Annual Report 2011

ANNUAL REPORT 2011

INSTITUTE OF NUCLEAR CHEMISTRY AND TECHNOLOGY EDITORS Prof. Jacek Michalik, Ph.D., D.Sc. Wiktor Smułek, Ph.D. Ewa Godlewska-Para, M.Sc.

PRINTING Sylwester Wojtas

GENERAL INFORMATION 7

MANAGEMENT OF THE INSTITUTE 9 MANAGING STAFF OF THE INSTITUTE 9 HEADS OF THE INCT DEPARTMENTS 9 SCIENTIFIC COUNCIL (2008-2011) 9 SCIENTIFIC COUNCIL (2011-2015) 11 ORGANIZATION SCHEME 13

SCIENTIFIC STAFF 14 PROFESSORS 14 SENIOR SCIENTISTS (Ph.D.) 14

CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY 17

– OXIDIZING RADICALS AND THEIR REACTIVITY IN IONIC LIQUIDS BASED ON NTf2 ANION J. Grodkowski, R. Kocia, J. Mirkowski, M. Nyga, A. Sulich, T. Szreder 19 FREE RADICAL REACTIONS OF NICOTINE K. Kosno, M. Celuch, J. Mirkowski, I. Janik, D. Pogocki 20 PRELIMINARY STUDIES ON RADIATION DEGRADATION OF AQUEOUS SOLUTION OF LINURON M. Celuch, A. Bojanowska-Czajka, K. Kulisa, J. Kisała, K. Kosno, D. Pogocki 23 REACTIVITY OF C-CENTRED RADICALS STABILIZED IN ZSM-5 ZEOLITE M. Sterniczuk, J. Sadło, G. Strzelczak, J. Michalik 25 MULTIFREQUENCY EPR STUDY ON γ-IRRADIATED BONE SUBSTITUTING BIOMATERIALS J. Sadło, G. Strzelczak, M. Lewandowska-Szumieł, M. Sterniczuk, J. Michalik 26 SURFACE MODIFICATION OF POLY(ESTERURETHANE) BY RADIATION-INDUCED GRAFTING OF N-ISOPROPYLACRYLAMIDE M. Walo, G. Przybytniak, M. Barsbay, P.A. Kavaklı, O. Guven 28 RADIATION-INDUCED REDUCTION OF CARBON DIOXIDE AS POSSIBLE EXPLANATION OF ABIOTIC FORMATION OF METHANE E.M. Kornacka, Z.P. Zagórski 30 STUDIES OF PHYSICOCHEMICAL PROPERTIES OF GELS BASED ON IRRADIATED WHEAT STARCH K. Cieśla, W. Głuszewski 31

CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY 37

ION EXCHANGE EVIDENCE FOR CHEMICAL ISOTOPE EFFECTS OF GALLIUM AND INDIUM IN AQUEOUS HCl SOLUTIONS I. Herdzik-Koniecko, S. Siekierski, J. Narbutt 39 NEW METHOD FOR DISSOLUTION OF THORIUM OXIDE K. Łyczko, M. Łyczko, I. Herdzik-Koniecko, B. Zielińska 41 LABELLING OF DOTATATE WITH CYCLOTRON PRODUCED 44Sc S. Krajewski, I. Cydzik, K. Abbas, A. Bulgheroni, A. Bilewicz, A. Majkowska-Pilip, F. Simonell 42

