische Wissenschaften-ISAS, Str.11, 44139 Dortmund, Germany

Interface Processes, Bunsen-Kichhoff

e-mail: [email protected] Recently, the Leibniz Institut für Analytische Wissenschaften started to maintain an X-ray fluorescence beam line at Delta a synchrotron located at the Technical University Dortmund. The experiment is set-up at a bending magnet. The double crystal monochromator equipped with either InSb(111) or Si(111) has a usable energy range from 1.5keV to 8keV. The beam line is designed for X-ray experiments under grazing incidence geometry and is equipped for experiments like Xray fluorescence, X-ray absorption, X-ray reflectivity, XANES, etc.

Spectrum of the polychromatic beam of BL2-the ISAS line.

This contribution presents the principles and the possibilities of synchrotron-based X-ray grazing incidence for the measurements of element distribution profiles at surfaces and interfaces. Different experiments are presented ranging from element-specific nanoparticle size distribution measurements to elucidate element distribution along model bio-membranes. This presentation is an invitation to colleagues from all disciplines to use the possibilities of the ISAS beamline.

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(P17) CHEMICAL SPECIATION OF INORGANIC BERYLLIUM FOR WORKING AREAS PARTICULATE MATTER SAMPLES: SEQUENTIAL EXTRACTION PROCEDURE DEVELOPMENT AND APPLICATION Thibaut Durand and Davy Rousset Institut National de Recherche et de Sécurité, Rue du Morvan CS60027, 54519 Vandoeuvre-lèsNancy, France e-mail: [email protected] It is well known that beryllium (Be) exposure is a concern in working areas and can lead to Be sensitization and chronic Be disease (CBD). Usually the method for determining occupational beryllium exposure requires to collect airborne particles by sampling a known volume of air through a filter disposed in a sampling device, for instance a closed-faced-cassette (CFC). Collected matter is digested in acid mixture prior to analysis of beryllium by spectrometry: electrothermal atomic absorption spectrometry (ETAAS), inductively coupled plasma atomic emission spectrometry (ICP-AES) or inductively coupled plasma mass spectrometry (ICP-MS). ICP-MS is particularly useful due to its very low detection limit capability with regards to low beryllium occupational exposure limits (50 ng.m-3, ACGIH 2010). However this method only allows total beryllium quantification, whereas Be-induced toxicity may be not only related to total concentration but also to particle size, surface area, number and chemical form1,2. In occupational environments, different beryllium species with various solubility could be encountered, from easily soluble beryllium salts to poorly soluble beryllium oxides. Difference in solubility will lead in different residence time in the body and different toxicity. It is then of prime importance to assess the proportion of beryllium species according to their solubility in occupational atmosphere. A four step sequential extraction procedure has been already developed for beryllium speciation4: it allows the separation of soluble salts, metallic beryllium, oxides and residual Be-containing silicates, using different extraction solutions. This procedure has been developed on bulk sample but it would not be directly applicable to CFC because it would require the removal of the filter from the cassette which could induce a bias by loosing material during transfer and by not taking into account cassette wall deposits. In this study, an improvement of the leaching procedure was proposed to have a direct and quick analytical method to perform speciation in solubility of inorganic beryllium collected on mixed cellulose ester (MCE) membranes disposed in CFC. The protocol consists on separating soluble salts, metal, oxides, and residual species with four specific extraction solutions (10 mL HCl 0.01M, 10 mL CuSO4 0.1M (in HCl 0.1M), 10 mL NH4HF2 1% (ABF), 15 mL HCLO4:HNO3:HCl:HF mixture) directly introduced subsequently into the CFC to take into account wall deposits. Four different beryllium species were investigated: soluble beryllium salts (BeF2 and BeSO4), beryllium metal (Be(0)), and beryllium oxide. These species, except for BeSO4, were tested separately, then in mixture. BeSO4 were only tested in mixture to highlight some problems of selectivity. After reaction with the corresponding extraction solution introduced in CFC, the solution is filtered with an adapted filtration device and the quantification of beryllium is performed by ICP-MS with matrix-matched calibration solutions. Influence of parameters such as solid/liquid ratio, extraction duration, temperature, solution concentration, was also investigated. Limits of detection were calculated for the four extraction solution-induced matrices by repeated analyses of blank solutions which have gone through the whole extraction procedure. Obtained LODs are low, ≤ 4.6 ng.m-3, (calculated for sampling duration of 8 h at flowrate of 2 L.min-1), lower than the tenth of the ACGIH limit value of 50 ng.m-3. Single specie tests have led to good -182 -

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recovery rates with at least 90% for each extraction solution, while mixture tests exhibited recoveries depending on the beryllium specie ratio initially introduced. Statistical analysis results for mixture have showed influence of each specie on the final result. Optimized method has been tested on samples from French factories for which a potential risk of beryllium exposure is suspected. Inhalable and respirable sampling devices have been used. Results were consistent regarding processes investigated. 1

KENT M.S., ROBINS T.G., MADL A.K. - Is total mass or mass of alveolar-deposited airborne particles of beryllium a better predictor of disease? A preliminary study of a beryllium processing facility. Applied Occupational and Environmental Hygiene, 2001, 16, pp. 539-558. 2 KELLEHER P.C., MARTYNY J.W., MROZ M.M., MAIER L.A., RUTTENBER A.J., YOUNG D.A., NEWMAN L.S - beryllium particulate exposure and disease relations in a beryllium machining plant. Journal of Occupational and Environmental Medicine, 2001, 43, pp. 238-249 3 PAUSTENBACH D.J., MADL A.K., GREENE J.F. - Identifying an appropriate occupational exposure limit (OEL) for beryllium: data gaps and current research initiatives. Applied Occupational and Environmental Hygiene, 2001, 16, pp. 527-538. 4 PROFUMO A., SPINI G., CUCCA L., PESAVENTO M. – Determination of inorganic beryllium species in the particulate matter of emissions and working areas. Talanta, 2002, 57, pp. 929-934.

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(P18) SELECTIVE AND NON-SELECTIVE EXCITATION/IONIZATION PROCESSES IN AR/HE MIXED PLASMAS Sohail Mushtaq1, Edward B. M. Steers1, Juliet C. Pickering2 and Karol Putyera3 1 London Metropolitan University, 166-220 Holloway Road, London, N7 8DB, UK 2 Blackett Laboratory, Imperial College London, London SW7 2BW, UK 3 Evans Analytical Group, 103 Commerce Blvd, Liverpool, NY 13088, USA E-mail: [email protected]

In low pressure analytical glow discharges (GD) such as Grimm-type sources, the plasma gas plays a vital role in the excitation and ionization processes in the discharge. As part of a wide study to identify unusual excitation processes affecting particular lines in GD, helium was added up to 60 % v/v to an argon plasma. The additional gas can drastically influence the emission intensities of the main plasma gas and sputtered analyte (Cu or Fe) due to selective excitation processes which are mainly dependant on the nature of the plasma gas and analyte. In order to understand better the excitation processes occurring, we have investigated the effect of Ar/He mixed plasmas on the electrical parameters, pressure required, sputter rate and emission intensities of sample (cathode) material and plasma gas. ‘Standard conditions’ (20 mA & 700 V with a 4 mm inner diam. anode tube) were used throughout. Spectral measurements were made using the Imperial College high resolution uv-vis Fourier transform spectrometer and involved over 370 spectral lines in the spectral range 200-900 nm. We discuss here the significance of the intensity changes recorded as the amount of helium in the plasma was varied. 1.0

Normalised intensity

Ar I emission lines: It is shown in Fig. 1 that when helium is added to the plasma gas, significant changes in the normalized profiles of the Ar I 811.531 nm line occur, clearly due to an increase in self-absorption. In general, as the helium concentration is increased, argon atomic lines in the 600 – 900 nm region (transitions to the 4s levels) show increasing amounts of self-absorption and self reversal suggesting an increase in the population of the metastable 4s levels. A significant increase in the number density of argon atoms in these states would cause major changes in the excitation processes in the discharge.

0.8 Ar I 811.531 nm

Pure Ar 90Ar + 10e 70 Ar + 30e 40 Ar + 60e

0.6

0.4

0.2

0.0

12318.50 12318.75 12319.00 12319.25 12319.50

-1 Wavenumber/ cm

Fig. 1 Normalized line profiles showing changes in self-reversal for various He Ar II emission lines: 53 argon ionic lines between 345 – 510 nm were studied in various argon/helium mixtures. In Fig. 2 the intensity ratios of argon ionic lines (IAr+He/IAr) are plotted against the Ar II excitation energy for 70% Ar + 30% He. The enhanced intensities of argon ionic emission lines with excitation energy ~ 20 eV are excited selectively by Penning excitation of ground state argon ions by helium metastable atoms, viz Aro+ + Hem → Ar+* + Heo + ΔE

(1)

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As there are two particles before and after the collision, conservation of energy and momentum can only be satisfied if the kinetic energy change, ΔE is small, so Penning excitation is a resonant reaction. The intensity of argon ionic lines from this energy group in particular strongly increases with the increase of helium concentration in the plasma. Fe II emission lines: 90 iron ionic lines between 230 and 285 nm were identified. In general their intensity does not change greatly, but Fig. 3 shows that a group of iron ionic lines, upper energy near to 19 eV, are excited by the non-selective Penning ionization by helium metastable atoms of ground state iron atoms, viz:

Fig. 2 Intensity ratios for argon ionic lines measured in 70%Ar + 30% He as a function of excitation energy (Cu sample).