99m 2 4 9 Tc-LABELLED VASOPRESSIN ANALOGUE d(CH2)5[D-Tyr(Et ),Ile ,Eda ]AVP AS A POTENTIAL RADIOPHARMACEUTICAL FOR SMALL-CELL LUNG CANCER (SCLC) IMAGING E. Gniazdowska, P. Koźmiński, K. Bańkowski 43 THE CONCEPT OF A HYBRID SYSTEM FOR TREATMENT OF LIQUID LOW- AND MEDIUM-LEVEL RADIOACTIVE WASTE G. Zakrzewska-Trznadel, A. Miśkiewicz, A. Jaworska-Sobczak, M. Harasimowicz 45 STUDIES ON THE LEACHING OF URANIUM FROM LOWER TRIASSIC PERIBALTIC SANDSTONES G. Zakrzewska-Trznadel, K. Kiegiel, K. Frąckiewicz, D. Gajda, E. Chajduk, I. Bartosiewicz, J. Chwastowska, S. Wołkowicz, J.B. Miecznik, R. Strzelecki 47 SYNTHESIS OF URANIUM DIOXIDE MICROSPHERES BY WATER AND NITRATE EXTRACTION FROM URANYL-ASCORBATE SOLS M. Brykała, A. Deptuła, W. Łada, T. Olczak, D. Wawszczak, T. Smoliński 48 SYNTHESIS OF PEROVSKITE BY COMPLEX SOL-GEL PROCESS FOR NUCLEAR WASTE IMMOBILIZATION T. Smoliński, A. Deptuła, T. Olczak, W. Łada, D. Wawszczak, M. Brykała, F. Zaza, A.G. Chmielewski 51

CENTRE FOR RADIOBIOLOGY AND BIOLOGICAL DOSIMETRY 55

OPTIMIZATION OF A FINGER-PRICK BLOOD COLLECTION METHOD FOR THE γ-H2AX ASSAY: POTENTIAL APPLICATION IN POPULATION TRIAGE M. Wojewódzka, A. Lankoff, M. Kruszewski 57 CLONOGENIC ABILITY DOES NOT CORRESPOND TO DNA DAMAGE INDUCED IN HUMAN CELLS TREATED IN VITRO WITH SILVER AND TITANIUM DIOXIDE NANOPARTICLES I. Grądzka, T. Bartłomiejczyk, T. Iwaneńko, M. Wojewódzka, A. Lankoff, M. Dusinska, G. Brunborg, I. Szumiel, M. Kruszewski 58 COMPARISON OF FREQUENCIES OF DICENTRIC CHROMOSOMES AND HISTONE γ-H2AX FOCI IN HUMAN LYMPHOCYTES X-IRRADIATED AT 4, 20 AND 37oC A. Lankoff, S. Sommer, I. Buraczewska, T. Bartłomiejczyk, T. Iwaneńko, H. Lisowska, A. Węgierek-Ciuk, I. Szumiel, I. Wewiór, A. Banasik-Nowak 59 THE EFFECT OF CONJUGATED LINOLEIC ACID (CLA) SUPPLEMENTATION ON LIPID RAFT PROPERTIES AND RADIOSENSITIVITY OF HUMAN COLON CANCER HT-29 CELLS I. Grądzka, B. Sochanowicz, K. Brzóska, G. Wójciuk, Ch. Degen, G. Jahreis, I. Szumiel 60

LABORATORY OF NUCLEAR ANALYTICAL METHODS 63

RADIOLYTIC DECOMPOSITION OF DICLOFENAC – ANALYTICAL, TOXICOLOGICAL AND PULSE RADIOLYSIS STUDIES A. Bojanowska-Czajka, G. Kciuk, M. Gumiela, G. Nałęcz-Jawecki, K. Bobrowski, M. Trojanowicz 64 ELABORATION OF OPTIMAL CONDITIONS OF GEOLOGICAL MATERIALS ANALYSIS FOR URANIUM DETERMINATION I. Bartosiewicz, E. Chajduk, M. Pyszynska, J. Chwastowska, H. Polkowska-Motrenko 68

LABORATORY OF MATERIAL RESEARCH 71

STRUCTURAL STUDIES IN Li(I) ION COORDINATION CHEMISTRY W. Starosta, J. Leciejewicz 73 NANOPORES WITH CONTROLLED PROFILES IN TRACK-ETCHED MEMBRANES B. Sartowska, O. Orelovitch, A. Presz, I. Blonskaya, P. Apel 77 IMPROVEMENT OF TRIBOLOGICAL PROPERTIES OF STAINLESS STEEL BY ALLOYING ITS SURFACE LAYER WITH RARE EARTH ELEMENTS USING HIGH INTENSITY PULSED PLASMA BEAMS B. Sartowska, J. Piekoszewski, L. Waliś, J. Senatorski, M. Barlak, W. Starosta, C. Pochrybniak, I. Pokorska 79 INAA AS A SOURCE OF INFORMATION FOR THE PROVENANCE OF ALABASTER SCULPTURES T. Śliwa, E. Pańczyk 80

POLLUTION CONTROL TECHNOLOGIES LABORATORY 85

MODELLING STUDY OF NOx REMOVAL IN FLUE GAS IN THE PRESENCE OF C2H6 UNDER ELECTRON BEAM IRRADIATION Y. Sun, V. Morgunov, A.G. Chmielewski 86 EMISSION PROCESSES IN THE BALTIC SEA REGION – PLASMA TECHNOLOGIES IN ENVIRONMENTAL PROTECTION (PlasTEP) S. Witman, A. Pawelec, A.G. Chmielewski 87

STABLE ISOTOPE LABORATORY 89

STABLE ISOTOPES METHODS FOR JUICE AUTHENTICITY CONTROL R. Wierzchnicki 91 STABLE ISOTOPE RATIO ANALYSIS TO CHARACTERIZE CHOSEN SAMPLES OF POLISH HONEY K. Malec-Czechowska, R. Wierzchnicki 92 LABORATORY FOR MEASUREMENTS OF TECHNOLOGICAL DOSES 95

A STUDY OF FILMS: CTA, B3 AND PVC AS POTENTIAL DOSIMETERS FOR DOSIMETRY AT LOW TEMPERATURES A. Korzeniowska-Sobczuk, K. Doner, M. Karlińska 96

LABORATORY FOR DETECTION OF IRRADIATED FOOD 99

INCT PARTICIPATES IN THE INTERCOMPARATIVE EXERCISE FOR QUALITY ASSURANCE ON TL, PSL AND EPR IRRADIATED FOOD DETECTION METHODS W. Stachowicz, M. Sadowska, G. Liśkiewicz, G.P. Guzik 100 EFFECTIVENESS OF DIFFERENT PROCEDURES OF MINERAL ISOLATION FROM IRRADIATED SPICES SUITABLE FOR THERMOLUMINESCENCE DETECTION METHOD M. Sadowska, W. Stachowicz 102

LABORATORY OF NUCLEAR CONTROL SYSTEMS AND METHODS 107

THE RADIOMETRIC PROBES FOR INDUSTRIAL MEASURING SYSTEMS A. Jakowiuk, E. Kowalska, J. Pieńkos, P. Filipiak, Ł. Modzelewski, J. Palige, J. Kraś 108 MOBILE DOSIMETRIC GATE A. Jakowiuk, E. Kowalska, J. Pieńkos, P. Filipiak, Ł. Modzelewski 109

PUBLICATIONS IN 2011 113 ARTICLES 113 BOOKS 119 CHAPTERS IN BOOKS 119 THE INCT PUBLICATIONS 121 CONFERENCE PROCEEDINGS 121 CONFERENCE ABSTRACTS 124 SUPPLEMENT LIST OF THE PUBLICATIONS IN 2010 137