-

Feo + Hem → Fe+* + Heo + e + ΔE (2)

range of positive values of ΔE. The process appears selective in Fig. 3 as the only lines emitted from levels closer to the helium metastable level are in VUV region below the lower wavelength limit of the Fourier transform spectrometer and therefore could not observed in this work.

10 Intensity ratio (IAr+He / IAr)

In this case, the additional particle produced allows energy and momentum conservation for a large

Fe II emission lines (b)

Hem

8 6 4 2 0

12

13

14

15

16

17

18

19

2

Excitation energy/ eV Cu II emission lines: With a copper cathode, 64 Fig. 3 Intensity ratios for iron ionic copper ionic lines were studied in the range 200 – emission lines measured in 40%Ar + 900 nm; a large number within 460 – 580 nm range 60% He as a function of excitation were observable in Ar-He plasmas. It is suggested energy using Fe sample. that these lines are predominately excited by asymmetric charge transfer between helium ions and ground state copper atoms (He-ACT) which is again a selective process.

+

+

Cuo + He → Cu * + Heo + ΔE

(3)

Several intense copper ionic lines with upper energies in the range 16.2 – 16.5 e\V were also recorded using Ar-He mixtures. It appears that these intense copper ionic lines may be the results of cascade effects. The increase in the population of highly excited levels of copper ionic lines by HeACT strongly affects the intensity of lines from lower levels. It was expected that these selective and non-selective processes would have significant effects on analytical applications of GD mass spectrometry. However, our MS studies using a Thermo Fisher Element GD MS showed a gradual increase in ion signal intensities of various minor and major constituents of matrix in Ar/He mixtures. The changes in intensities were not as dramatic as was expected from the considerable signal enhancements due to changes in excitation and ionization processes shown by our OES studies.

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(P19) THE MICROWAVE PHOTOCHEMICAL REACTOR FOR THE ON-LINE OXIDATIVE DECOMPOSITION OF P-HYDROXYMERCURYBENZOATE (PHMB)-TAGGED PROTEINS AND THEIR DETERMINATION BY LC-COLD VAPOUR GENERATION ATOMIC FLUORESCENCE DETECTION Beatrice Campanella1, Jose González Rivera2, Carlo Ferrari3, Massimo Onor1, Emanuela Pitzalis1, Alessandro D’Ulivo1 and Emilia Bramanti1 1

C.N.R., Institute of Chemistry of Organometallic Compounds, UOS of Pisa, Via Moruzzi, 1, 56124 Pisa, Italy. 2 Chemical Engineering Department, University of Guanajuato, Noria Alta s/n 36050, Guanajuato, Gto. Mexico. 3 National Research Council of Italy, C.N.R., Istituto Nazionale di Ottica, INO – UOS Pisa, Area di Ricerca, Via G. Moruzzi 1, 56124 Pisa (Italy).

e-mail: [email protected] Chemical labelling in combination with mass spectrometry is appointed as a modern approach for quantifying biopolymers, especially proteins. Protein labelling approaches are generally based on elemental mass spectrometry techniques, specifically inductively coupled plasma-mass spectrometry (ICP-MS). In this work we present a novel method for the characterization and determination of proteins labeled with p-hydroxymercurybenzoate (pHMB, an organic mercury species widely used for mercaptan and thiolic compound labeling), based on the on line oxidation of pHMB-labelled proteins with a novel on-line UV/microwave (MW) photochemical reactor, followed by cold vapour generation atomic fluorescence spectrometry (CVG-AFS) detection [1,2]. MW/UV process leaded to the quantitative conversion of pHMB and protein-pHMB complexes to Hg(II), with a yield between 89±0.5% without using chemical oxidating reagents and avoiding the use of toxic carcinogenic compounds. The MW/UV oxidation system and the CVGAFS detection system has been hyphenated with reversed phase (RP) and size exclusion (SEC) liquid chromatography. Acetonitrile (ACN), one of the typical organic eluents in RPC, does not affect sensitivity when MW/UV oxidation system is used. LC-MW/UV-CVGAFS method has been applied to the characterization, separation and determination of several thiolic proteins (albumins, beta-lactoglobulin and k-casein) using SEC and RPC. Several denaturation systems (8 M urea, 3 M GdmSCN, 0.2% SDS, thermal denaturation, 20% methanol, 50% trifluoroethanol) have been employed to study pHMBovalbumin complexes, using ovalbumin as a model protein. The maximum number of titrated SHgroups for OVA has been obtained denaturing the protein with 0.2% SDS at room temperature (2.7 ±0.3 SH- groups). SEC-MW/UV-CVGAFS has also been applied to the study of thiolic proteins in human plasma from normal donors and from patients affectd by amyloidosis. Finally, the potentialities of RPCMW/UV-CVGAFS have been explored for the characterization of proteic tryptic digests. REFERENCES [1] V. Angeli, C Ferrari, I. Longo, M. Onor, A. D’Ulivo and E. Bramanti. Analytical Chemistry 83 (2011) 338-343. [2] Valeria Angeli, Simona Biagi, Silvia Ghimenti, Massimo Onor, Alessandro D'Ulivo, Emilia Bramanti. Spectrochimica Acta B, 66 (2011) 799–804.

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(P20) STUDY OF THE INTERACTION OF CHLORINATED AND SULFOCHLORINATED PARAFFINS WITH GELATIN B AND SKIN POWDER. A MODEL FOR FATTENING IN THE LEATHER TANNING PROCESS1 Valentina Della Porta1, Susanna Monti1, Massimo Onor1, Alessandro D’Ulivo1, Emanuela Pitzalis1, Alice D’Allara2 and Emilia Bramanti1 1 2

C.N.R., Institute of Chemistry of Organometallic Compounds, UOS of Pisa, Via Moruzzi, 1, 56124 Pisa, Italy. ENEA, UTTMATF, Via Ravegnana 186 48018 Faenza.

e-mail: [email protected]

Fattening is crucial to confer exceptional softness, smoothness and elasticity on leather. Indeed, at the end of the tanning process leather does not contain enough lubricant to prevent it from drying into a hard mass. Fatting agents have the role of lubricating both the surface of collagen fibers and interfibrillar spaces by replacing water. Chlorinated and sulfo chlorinated paraffins (CPs and SCPs) are common fatting agents employed in the leather industry because it is supposed that they interact effectively with the collagen matrix. The most abundant collagen type consists of three polypeptide chains arranged in tight triplehelical structures where the conformation of each chain depends on the presence of glycine (GLY) and the high content of proline (PRO) and hydroxyproline (HPR). Fibrillar collagens contain uninterrupted sequences of GLY-X-Y triplets which are flanked by terminal globular domains (telopeptides). A careful analysis of the primary structure of collagen reveals the presence of some patterns and motifs, which may consist of a periodic distribution of certain sequences or features. For example, polar and hydrophobic residues are periodically clustered along the sequence of collagen I every 234 residues. Differently from fibrillar collagen, gelatin is a heterogeneous mixture of water-soluble proteins of high average molecular masses. These proteins are extracted by boiling skin, tendons, ligaments, bones, etc. in water. Little is known about the interactions of CPs/SCPs with collagen and gelatin. In this work we have performed experimental (FTIR spectroscopy) and computational (MD simulations) studies of the interaction of collagen, gelatin and skin powder with CPs and SCPs. The investigation of the reaction mechanisms involved in CPs/SCPs action on collagen can be a good starting point for the development of natural environmental-friend fatting agents1 and the definition of more effective and efficient industrial processes. (1)

Life + EU Project ENV/IT/364 “ECOFATTING”

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(P21) OPTIMIZATION OF ANALYTICAL TESTS FOR THE CHARACTERIZATION AND VALIDATION OF MERCURY-SORBENT MATRICES1 Massimo Onor, Emanuela Pitzalis, Alessandro D’Ulivo, Valentina Della Porta, Marco Carlo Mascherpa and Emilia Bramanti 1

C.N.R., Institute of Chemistry of Organometallic Compounds, UOS of Pisa, Via Moruzzi, 1, 56124 Pisa, Italy.