NUKLEONIKA 139

INTERVIEWS IN 2011 143

THE INCT PATENTS AND PATENT APPLICATIONS IN 2011 144 PATENTS 144 PATENT APPLICATIONS 144

CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2011 146

Ph.D./D.Sc. THESES IN 2011 148

Ph.D. THESES 148 D.Sc. THESES 148

EDUCATION 149 Ph.D. PROGRAMME IN CHEMISTRY 149 TRAINING OF STUDENTS 149

RESEARCH PROJECTS AND CONTRACTS 151 RESEARCH PROJECTS GRANTED BY THE NATIONAL SCIENCE CENTRE IN 2011 151 DEVELOPMENT PROJECTS GRANTED BY THE NATIONAL CENTRE FOR RESEARCH AND DEVELOPMENT IN 2011 151 INTERNATIONAL PROJECTS CO-FUNDED BY THE MINISTRY OF SCIENCE AND HIGHER EDUCATION IN 2011 152 STRATEGIC PROJECT “NEW TECHNOLOGIES SUPPORTING DEVELOPMENT OF SAFE NUCLEAR ENERGY” 153 STRATEGIC PROJECT “ADVANCED TECHNOLOGIES FOR GAINING ENERGY” 153 IAEA RESEARCH CONTRACTS IN 2011 153 IAEA TECHNICAL AND REGIONAL CONTRACTS IN 2011 154 PROJECTS WITHIN THE FRAME OF EUROPEAN UNION FRAME PROGRAMMES IN 2011 154 EUROPEAN REGIONAL DEVELOPMENT FUND: BALTIC SEA REGION PROGRAMME 154 INTERNATIONAL RESEARCH PROGRAMMES IN 2011 154 STRUCTURAL FUND: OPERATIONAL PROGRAMME INNOVATIVE ECONOMY 155

LIST OF VISITORS TO THE INCT IN 2011 156

THE INCT SEMINARS IN 2011 158

LECTURES AND SEMINARS DELIVERED OUT OF THE INCT IN 2011 159 LECTURES 159 SEMINARS 163

AWARDS IN 2011 164

INDEX OF THE AUTHORS 166 GENERAL INFORMATION 7

GENERAL INFORMATION

Poland decided to start a national nuclear energy programme 55 years ago and the Insti- tute of Nuclear Research (IBJ) was established. Research in nuclear and analytical chemistry, nuclear chemical engineering and technology (including fuel cycle), radiochemistry and radiation chemistry, and radiobiology were carried out mainly in the Chemistry Divi- sion, located in Warsaw Żerań, which became the interdisciplinary Institute of Nuclear Chemistry and Technology (INCT) in 1983. The INCT is Poland’s most advanced institution in the fields of radiochemistry, radiation chemistry, nuclear chemical engineering and technology, application of nuclear methods in material engineering and process engineering, radioanalytical techniques, design and production of instruments based on nuclear techniques, environmental research, cellular radiobiology, etc. The results of work at the INCT have been implemented in various branches of the national economy, particularly in industry, medicine, environmental protection and agriculture. Basic research is focused on: radiochemistry, chemistry of isotopes, physical chemistry of separation processes, cellular radiobiology, and radiation chemistry, particularly that based on pulse radiolysis method. With its nine electron accelerators in operation and with staff experienced in the field of electron beam application, the Institute is one of the most advanced centres of science and technology in this domain. The Institute has four pilot plants equipped in six electron accelerators: for radiation sterilization of medical devices and transplantation grafts; for radiation modification of polymers; for removal of SO2 and NOx from flue gases; for food hygiene. The electron beam flue gas treatment in EPS Pomorzany with the accelerators power over 1 MW is a biggest radiation processing facility ever built. The Institute trains many of IAEA’s Fellows and plays a leading role in agency regional projects. Because of its achievements, the INCT has been nominated the IAEA’s Collabo- rating Centre in Radiation Technology and Industrial Dosimetry (www-naweb.iaea.org/ na/collaborating-centres.html). The INCT has started implementing several projects in the programme “Innovative Economy” POIG, granted on the basis of high evaluation of the Institute’s achievements: • Centre of Radiochemistry and Nuclear Chemistry – meeting the needs of nuclear power and nuclear medicine; • Analysis of thorium usage effects in a power nuclear reactor (coordinated by the Insti- tute of Atomic Energy); • Analysis of the possibilities of uranium extraction from indigenous resources (in cooperation with the Polish Geological Institute – NRI); • New generation of intelligent radiometric tools with wireless data transmission; • Development of a multi-parametric triage approach for an assessment of radiation exposure in a large-scale radiological emergency; • New generation of electrical wires modified by radiation. The INCT is a leading institute in Poland regarding the implementation of nuclear energy related EU projects. Its expertise and infrastructure was the basis for participation in EURATOM and FP7 grants: • ACSEPT: Actinide Recycling by Separation and Transmutation; • ADVANCE: Ageing Diagnostics and Prognostics of Low-voltage I&C Cables; • IPPA: Implementing Public Participation Approaches in Radioactive Wastes Disposal; • MULTIBIODOSE: Multidisciplinary Biodosimetric Tools to Manage High Scale Radio- logical Casualties; • NEWLANCER: New MS Linking for an Advanced Cohesion in Euratom Research. The mission of the INCT is the implementation of nuclear energy for social development, health and environmental protection. The Institute represents the Polish Government in Euroatom Fuel Supply Agency, in Fuel Supply Working Group of Global Nuclear Energy Partnership and in Radioactive 8 GENERAL INFORMATION Waste Management Committee of the Nuclear Energy Agency (Organisation for Economic Co-operation and Development). The Institute is listed in the cathegory I of scientific institutions based on the evaluation of the Ministry of Science and Higher Education. The INCT Scientific Council has rights to grant D.Sc. and Ph.D. degrees in the field of chemistry. The Institute carries out third level studies (doctorate) in the field of nuclear and radiation chemistry and in 2011 one D.Sc. and four Ph.D. theses were defended. In 2011, the INCT scientists published 67 papers in scientific journals registered in the Philadelphia list, among them 39 papers in journals with an impact factor (IF) higher than 1.0. Five scientific books and 17 chapters in the books were written by the INCT research workers. The INCT had actively participated in the numerous events associated with the In- ternational Year of Chemistry (IYC 2011) and the 100th Anniversary of Maria Skłodowska- -Curie Nobel prize in chemistry. We took part, among others, in exhibition in Brussels “Maria Skłodowska-Curie in science, yesterday and today”, in education project “Follow- ing Maria Skłodowska-Curie – questioning”, in main IYC 2011 event – scientific picnic in the Institute of Physical Chemistry and in the lectures and exhibitions in Adam Mickiewicz University in Poznań under the name “Life and work of Maria Skłodowska-Curie – women in science”. Annual awards of the INCT Director-General for the best publications in 2011 were granted: • first degree award to Krzysztof Bobrowski for the chapter “Chemistry of sulfur-centered radicals” in the book “Recent trends in radiation chemistry”; • second degree award to Andrzej Pawlukojć for five publications on the structure and dynamics of charge transfer (CT) complexes published in international journals with high IF; • third degree award to Janusz Leciejewicz and Wojciech Starosta for five publications on the properties of new complexes of uranium, lead, zinc and lithium with a pyridazine- -carboxylic ligand published in “Acta Crystallographica”. The research teams in the INCT were involved in organization of 11 scientific meetings: • Polish National Group Meeting in the frame of IPPA FP7 EU Project (5 April 2011, Warszawa, Poland); • Seminar on the Exchange of Information on Nuclear Safety and Radiological Protec- tion with participation of government delegations of Austria and Poland (25-26 May 2011, Warszawa, Poland); • Polish National Group Meeting in the frame of IPPA FP7 EU Project (1 July 2011, Warszawa, Poland); • Plas TEP Summer School and Training Course in Warsaw/Szczecin (25 July-5 August 2011, Warszawa/Szczecin, Poland); • Workshop “Current trends in radiation chemistry research” (26 August 2011, Warszawa, Poland); • International Conference on Development and Applications of Nuclear Technologies NUTECH-2011 (11-14 September 2011, Kraków, Poland); • Polish Reference Group Meeting in the frame of IPPA FP7 EU Project (20 September 2011, Warszawa, Poland); • XI Training Course on Radiation Sterilization and Hygenization (20-21 October 2011, Warszawa, Poland); • Coordination Meeting on Radiation Engineered Nanostructures – Supporting Radia- tion Synthesis and the Characterization of Nanomaterials for Health Care, Environ- mental Protection and Clean Energy Applications, RER/8/014 (16-18 November 2011, Warszawa, Poland); • 1st Workshop in the frame of IPPA FP7 EU Project (24 November 2011, Warszawa, Poland); • IX Conference “For the city and environment – problems of waste disposal” (28 No- vember 2011, Warszawa, Poland). The INCT also is editor of the scientific journal “Nukleonika” (www.nukleonika.pl). MANAGEMENT OF THE INSTITUTE 9

MANAGEMENT OF THE INSTITUTE

MANAGING STAFF OF THE INSTITUTE

Director Prof. Andrzej G. Chmielewski, Ph.D., D.Sc.