e-mail: [email protected] Atomic absorption spectrometry (AAS) and atomic fluorescence spectrometry (AFS) apparata were optimized to fast characterize the metal mercury adsorption capacity of carbon-based sorbents in the gas phase and in solution. These apparata was developed in the framework of an European project devoted to the optimization and production of a novel sorbent deriving from the pyrolitic conversion of waste tyres into activated carbon for the removal of mercury from gas streams impregnated with a sodium sulfide solution in order to improve its mercury binding capacity. In order to test the sorption properties in the gas phase, a selected amount of mercury released in an argon flow by a permeation tube kept thermostated at selected temperatures was delivered directly to the AAS or through a cartridge preloaded with activated carbon materials to be tested by switching two position six-port inert automated valve. In each experiment, accurately weighted amount of sorbents (in function of its capacity toward mercury determined in preliminary experiments) were charged into the fixed-bed reactor. The sorbent bed was maintained in place between two plugs of quartz wool tested, to be inert toward mercury. Prior to each adsorption experiment, the reactor was fully equilibrated at the desired temperature. Each sorption test was repeated at least three times and was reproducible to provide results within 3% for homogeneous samples. The gas flow rate was kept constant during the experiments by a mass flow controller (Brooks). AAS was used as mercury analyzer to continuously measure the elemental mercury Hg0 at the outlet. This instrumental set up allowed us the study of adsorption kinetic and the capacity of the sorbents. The mercury adsorption/binding capacity was also evaluated in solution in the perspective of an employment of the sorbent also for mercury removal from waste waters. For these experiments flow injection analysis coupled to Atomic Fluorescence Detector (FIA-AFS) was carried out in batch on samples (0.6-1 mg/mL) suspended and vortexed in Ultrapure water/4% methanol with 0.5 mM Hg(II) at different times. After centrifugation the surnatant was diluted 10 times and analyzed by FIA-AFS. The characterization of sorbents was completed with the analysis by a DMA-80 mercury analyser (FKV) of sorbents after the adsorption of mercury for closing the mass-balance of entire process. 1

EU project LIFE+2011 ENV/IT/109 “Low cost sorbent for reducing mercury emissions”

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Poster Abstracts

(P22) IMPROVEMENTS IN THE DETERMINATION OF SULFIDE, CYANIDE AND THIOCYANATE BY CHEMICAL VAPOR GENERATION COUPLED WITH HS-GC-MS Massimo Onor1, Sara Ammazzini1,2, Enea Pagliano3, Emanuela Pitzalis1, Emilia Bramanti1 and Alessandro D’Ulivo1 1

C.N.R., Institute of Chemistry of Organometallic Compounds, UOS of Pisa, Via Moruzzi, 1, 56124 Pisa, Italy 2 University of Pisa, Department of Chemistry and Industrial Chemistry, Via Risorgimento, 35 56125 Pisa, Italy 3 National Research Council Canada, Ottawa, Ontario K1A 0R9, Canada e-mail: [email protected] The use of trialkyloxonium salts has been recently proposed for the determination of anionic species by chemical vapour generation (CVG) coupled with head-space gas chromatography mass spectrometry (HS-GC-MS). In particular the use of aqueous Et3O+ BF4reagent is attractive because it is able to generate volatile ethyl derivatives of chloride, bromide, iodide, sulfide, cyanide, thiocyanate, nitrite and nitrate [1]. Fluoride can be also determined by using aqueous Et3O+ FeCl4 [2] Some anions such as sulfide, cyanide and thiocyanate show detection limits in the range of 200400 ng/mL, which are more than two orders of magnitude worse than those obtained for the other anions. In the present work is reported a study for the optimization of the reaction conditions with the aims to get significative improvements in the sensitivity of CVG-HS-GC-MS determination of these anions. The experimental parameters, which are considered to play a role in the generation efficiency of volatile ethyl derivatives are: the reaction temperature, the amount of ethylating agent and the concentration of ammonia buffering solution. All experiments were performed by using a GC-MS system (Agilent 5975c mass spectrometer and 6850 gas-chromatograph equipped with head space autosampler and incubating tool (Combi PAL CTC .). Temperature was varied in the range of 30-90 °C, the concentration of Et3O+ BF4 was varied in the range of 1-1000 mM and the concentration of ammonia in the range of 2.5-2500 mM. The optimized reaction conditions are 70 °C , Et3O+ BF4 = 250 mM , NH3 = 500 mM, respectively for sulfide and cyanide, 70 °C , Et3O+ BF4 = 250 mM , NH3 = 750 mM for thiocyanate. Under optimized conditions the detection limits (3s) are 0.08, 35 and 1.7 ng/mL for sulfide, cyanide and thiocyanate, respectively (1 mL headspace injected, 2 ml of sample plus 3 ml of reagents and internal standards in 10 ml vial), which represent improvement factors of 4103,10, 160 with respect to the previously reported figures [1]. Application to biological samples (thiocyanate and other anions in human saliva and plasma) and certified reference material (free cyanide and sulfide in 0.1% NaOH RTC-Fluka) are reported. [1] A. D’Ulivo, E. Pagliano, M. Onor, E. Pitzalis, R. Zamboni, Anal. Chem., 2009, 81 (15), pp 6399–6406 [2] E. Pagliano, J. Meija, J. Ding, R. E. Sturgeon, A. D’Ulivo, Z. Mester, Anal. Chem., 2013, 85 (2), pp 877–881

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XXXVIII CSI 2013

Poster Abstracts

(P23) DEVELOPMENT AND EVALUATION OF DESOLVATION SYSTEM FOR DROPLET DIRECT INJECTION NEBULIZER Yuki Kaburaki1, Tomokazu Kozuma1, Akito Nomura1, Takahiro Iwai1, Hidekazu Miyahara1, Akitoshi Okino 1 1

Department of Energy Sciences, Tokyo Institute of Technology, Japan

e-mail: [email protected] In recent years, there is growing interesting in trace element analysis for single cell or single nano-particle. For example, cause of cancer or Alzheimer disease is hoped to be figured out by trace element in single cell[1]. Inductively Coupled Plasma Mass Spectrometry (ICP-MS) has been widely used for trace element analysis because of analytical figure of merit. However, conventional sample introduction system for ICP-MS consumes large amount of sample solution. So, it is difficult to realize individual single cell analysis. In our previous research, droplet direct injection nebulizer (D-DIN) was developed. D-DIN can introduce into the ICP droplet of diameter 30 to 70 μm. By including cells in a droplet, this system enables to introduce single call to ICP. In 2012, we applied D-DIN system to ICP Time of Flight Mass Spectrometry (ICP-TOFMS) to realize multi-element analysis in a droplet sample. But, signal intensity of small droplet was higher than that of larger droplet. From this result, it was suggested that desolvation was not enough so the droplet size was too large. Thus, we developed desolvation system for D-DIN. Schematic of the system is shown in Fig. 1. Heating part is 150 mm of length and the gas temperature was measured by a thermocouple. Cooling part is used copper pipe spiral of 80 mm in length and cooled through water inside the pipe. Droplet has heated by around 200℃ heating carrier gas before introducing to ICP. The temperature in cooling part was around 10℃ for working as a condenser. To investigate effect of the heating system, we applied the system to ICPAtomic Emission Spectrometry (AES). By using the droplet desolvation system, emission intensity of Ca ion enhanced about 10 times compare with normal system. Excitation temperature and electron number density was measured when droplet was introduced into the plasma. Excitation temperature was decrease of about 150 ℃ and electron number density did not change. These results show that stability of the plasma was not affect. To remove the water vapor, Fig. 1 Schematic of droplet desolvation cooling system was applied after the heating system. The spectroscopic characteristics such as emission intensity, excitation temperature and electron density will be presented. References H. Haraguchi et al., J. Anal. At. Spectrom., 19, 4 (2004).