Deputy Director for Research and Development Prof. Jacek Michalik, Ph.D., D.Sc.

Deputy Director of Finances Wojciech Maciąg, M.Sc.

Deputy Director of Maintenance and Marketing Roman Janusz, M.Sc.

Accountant General Maria Małkiewicz, M.Sc.

HEADS OF THE INCT DEPARTMENTS

• Centre for Radiation Research and Technology • Laboratory of Nuclear Analytical Methods Zbigniew Zimek, Ph.D. Halina Polkowska-Motrenko, Ph.D., D.Sc, professor in INCT • Centre for Radiochemistry and Nuclear Chemistry • Stable Isotope Laboratory Prof. Jerzy Ostyk-Narbutt, Ph.D., D.Sc. Ryszard Wierzchnicki, Ph.D. • Centre for Radiobiology and Biological • Pollution Control Technologies Laboratory Dosimetry Andrzej Pawelec, Ph.D. Prof. Marcin Kruszewski, Ph.D., D.Sc. • Laboratory for Detection of Irradiated Food • Laboratory of Nuclear Control Systems Wacław Stachowicz, Ph.D. and Methods Jacek Palige, Ph.D. • Laboratory for Measurements of Technological Doses • Laboratory of Material Research Anna Korzeniowska-Sobczuk, M.Sc. Wojciech Starosta, Ph.D.

SCIENTIFIC COUNCIL (2008-2011)

1. Prof. Grzegorz Bartosz, Ph.D., D.Sc. 4. Prof. Stanisław Chibowski, Ph.D., D.Sc. University of Łódź Maria Curie-Skłodowska University 2. Prof. Aleksander Bilewicz, Ph.D., D.Sc. 5. Prof. Rajmund Dybczyński, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology Institute of Nuclear Chemistry and Technology 3. Prof. Krzysztof Bobrowski, Ph.D., D.Sc. 6. Prof. Zbigniew Florjańczyk, Ph.D., D.Sc. (Vice-chairman) (Chairman) Institute of Nuclear Chemistry and Technology Warsaw University of Technology 10 MANAGEMENT OF THE INSTITUTE