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XXXVIII CSI 2013

Poster Abstracts

(P24) STUDY OF THE EXCITATION PROCESSES INVOLVING OXYGEN AS AN ADDED GAS IN A NEON ANALYTICAL GLOW DISCHARGE PLASMA Sohail Mushtaq1, Edward B. M. Steers1 and Juliet C. Pickering2 1 2

London Metropolitan University, 166-220 Holloway Road, London, N7 8DB, UK Blackett Laboratory, Imperial College London, London SW7 2BW, UK

E-mail: [email protected]

Energy /eV

Investigations of the effects of oxygen as an added gas in a neon analytical glow discharge plasma with various samples (cathodes) over a wide spectral range have been undertaken using a Grimmtype Glow Discharge (GD) source and Fourier Transform Optical Emission Spectroscopy (FTOES). Significant variations to the relative spectral line intensities of both the sputtered matrix and plasma gas are observed in presence of oxygen. Penning ionisation and Asymmetric Charge Transfer (ACT) are shown to be involved. It is obvious from Fig. 1 that there are Energy level of various elements several copper ionic energy levels close to the ionization energy of neon 22 Ne-ACT  +  Neo    (~ 21.564 eV), which are suitable for     asymmetric charge transfer, viz: 20    (1) Cuo + Ne+ → Cu+* + Neo + ΔE,      where the subscript o and superscript * 18 Penning Ionization represent ground and excited states Nem    respectively, and ΔE is the small energy 16  difference which can be either positive + O 14 (exoergic) or negative (endoergic). Both    exoergic Ne-ACT and endoergic Ne-ACT    12 are possible in case of copper sample.   Copper ionic emission lines which are     10 selectively excited by Ne-ACT can be Cu Ne O identified in 240 – 275 nm range. Added Fig. 1 Schematic representation of some energy levels of gas can also be involved in ACT excitation; relevant elements (atomic in blue, ionic in red). Only the however, copper does not possess ionic region of interest from 10 eV up to 22 eV is shown. 1.2 energy levels suitable for ACT involving Cu II 272.168 nm, 21.380 eV oxygen ions. Cu II 242.443 nm, 21.378 eV EY(Ne + O2) / EY(Ne)

1.0

Cu II 246.850 nm, 21.410 eV Cu II 248.579 nm, 21.378 eV Cu II 252.930 nm, 21.410 eV Cu II 270.096 nm, 21.410 eV

0.8 0.6 0.4 0.2 0.0

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Fig. 2 Emission yield ratios against various oxygen concentrations for selected Cu II lines (700 V & 20 mA.)

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The presence of oxygen in a neon plasma reduces the sputter rate, therefore, ‘emission yield’ (EY), i.e., the intensity divided by the sputter rate and the concentration of analyte in the sample, of analyte lines have also been determined. In Fig. 2 the emission yield ratios (EYNe+O2/EYNe) of selected Cu II lines excited by Ne-ACT are plotted against various oxygen concentrations in neon. It is appeared that in neon/oxygen mixed plasmas, Cu II lines excited by Ne-ACT are reasonably weaker, probably due to

XXXVIII CSI 2013

Poster Abstracts

Intensity ratio (INe + O2 / INe)

quenching of neon ions and respectively reduction of NeACT. It is evident in Fig. 3 that by OES studies that there is significant decrease in Ne II spectral lines with the addition of oxygen in plasma gas. This is first thorough OES study of Ne/O2 plasmas in Grimm-type 1.2 Ne II 321.819 nm, 56.301 eV - 52.449 eV glow discharges. So far no Ne II 319.858 nm, 56.366 eV - 52.491 eV systematic MS studies on 1.0 Ne II 338.842 nm, 56.406 eV - 52.748 eV Ne/O2 mixed plasmas have Ne II 421.974 nm, 59.110 eV - 56.172 eV been carried out with similar Ne II 439.199 nm, 59.123 eV - 56.301 eV 0.8 sources and discharge Ne II 440.930 nm, 59.123 eV - 56.312 eV conditions. 0.6

The Cu ionic energy levels 0.4 close to the neon metastable levels (16.62 & 16.72 eV) (see Fig. 1) may be populated 0.2 by Penning ionization viz: Cuo + Nem* → Cu+* + Neo + e0.0 + ΔE (2) 0.0 0.2 0.4 0.6 and also by cascade processes Oxygen concentration (% v/v) from higher levels. The Fig. 3 Intensity ratios of selected neon ionic lines vs oxygen concentrations. (700 V, 20 mA, 4 mm diam anode tube). corresponding Cu II emission lines occur in the 213 – 230 nm wavelength range. These Cu II lines are decreased with the addition of oxygen to the plasma, probably due to quenching of Nem atoms. However, the decreases in intensities of these emission lines are less than those for the lines excited by Ne-ACT. 6

Ne I 640.225 nm, 16.619 eV - 18.555 eV 5

Intensity (a.u.)

A comprehensive investigation of Ne I spectral line profiles has been carried out in pure Ne and Ne/O2 mixed plasmas. It appears that the large increase in the observed intensities of Ne I lines is occurred due to reduction of selfabsorption, when oxygen is added to plasma gas (see Fig 4).

4

Pure Ne 0.20% O2 0.40% O2

3

0.80% O2

2

1 Results of neon/oxygen are also compared with the case of argon/oxygen 0 mixtures. In presence of oxygen, it is 15614.8 15615.0 15615.2 15615.4 15615.6 -1 observed that sputter rate decreases Wavenumber / cm significantly more in neon than in argon. Fig. 4 Lines profiles of Ne I 640.225 nm, showing The energy transfer collisions of Nem self-reversal in some cases self-absorption for atoms play a dominant role to both various oxygen concentration in neon discharge. dissociate the oxygen molecule and excite directly one of the dissociative products to energy levels which emit a group of intense oxygen lines in near-infrared region. Such a resonant energy transfer between Arm atoms and the ground state molecules of oxygen in these particular levels is not possible in argon/oxygen mixtures.

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XXXVIII CSI 2013

Poster Abstracts

(P25) INVESTIGATIONS ON THE USE OF AMMONIA AS A REACTION GAS TO OVERCOME INTERFERENCES IN RARE EARTH ELEMENTS BY ICP-MS Jessee Severo Azevedo Silva1, Tatiane de Andrade Maranhão2, Daniel L. Galindo Borges1, Vera Lucia A. Frescura1 and Adilson José Curtius1 1 2

Universidade Federal de Santa Catarina, Florianópolis, SC, Brazil Universidade Federal do Rio Grande do Norte, Natal, RN, Brazil

e-mail: [email protected] The interest in rare earth elements (REE) research in different areas has grown significantly since China, in 2009, decided to reduce the amount of REE exported to foreign countries. For many years China had been the greatest supplier and detainer of the technologies for the production of REE. After China’s restriction, many countries started to establish policies to increase REE production, which requires investment in specific research fields. Analyses of samples containing REE require sensitive and multielement techniques and, in this case, the most attractive technique is ICP-MS. However, REE determination by ICP-MS can be difficult, since these elements are susceptible to polyatomic interferences. The use of a reaction/collision cell, in which a reactive or collisional gas is used, is well reported as a solution to overcome polyatomic interferences. In this work, a study to evaluate the effect of NH3 in reducing polyatomic interferences and on the signal of four REE was carried out. Blank solutions, containing only the interfering elements, and solutions containing the analytes and interfering elements were analyzed using different gas flow rates. All isotopic signals were monitored for each of the analytes (Gd, Lu, Nd ad Yb) in both solutions. The signal for possible secondary ions formed with the analytes (IO+ or INH3) was also monitored. The study showed an important formation of polyatomic interfering ions in the plasma environment, which could cause an increasing in the signal of the analytes, as can be seen in Figures 1 to 4 (A) . The use of NH3 is effective in reducing these interferences. The effect of ammonia on the analyte signal was investigated and the results showed that NH3 causes a significant decrease in the signal for all analytes. Overall, as shown Figures 1 to 4 (B), ammonia gas flows ranging between 0.4 and 0.6 mL min-1 were proven effective in reducing interference effects of polyatomic ions over REE signals, which leads to the assumption that interference-free determination of the REE is feasible under these conditions. The monitoring of secondary ions formation with the analytes revealed that for Lu the use of NH3 contributes significantly to the formation of the ion mass 191, at low flow rate, but at higher flow rate the signal for this ion decreases (Figure 1 C). For Yb the formation of secondary ions was not observed. The monitoring of Gd secondary ions showed that the signal for the ion mass 171,172, 173, 174 and 176 is significantly high at absence of NH3 and at low gas flow rate a slight increase in the signal occurs (Figure 3 C). This suggests that the secondary ions formation occurs mostly in the plasma environment. For Nd the behavior is very similar, but no one contribution of the NH3 gas on the signal increasing is observed (Figure 4 C).

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XXXVIII CSI 2013

Poster Abstracts

60000

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Figure 1. Effect of NH3 in the Lu signal for: (A) 10 µg L-1 Gd and Tb blank solution; (B) 10 µg L-1 Lu, Gd and Tb solution; and (C) in the signal of LuO+ or LuNH3+. 48000

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Figure 3. Effect of NH3 in the Gd signal for: (A) 10 µg L-1 Nd, Ce, Pr and La blank solution; (B) 10 µg L-1 Gd, Nd, Ce, Pr and La solution; and (C) in the signal of GdO+ or GdNH3+. 200

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Figure 4. Effect of NH3 in the Nd signal for: (A) 10 µg L-1 Ru and Te blank solution; (B) 10 µg L-1 Nd, Ru and Te solution; and (C) in the signal of NdO+ or NdNH3+.

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XXXVIII CSI 2013

Poster Abstracts

(P26) STUDY OF TETRACYCLINE FRAGMENTATION WITH LC-MS Martin Šala,1 Drago Kočar,2 Tadeja Lukežič,3 Gregor Kosec3 and Hrvoje Petkovič3 1

National Institute of Chemistry, Laboratory for analitical chemistry, Hajdrihova 19, 1000 Ljubljana, Slovenia 2 University of Ljubljana, Faculty of chemistry and chemical technology, , Aškerčeva 5, 1000 Ljubljana, Slovenia 3 Acies Bio, d.o.o., Tehnološki park 21, 1000 Ljubljana Slovenia e-mail: [email protected] Tetracyclines are a class of medically important broad spectrum antibiotics that were discovered more than 60 years ago as fermentation products of soil bacteria from the group of actinomycetes. The core structure of tetracyclines consists of four rings, of which one is usually aromatic and their biosynthesis is is catalysed by complex enzymatic systems termed polyketide synthases. Massive use of this class of antibiotics led to wide-spread occurrence of resistance genes, thus there is immense need to develop new antibiotics with novel mode of action. In addition to the typical TCs, which bind strongly to bacterial ribosomes and inhibit translation, second group of TCs, the so-called atypical TCs, with yet unknown mode of action, such as anhydrotetracycline, 6thiatetracycline and chelocardin (CHD). Considering CHD displays unusual tetracycline backbone and potent antibacterial activity with a mode of action fundamentally different from other TCs, CHD backbone can serve as suitable scaffold for biosynthetic engineering of novel antibacterials, which could be further derivatised through semi-synthetic efforts in order to develop compounds active against multi resistant pathogen strains. In search for new potentially medically useful tetracyclines, fast and simple identification and determination of their structure is of great importance. MS/MS determination of these class of compounds is based on the most abundant MRM transitions, where neutral loss of amino group, water or in some cases both occurs. Up to now fragmentation of tetracyclines was not studied in detail. We have investigated the fragmentation pathways of the most common clinically used tetracyclines as well as some structurally unusual tetracyclines. We also discuss the different fragmentation patterns of epimeres.

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XXXVIII CSI 2013

Poster Abstracts

(P27) METHOD DEVELOPMENT FOR THE ANALYSIS OF ORGANOPHOSPHORUS COMPOUNDS IN LIPF6-BASED ELECTROLYTES Vadim Kraft, Martin Grützke, Martin Winter and Sascha Nowak* University of Münster, MEET Battery Research Centre, Corrensstraße 46, 48149 Germany *e-mail: [email protected] Lithium-ion batteries are widely used in modern consumer electronics and are increasingly used for electric vehicles. Due to the high energy density and good cycling stability these energy storage systems become more and more important for the economy. The main disadvantage of the batteries is limited cycle life due to unwanted chemical reactions for example of the electrolytes. Furthermore the high temperature accelerates the decomposition. To increase the efficiency of Liion batteries and understanding of the degradation steps is necessary. A series of experiments with commercially available non-aqueous LiPF6-based electrolytes has been carried out. The samples were stored at various temperatures for several weeks and analysed to investigate the thermal influence on the decomposition reactions. The separation of the decomposition products was performed by an ion chromatography system (IC). For improving of the separation different columns were used. Also a gradient step for the reduction of the retention time was applied. For the elucidation of the structural formula of the compounds the IC was coupled to electrospray ionization (ESI-MS).

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XXXVIII CSI 2013

Poster Abstracts

(P28)

IN-SITU MÖSSBAUER SPECTROSCOPY AS A NON-DESTRUCTIVE TOOL TO ANALYZE LITHIUM-ION BATTERY AGING Sascha Weber1, Thorsten Langer1,2, Falko Schappacher1, Rainer Pöttgen2 and Martin Winter1 1

MEET Battery Research Center, University of Münster, Corrensstr. 46, 48149 Muenster, Germany 2 Institute of Inorganic and Analytical Chemistry, University of Münster, Corrensstr. 28/30, 48149 Muenster, Germany e-mail: [email protected] Lithium ion batteries suffer from capacity loss effects that shorten their lifetime. This is commonly called battery aging. To analyze the processes that occur in the cell and lead to the capacity loss it is important to develop analytical methods that can not only be applied under post-mortem conditions but also in-situ to a lithium ion full cell. Commonly Mössbauer spectroscopy is used to characterize new materials synthesized to be used as the electrochemically active part of lithium ion battery electrodes. Several groups have in-situ cells to characterize e.g. LiFePO4 electrodes. developed special We present the application of Mössbauer spectroscopy on a lithium ion full cell in pouch bag design. The cell consists of a LiFePO4 cathode and a graphite anode and uses organic electrolyte. Mössbauer spectra were recorded at several state of charge (SOC) levels and at several state of health (SOH) levels of the battery. From the recorded spectra the ratio of lithiated (LiFePO4) and delithiated (FePO4) active material was extracted and could be attributed to a certain SOC. Furthermore a shift of the phase ratio in dependence of the cell’s lifetime has been detected. This is correlated with the loss of capacity. So it is possible to assume that the amount of available lithium ions in the cell is too low to recharge all particles of the active material.

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XXXVIII CSI 2013

Poster Abstracts

(P29) COMPARISON OF VARIOUS SPECTROSCOPIC IMAGING TECHNIQUES FOR INVESTIGATION OF HG AND SE METABOLISM IN PLANT TISSUES Marta Debeljak1, Johannes Teun van Elteren1, Katarina Vogel-Mikuš2, Alessandra Gianoncelli3, David Jezeršek3 1

National Institute of Chemistry, Hajdrihova 19, 1000 Ljubljana, Slovenia Department of Biology, Biotechnical Faculty, University of Ljubljana, Večna pot 111, 1000 Ljubljana, Slovenia 3 Synchrotrone Elettra, Strada Statale 14, 34149 Basovizza, Trieste, Italy 2

e-mail: [email protected] Mercury (Hg) is one of the most toxic metals found in the environment, known to accumulate in food webs with a biomagnification pattern at successive trophic levels. Uptake, transport and transformation of Hg in plants depend on the soil properties as well as the plants metabolic processes. Since selenium (Se) resembles the chemical properties of sulphur and has a high affinity to bind Hg, Se could play an important role in mercury detoxification. Therefore, knowledge on the behaviour of Hg and Se in plant organisms might help us to characterize Hg and Se uptake and distribution in plant tissues and additionally aid in the development of phytoremediation techniques and lowering of Hg uptake into food webs. This work focused on the development/application of imaging of spatial distribution of Hg and Se in plants at the macro (organ/tissue) and micro (tissue/cellular) level. Plants (Zea mays L. and Helianthus annuus L.) were grown in hydroponic nutrient solution with 0.8 mg/kg Se(IV) or Se(VI) in commercial pot substrate amended with 50 mg/kg of HgCl2. The samples were prepared using cryo-fixation/microtoming. For elemental imaging both laser ablation-ICPMS and synchrotron radiation-based micro-X-ray fluorescence spectrometry techniques were used for fast, low-resolution (> 8 μm) mapping of large areas (≥ 1 mm2) and high-resolution (sub-μm) mapping of small areas (≤ 0.05 mm2), respectively.

B)

A)

Figure 2: Microscopic image (Nikon Eclipse TE200 inverted microscope) of a maize root sample cross-section subjected to laser ablation (A) and the mercury distribution (mg/kg) in this section (B).

Laser ablation-ICPMS mapping was conducted with a 213 nm Nd:YAG laser interfaced with a quadrupole ICPMS instrument; calibration was realized with Se and Hg-spiked Tissue freezing medium® embedding resin. 2D mapping via conventional parallel line scanning protocols was found to be unusable due to sorption of mercury onto the internal parts of the LA device, giving

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XXXVIII CSI 2013

Poster Abstracts

rising to memory effects resulting in serious loss of resolution and inaccurate quantification. Spot analysis on a virtual grid on the surface of the sample using washout times of 10 s in between spots greatly alleviated problems related to these memory effects. µ-XRF measurements of the Hg and Se distribution were performed at the ID22 beamline, ESRF, Grenoble (France); the energy was set at 13 keV and the beam was focused using a KirkpatrickBaez mirror to generate a 3.5  1.5 µm2 spot size. µ-XRF measurements of the Se distribution were also performed at the TwinMic beamline, synchrotron Elettra, Trieste (Italy); the energy was set at 1.64 keV and the beam was focused using a zone plate to generate a 1.2 µm2 spot size. A)

Figure 3: Microscopic image (Nikon Eclipse TE200 inverted microscope) of a maize root sample cross-section with the marked region of interest (A) and the mercury distribution (counts/sec) in a maize root by µ-XRF at the ID22 beamline, Grenoble, showing retention of Hg in the endodermis and cortex (B), where it is colocalized with sulphur (C).  

Imaging with the mentioned techniques led to the following findings: i) Hg was localized mainly in root epidermis and endodermis (Figure 1); ii) High-resolution imaging showed that Hg was also present in the cortex and that it was colocalized with sulphur, hereby confirming that Hg preferentially binds to sulphur ligands (Figure 2); iii) In Se(IV)-treated plants, Se was mainly localized in epidermal and sub-epidermal root tissues, while in Se(VI)-treated plants higher concentrations were seen in root cortex, indicating that Se(VI) is more mobile than Se(IV); iv) In Se(VI)-treated plants Se was readily translocated to the leaves, where it mainly accumulated in leaf mesophyll (Figure 3).

Figure 4: X-ray absorption image (A) and distribution of selenium (counts/sec) in sunflower leaf sample by µ-XRF at the TwinMic beamline, Trieste, showing Se accumulation in leaf palisade mesophyll (B).

All imaging techniques proved to be suitable for Se localization in plant tissues. Although the SRµ-XRF techniques generated higher resolution image maps, laser ablation-ICPMS is a technique which is better accessible and less time consuming.

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XXXVIII CSI 2013

Poster Abstracts

(P30) SIZE CHARACTERISATION OF METALS IN TUNNEL WASH WATER AS A FUNCTION OF TIME AND DETERGENT Jon-Henning Aasum1, Elin Gjengedal1 and Sondre Meland1, 2 1

Department of Plant and Environmental Sciences, Norwegian University of Life Sciences, PO Box 5003, N-1432 Ås, Norway

2

Norwegian Public Roads Administration, Environmental Assessment Section, PO Box 8142 Dep, N-0033 Oslo, Norway e-mail: [email protected]

Contaminated water from roads, including water from washing of tunnels, can be a threat to lakes and rivers. The tunnels in Norway are regularly cleaned in the form of sweeping and washing with water to avoid unfavourable conditions in the tunnel such as bad air quality, accumulation of dirt, and corrosion on the tunnel walls and other technical infrastructure. The washing frequency is dependent on the traffic. Hence, tunnels with annual average daily traffic (ADT) above 15 000 vehicles are washed at least 6 times/year while tunnels with ADT below 4000 vehicles are washed once every fifth year. In brief, tunnels are washed by using detergent and high pressure cleaning leading to large volumes of highly contaminated water. The detergent concentrations in the discharged tunnel wash water typically ranges between 0.2 % and 0.5 % volume concentration. The washing process often leads to emissions of partly highly polluted wastewater. Due to the high pollutant content in the tunnel wash water there is now common practice to treat the wash water before it is discharged to a nearby recipient. The most frequent applied method is to build sedimentation basin inside or outside the tunnel. This is reasoned by the fact that a lot of the contaminants are associated to particles. Hence, the treatment of tunnel wash water is based on sedimentation processes removing particle-associated contaminants, and therefore, the removal of dissolved contaminants, i.e. the mobile and assumed bioavailable fraction, is considered low. Currently there is little information on how the detergent affects the sedimentation processes, and the present study aimed to investigate how the detergent influenced this process by size fractionating metals in tunnel washing water as a function of time and detergent concentrations. It is important to obtain knowledge of the effect of detergent on fractionation of metal in tunnel wash water to optimize procedures for operation of the sedimentation basin and thereby minimize the impact on the natural environment. The cleaning process was simulated in a lab and the metals were separated depending on particular and molecular size using filters and a centrifuge. The conditions of the sedimentation basin used to remove contaminates from the wash water was simulated in the laboratory using 15 L rectangular plastic water tanks (Asaklitt) stored at 3 – 4 °C for three weeks. Wash water was obtained during washing of the 3.8 km long Nordby tunnel situated along E6 south of City of Oslo (Akershus county). The tunnel has two separate tubes with four lanes. The ADT is approximately 40 000 vehicles/day. Varying amounts of the detergent (TK 601, Teknisk Kjemisk Produksjon AS) was added to the wash water, resulting in 0, 0.5 and 3.0 % volume concentrations. Each treatment was conducted in triplicates. There were therefore a total of 10 water tanks, including a water tank with distilled water.

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A sampling system was constructed in the cooling room to avoid contamination of the water during the experiment. This system included two pumps, which pumped water from the water tanks at a set depth, half the depth of the tank, to a three-way valve. This sent the water through for sample collection, or to a 0.45 μm filter (GWV High Capacity Groundwater Sampling Capsules with 0.45 μm Versapor membrane, Pall Life Sciences). The filtered samples were then further processed by using a centrifugal tube with a 10 kDa filter (Amicon® Ultra-15 10K Centrifugal Filter Devices, Merck Millipore Ltd.) and centrifuged at 5000g for 15 minutes. Thus, the following size fractions were obtained: particulate (>0.45 µm), colloidal (0.45 µm – 10 kDa) and low molecular mass fractions (< 10 kDa). The water tanks were left still for 21 days after the addition of the detergent to allow sedimentation. Using the sampling system, water samples were collected after 0, 30 minutes, 1 day, 3 days, 9 days and 21 days after the start time. The total, filtered and centrifuged samples were then analysed for concentrations of metals using ICP-MS (AGILENT 8800 QQQ instrument). In addition to metals, the pH, conductivity, TOC, DOC, concentrations of anions and the concentrations of tensides in the water were determined. Currently, the water samples are being analysed and the results will be presented at the conference.

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(P31) DIRECT DETERMINATION OF BROMINE IN PLASTIC MATERIALS BY MEANS OF SOLID SAMPLING HIGH-RESOLUTION CONTINUUM SOURCE GRAPHITE FURNACE MOLECULAR ABSORPTION SPECTROMETRY María R. Flórez, E. García-Ruiz, Martín Resano Department of Analytical Chemistry, University of Zaragoza, Zaragoza, Spain, 50009 e-mail: [email protected] The ubiquity of plastic materials and the huge amount of plastic waste generated in the modern world has led to a growing concern in terms of the environmental impact. In this context, special attention is being paid to the variety of different inorganic and organic additives incorporated to the structure of the polymers to enhance their qualities and their leakage to the environment. Most polymeric materials, and particularly those aiming to be employed in the production of electronic devices, electrical appliances, clothing and furniture, are very often protected against ignition by the addition of the so-called brominated flame retardants (BFRs). While new environmentally safe flame-retardants alternatives are being investigated, regulations and restrictions in the use of organo-BFRs are being implemented in order to lower the impact by legally banning or setting maximum limits to total contents. It is essential then to have robust analytical methods for monitoring the presence of these compounds in raw plastic materials. Whenever the purpose is to have information about total BFRs content (most legal limits are established regarding this parameter) rather than or prior to gather information for each isolated compound, determination of total Br content in the sample becomes a reliable indicative. Most usual methods for determining Br in BFRs require extensive sample preparation steps to have the sample in an appropriate liquid form. This step needs to be thoroughly controlled in order to minimize the risk of Br losses due to its high volatility. Few approaches have been made up to date focusing on the development of methods for the direct determination of the solid materials, Thus, some more work stills to be needed regarding the development of simple and fast methodological approaches with enough sensitivity to fulfil the requirements of the current EU regulations concerning the use of BFRs in electrical and electronic equipment. It is the goal of this paper to develop a simple procedure for the direct determination of total Br content in plastic samples by means of high-resolution continuum source graphite furnace molecular absorption spectroscopy. This method is based in the formation of the diatomic molecule CaBr,1 stable in gas phase at relatively high temperature, and the recording of its molecular spectra in the vicinity of 625.315 nm, using aqueous standards for calibration. References 1. M. D. Huang, H. Becker-Ross, S. Florek, U. Heitmann, M. Okruss, Spectrochim. Acta Part B, 2013, 63, 566–570

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(P32) CHANGES IN CHEMICAL COMPOSITION OF URBAN PM2.5 BETWEEN 2010 AND 2013 IN HUNGARY Tamás Szigeti1, Mihály Óvári1, Franco Lucarelli2, Gyula Záray1, Victor G. Mihucz1 1

Department of Analytical Chemistry, Eötvös Loránd University, 1117 Budapest, Hungary Department of Physics and Astronomy, University of Florence/INFN, 50019 Sesto Fiorentino, Italy 2

e-mail: [email protected] Aerosol particles play a key role in urban air quality because their adverse effects on human health and local environment. In the new EU Directive (2008/50/EC), an annual mean PM2.5 (particles with aerodynamic diameter smaller than 2.5 μm) concentration of 25 μg/m3 has been set as target value as of 1st of January 2010. However, the monitoring of the chemical composition of PM2.5 is still not regulated. PM2.5 sampling was performed about 15 m away from a busy road in the city centre of Budapest, Hungary. High-volume aerosol sampler (30 m3/h) was used for the collection of the aerosol particles for 96 hours (from Monday morning to Friday morning) in the first week of each month from June 2010 onto 150 mm quartz fibre filters (Whatman QM-A). Field blanks were also employed. The analyses included (i) gravimetric determination of PM2.5 mass concentration; (ii) trace element determination (Bi, Cd, Co, Cr, Cu, Fe, Ga, Li, Mn, Mo, Ni, Pb, Pt, Rb, Sb, Sn, Te, Tl, U, V, Zn) after microwave‐assisted aqua regia and sonication‐assisted water extraction by inductively coupled plasma sector field mass spectrometry; (iii) evaluation of major ion concentrations in the aerosol samples subjected to sonication‐assisted water extraction by ion chromatography; (iv) assessment of total carbon and its water soluble part by a C/N analyzer; (v) determination of organic and elemental carbon by a thermal-optical transmission technique using a Sunset Laboratory OC/EC analyser. Seasonal variation was observed in: (i) the PM2.5 mass concentration; (ii) some trace element concentration (i.e., Fe, Zn, Pb, Cd and Tl); (iii) the major anion content (sulphate vs nitrate). The financial support through grant TÁMOP-4.2.2/B-10/1-2010-0030 is hereby acknowledged.

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(P33) DETERMINATION OF FLUORINE USING HIGH RESOLUTION CONTINUUM SOURCE MOLECULAR ABSORPTION SPECTROMETRY (HR-CS MAS) René Nowka and Heike Gleisner Analytik Jena AG, Konrad Zuse Straße 1, 07745 Jena, Germany e-mail: [email protected] For the first time, state of the art atomic absorption technology (HR-CS AAS) allows the determination of non-metals with an AAS instrument, contrAA Analytik Jena AG Germany. The spectrometer used is equipped with a high intense continuum radiation source (Xe short arc lamp), a high resolution double Echele monochromator and a CCD array detector. By converting the analytes not into atoms like in conventional line source AAS but into characteristic molecules allows the determination of nonmetals eg fluorine by molecular absorption spectrometry (MAS). HR-CS MAS is a new, sensitive method for the analysis of the total content of fluorine and other non metals in aqueous and organic solutions as well as directly in solids – independent of the bonding form. This study shows the determination of fluorine in concentrated nitric and sulfuric acid without complicated sample preparation. Both, free as well as organically or inorganically bound fluoride is converted to the target molecule gallium mono fluoride (GaF) in a graphite furnace for subsequent spectrometric determination. This means, for the first time, a simple, fast and reliable spectrometric method is available for fluorine determination in almost every matrix and over a wide concentration range. Graphite furnace HR-CS MAS is a precise, robust and interference free as graphite furnace AAS and is not subject to any restrictions with regard to the pH value and the sample matrix, so that sample preparation is reduced to a minimum.

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(P34) DETERMINATION OF TRACE ELEMENTS IN BLACK AND WHITE PEPPERS BY XRF SPECTROMETER EQUIPPED WITH POLARIZATION OPTICS AND ITS DEVELOPMENT TO IDENTIFICATION OF THEIR PRODUCTION AREA Akiko Hokura1, Megumi Shibasawa1 and Noriko Kuze2 1

Department of Green and Sustainable Chemistry, Tokyo Denki University Senju-Asahicho, Adachi, Tokyo 120-8551 Japan 2 Kaneka Sun Spice Co., Ltd, Juso-higashi, Yodogawa, Osaka 532-0023 Japan e-mail: [email protected] Agricultural products are increasingly labeled with their geographical origin in many countries. Geographical identification can be useful for branding strategy purposes and to help consumers in their selection of foodstuffs. Spices are commonly used all over the world. The large quantities of spices are imported from Asian countries to Japan. The technique for determination of the geographic origin of agricultural products is needed. Mineral composition is one of the useful factors for that. The aim of this study is to develop the analytical method for determination of trace elements in spices such as black and white peppers by XRF. The chemometrics analyses using the data are conducted for determination of their geographic origin. Black and white peppers produced in south-eastern Asia were used in this study. The pepper sample was milled and homogenized. The weighed amount of 0.5 g was pressed into a tablet and subjected to XRF analysis. An XRF spectrometer equipped with polarization optics, Epsilon 5 (PANalytical), was used to determine the elemental concentration.

Figure 1: Linear Discriminant Analysis plot showing excellent separation of the different production area of black pepper. Eq. 1 y = - 0.0071[Cl] + 0.0008[K] - 0.0205[Ca] + 0.1098[Mn] - 0.7333[Cu] 0.7581[Rb] + 0.0042[Sr] + 75.4225 Eq. 2 y = 0.0087[Cl] - 0.0028[K] - 0.0493[Ca] + 0.561[Mn] - 1.2705[Cu] + 1.0703[Rb] + 2.2167[Sr] - 4.6172 Eq. 3 y = - 0.5431[Cl] + 0.0242[K] + 0.0617[Ca] - 9.3196[Fe] + 2.757[Mn]+4.4237[Cu] - 41.9998[Rb] + 1675.75

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We successfully demonstrated to determine the multielement concentrations in spices with a rapid and easy way using the XRF spectrometer. The minimum detection limits for 11 elements (Cl, K, Ca, Mn, Fe, Cu, Zn, Br, Rb, Sr, Cd) were sub-ppm levels. The principal component analysis (PCA) and the linear discriminant analysis were carried out by using the elemental concentration of peppers to determine their geographic origin. Black peppers of south-eastern Asia were characterized based on their elemental composition (Fig. 1). The presented method demonstrated the effectiveness of determining the geographic origin of spices. [1] M. Shibasawa, N. Kuze, K. Inagaki, I. Nakai, A. Hokura, Adv. X-Ray. Chem. Anal., Japan, 43, 369-380 (2012). This work was partially supported by Research Institute for Science and Technology of Tokyo Denki University. Grant Number Q11E‐05/ Japan.

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(P35) DETERMINATION OF SELENIUM USING CHEMICAL AND PHOTOCHEMICAL VOLATILE COUMPOUNDS GENERATION COUPLED WITH ATOMIC ABSORPTION SPECTROMETRY Marcela Rybinova1, Vaclav Cerveny1 and Petr Rychlovsky1 1

Charles University in Prague, Faculty of Science, Department of Analytical Chemistry, Albertov 6, CZ-128 43 Prague 2, Czech Republic e-mail: [email protected] Selenium is one of the elements for which there is a thin border between their essential and toxic concentrations in environmental system; therefore it is necessary to pay attention to their determination. Presented study was focused on the determination of selenium in aqueous samples using two methods of its volatile compounds generation. First, newly emerging technique of UVphotochemical generation was used and then conventional chemical generation was applied for comparison. Atomic absorption spectrometry with the externally heated quartz tube (QF-AAS) was chosen for the detection with both approaches. The principle of conversion of nonvolatile precursors (inorganic selenium(IV)) from the condensed phase to volatile species is different. To be specific, in the case of UV-photochemical generation, volatile compounds are formed by the effect of UV irradiation in the presence of a low molecular weight organic acid (formic, acetic, propionic or malonic). Reaction mechanism remains the subject of discussion. In contrast to UV-photochemical generation, chemical generation is based on reaction with a reducing agent, most commonly NaBH4, with the involvement of high-purity mineral acid (generation according to ”hydrogen transfer theory”). For UV-photochemical generation, attention was first paid to the construction of the photoreactor. Photoreactor was realized by attaching reaction coil to the surface of low-pressure Hg vapor UV lamp (20 W, 254 nm). The subject of interest was the material and the length of the coil. PTFE and quartz tubes of different diameters were tested. Optimum experimental conditions for UVphotochemical volatile compounds generation using formic acid were found after the completion of the apparatus. Formic acid was chosen for the study as a representative of simple organic acids. Following key parameters were optimized: the sample flow rate, the carrier gas flow rate as well as the auxiliary hydrogen flow, the concentration of formic acid or the concentration of additives. Analyte response was significantly increased by adding HNO3. With the instrumental setup and the optimum analytical conditions, a detection limit of 39 ng L–1 Se(IV) with a repeatability of 1.7 % (RSD, n = 10) was obtained. Similarly, optimum experimental conditions for more frequently used chemical generation were studied. Some of the tested parameters were the same, e.g. the sample flow rate or the carrier gas flow rate, others were logically different. Namely the concentration and the flow rate of the reducing agent NaBH4 or the concentration of HCl, which was required for acidification of the reaction mixture. A detection limit of 105 ng L–1 Se(IV) with a repeatability of 1.3 % (RSD, n = 10) was achieved by chemical volatile compounds generation. As the results show, UV-photochemical generation is a useful alternative to the conventional chemical generation technique. Not only because of its low detection limits obtained but also because of high sensitivity (comparison of slopes of calibration curves). Acknowledgments This work was supported by MSMT (project No. MSM 0021620857), Charles University in Prague (project SVV267215 and project UNCE 204025/2012).

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(P36) EFFECT OF ZINC IN HISTORICAL IRON BASED INK CONTAINING DOCUMENTS: A MULTI-SPECTROSCOPIC APPROACH Marta Manso1, Ana Mafalda Cardeira1,2, Tânia Rosado3, Mara Silva3, Agnès Le Gac1,4, Sofia Pessanha1, Mauro Guerra1, Stéphane Longelin1, Ana Teresa Caldeira3, António Candeias3,5 and Maria Luísa Carvalho1 1

Centro de Física Atómica da Universidade de Lisboa, Av. Professor Gama Pinto 2, 1649-003 Lisboa, Portugal 2 Faculdade de Belas-Artes da Universidade de Lisboa, Largo da Academia Nacional de Belas Artes, 1249-058 Lisboa, Portugal 3 Laboratório HERCULES e Centro de Química de Évora, Universidade de Évora, Largo Marquês de Marialva 8, 7000 Évora, Portugal 4 Departamento de Conservação e Restauro, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, Campus de Caparica, 2829-516 Caparica, Portugal 5 Laboratório José de Figueiredo, Direção Geral do Património Cultural, Rua das Janelas Verdes 37, 1249-018 Lisboa, Portugal e-mail: [email protected] Biodeterioration phenomena represent a complex of physical and chemical alteration processes in various materials, such as those constituting the objects that represent our cultural heritage [1]. Storage documents inside structures intended for their preservation has created new manmade environments for microbial species such as fungi and bacteria to inhabit [2]. Microorganisms such as fungi and bacteria are the most important agents of biodeterioration in museums, storage rooms, libraries, collections and restoration studios. Historical material made of paper and parchment with high amounts of organic binders is especially susceptible to fungal deterioration [3, 4]. In this work, X-ray fluorescence analyses were carried out on documents from the 13th to the 16th century to infer the inks potential effect on their preservation. Two types of iron-based inks were identified on each document, one containing mainly iron and the other one, iron and zinc. These documents, either on parchment or paper support, were all strongly attacked by microorganisms exhibiting dark brownish stains all over them. Nevertheless, this biological alteration was not observed in the adjacent areas to inks containing zinc. In fact the presence of a light aureole around the written text may confirm the assumption that this element inhibits the degradation process of both support and ink. Microbiologic assays were performed aseptically, collecting several samples from the areas of the document with significant contamination and degradation. The samples were inoculated in a selective culture media and identified according to the macroscopic and microscopic features. For the evaluation of microflora proliferation a combination of spectroscopic approach using scanning electron microscopy (SEM), scanning electron microscopy coupled with energy dispersive X-ray spectrometry (SEM-EDS) and also Raman microscopy to detect alteration products were used. The microbiological study allowed the identification of filamentous fungi, yeast strains (mainly Rhodotorula sp.) and a few bacterial strains.

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Keywords: biodeterioration; historical documents; metal based inks; spectroscopy techniques References: [1] F. Pinzari, G. Pasquariello, A. De Mico. Biodeterioration of Paper: A SEM Study of Fungal Spoilage Reproduced Under Controlled Conditions. Macromolecular Symposia 238 (1), 2006, pp. 57-66. [2] M. Montanari, V. Melloni, F. Pinzari, G. Innocenti.Fungal biodeterioration of historical library materials stored in Compactus movable shelves." International Biodeterioration & Biodegradation 75 (0), 2012, pp. 83-88. [3] K. Sterflinger, F. Pinzari. The revenge of time: fungal deterioration of cultural heritage with particular reference to books, paper and parchment. Environmental Microbiology 14 (3), 2012, pp. 559-566. [4] L. K. Kraková, S.A. Chovanová, A. Selim, A. Šimonovičová, A. Puškarová, A. Maková, D. Pangallo. A multiphasic approach for investigation of the microbial diversity and its biodegradative abilities in historical paper and parchment documents. International Biodeterioration & Biodegradation 70 (0), 2012, pp. 117-125. Acknowledgments: This work was partially supported by the Fundação para a Ciência e Tecnologia – The Awakening of the Manuelin foral charters: science and technology insights into the masterpiece SPTDC/EAT-EAT/112662/2009. Marta Manso and Sofia Pessanha acknowledge the support of Fundação para a Ciência e Tecnologia for the grants SFRH/BPD/70031/2010 and SFRH/BD/60778/2009, respectively. Authors would like to thank Silvestre Lacerda, Director of the National Archive Torre do Tombo, Sónia Domingues, Anabela Ribeiro and Mário Costa for the support, the suggestions, and the fruitful discussions.

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(P37) EVALUATION OF CALCIUM AND PHOSPHORUS IN TOOTH ENAMEL EXPOSED TO BLEACHING GEL Godinho J.1, Pessanha S.2, Silveira J1, Mata A.1, Carvalho M.L.2 1

Grupo de investigação em Bioquímica e Biologia Oral, Unidade de Investigação em Ciências Orais e Biomédicas da Faculdade de Medicina Dentária da Universidade de Lisboa, Cidade Universitária 1649-003 Lisboa, Portugal 2 Centro de Física Atómica da Universidade de Lisboa, Av. Professor Gama Pinto 2 1649-003 Lisboa, Portugal The purpose of this work is to assess whether the elemental content of Ca and P in tooth enamel is altered when bleaching the teeth with a bleaching gel containing 10 % (w/w) of carbamide peroxide. Ten anterior healthy teeth, extracted for periodontal or orthodontic reasons, were selected and preserved in a 0.5% (w/w) chloramine solution for no longer than 6 months. After confirming that there were no irregularities in the vestibular surfaces of the teeth, cuts were made in order to obtain 8 mm x 2 mm samples. The samples were then treated with the bleaching product through 8-hour periods during 14 days accordingly to manufacturer instructions and placed in artificial saliva between each application to simulate the oral environment. The elemental content of the teeth before and during treatment was determined by means of micro Energy Dispersive X-Ray Spectrometry (-EDXRF). The equipment used consists on an X-ray tube OXFORD XTF5011 with a Mo anode and a Silicon Drift Detector (SDD) Vortex-60EX® with an active area of 50 mm2 and a 12.5 μm thickness Be window. The radiation emitted by the X-ray tube is focused by means of polycapillary optics, allowing a focal spot of 100 μm. The quantitative analysis of the samples was carried out using WinAXIL software package (Canberra, Belgium) and statistical treatment performed by SPSS V.21 (IBM, USA). In this preliminary study a tendency for a decrease in Ca and P concentrations after bleaching treatment was observed.

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(P38) ASSESSMENT OF ESSENTIAL ELEMENTS AND HEAVY METALS CONTENT ON MYTILUS GALLOPROVINCIALIS FROM RIVER TAGUS ESTUARY I. Santos1, M. Diniz2, M. L. Carvalho3, J. P. Santos1 1

CFA, Departamento de Física, Faculdade de Ciências e Tecnologia, FCT, Universidade Nova de Lisboa, 2829-516 Caparica, Portugal 2 REQUIMTE, Departamento de Química, Centro de Química Fina e Biotecnologia, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, Quinta da Torre 2829-516, Caparica, Portugal 3 Centro de Física Atómica Universidade de Lisboa, Av. Prof. Gama Pinto 2, 1649-003, Lisboa, Portugal e-mail: [email protected] European countries are one of the largest producers and consumers of mussels whether collected in the open sea or produced in aquaculture. In this work we analyze the trace elemental content in edible tissue of Mytilus galloprovincialis collected in 4 different sampling areas in the mouth of river Tagus estuary in Lisbon. One of the sampling points was considered clean and it was at the sea coast in Cascais. The other three regions were closer to the city and may include contaminated areas: Trafaria, Cacilhas on the south and Belem on the north. The concentrations of essential elements (S, K, Ca, Fe, Cu, Zn, As, Br and Sr) were obtained by energy dispersive x-ray fluorescence spectrometry, while toxic elements (Cr, Cd, Hg, Se and Pb) were obtained by inductively coupled plasma mass spectrometry (ICP-MS). The latter technique was used owing to its higher sensitivity, since these elements were not detected by the first technique. Potassium and S are present at the highest concentration in all the studied samples reaching 4520 ug.g-1 and 2500 ug.g-1 (fresh weight) respectively in the sea coast samples. The highest levels for toxic elements were found in two areas close to the city: 0.09 ug.g-1 and 0.33 ug.g-1 for Cd and Pb (fresh weight) respectively, both exceeding the maximum allowed values (0.05 ug.g-1 and 0.30 ug.g-1 respectively). Concerning the other toxic elements no values above the recommended regulations were found. The results obtained for toxic elements were submitted to the Kruskall Wallis test in order to check significant difference between the elemental concentrations in mussel tissues from clean and contaminated sampling sites. The difference was significant to Pb, Cd and Se (p