Prof. 7. Prof. Zbigniew Galus, Ph.D., D.Sc. 24. Halina Polkowska-Motrenko, Ph.D. D.Sc., University of Warsaw professor in INCT Institute of Nuclear Chemistry and Technology Prof. 8. Prof. Henryk Górecki, Ph.D., D.Sc. Wrocław University of Technology 25. Grażyna Przybytniak, Ph.D., D.Sc., professor in INCT Prof. 9. Prof. Leon Gradoń, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology Warsaw University of Technology 26. Prof. Leon Pszonicki, Ph.D., D.Sc. 10. Jan Grodkowski, Ph.D., D.Sc., professor Institute of Nuclear Chemistry and Technology in INCT Institute of Nuclear Chemistry and Technology 27. Jarosław Sadło, Ph.D. Institute of Nuclear Chemistry and Technology 11. Edward Iller, Ph.D., D.Sc., professor in NCBJ National Centre for Nuclear Research 28. Ryszard Siemion, M.Sc. PKN ORLEN 12. Tomasz Jackowski, M.Sc. Ministry of Economy 29. Prof. Irena Szumiel, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology 13. Iwona Kałuska, M.Sc. Institute of Nuclear Chemistry and Technology 30. Prof. Marek Trojanowicz, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology 14. Prof. Marcin Kruszewski, Ph.D., D.Sc. (Vice-chairman) 31. Hanna Ewa Trojanowska, M.Sc. Institute of Nuclear Chemistry and Technology Undersecretary of State in the Ministry of Economy 15. Prof. Marek Wojciech Lankosz, Ph.D., D.Sc. 32. Andrzej Tyrała, M.Sc. AGH University of Science and Technology Warszawskie Zakłady Farmaceutyczne POLFA S.A. 16. Prof. Janusz Lipkowski, Ph.D., D.Sc. 33. Piotr Urbański, Ph.D., D.Sc., professor Institute of Physical Chemistry, Polish Academy in INCT of Sciences (Vice-chairman) 17. Zygmunt Łuczyński, Ph.D. Institute of Nuclear Chemistry and Technology Institute of Electronic Materials Technology 34. Lech Waliś, Ph.D. 18. Prof. Andrzej Marcinek, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology Technical University of Łódź 35. Maria Wojewódzka, Ph.D. 19. Prof. Bronisław Marciniak, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology Adam Mickiewicz University 36. Prof. Zbigniew Zagórski, Ph.D., D.Sc. 20. Wojciech Migdał, Ph.D., D.Sc., professor Institute of Nuclear Chemistry and Technology in INCT Institute of Nuclear Chemistry and Technology 37. Grażyna Zakrzewska-Trznadel, Ph.D., D.Sc., professor in INCT 21. Prof. Jerzy Ostyk-Narbutt, Ph.D., D.Sc. (Vice-chairman) Institute of Nuclear Chemistry and Technology Institute of Nuclear Chemistry and Technology 22. Jan Paweł Pieńkos, Eng. 38. Zbigniew Zimek, Ph.D. Institute of Nuclear Chemistry and Technology Institute of Nuclear Chemistry and Technology 23. Dariusz Pogocki, Ph.D., D.Sc., professor in INCT Institute of Nuclear Chemistry and Technology

HONORARY MEMBERS OF THE INCT SCIENTIFIC COUNCIL (2008-2011)

1. Prof. Antoni Dancewicz, Ph.D., D.Sc. 2. Prof. Sławomir Siekierski, Ph.D. MANAGEMENT OF THE INSTITUTE 11 SCIENTIFIC COUNCIL (2011-2015)

1. Prof. Grzegorz Bartosz, Ph.D., D.Sc. 19. Anna Lankoff, Ph.D., D.Sc., professor University of Łódź in INCT Institute of Nuclear Chemistry and Technology 2. Prof. Aleksander Bilewicz, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology 20. Prof. Marek Wojciech Lankosz, Ph.D., D.Sc. AGH University of Science and Technology 3. Prof. Krzysztof Bobrowski, Ph.D., D.Sc. (Vice-chairman) 21. Prof. Janusz Lipkowski, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology Institute of Physical Chemistry, Polish Academy of Sciences 4. Marcin Brykała, M.Sc. Institute of Nuclear Chemistry and Technology 22. Zygmunt Łuczyński, Ph.D. Institute of Electronic Materials Technology 5. Prof. Andrzej G. Chmielewski, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology 23. Prof. Jacek Michalik, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology 6. Andrzej Chwas, M.Sc. Ministry of Economy 24. Wojciech Migdał, Ph.D., D.Sc., professor in INCT 7. Jadwiga Chwastowska, Ph.D., D.Sc., professor Institute of Nuclear Chemistry and Technology in INCT Institute of Nuclear Chemistry and Technology 25. Prof. Jarosław Mizera, Ph.D., D.Sc. Warsaw University of Technology 8. Krystyna Cieśla, Ph.D., D.Sc., professor in INCT 26. Prof. Jerzy Ostyk-Narbutt, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology Institute of Nuclear Chemistry and Technology 9. Jakub Dudek, Ph.D. 27. Andrzej Pawlukojć, Ph.D., D.Sc., professor Institute of Nuclear Chemistry and Technology in INCT Institute of Nuclear Chemistry and Technology 10. Prof. Rajmund Dybczyński, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology 28. Dariusz Pogocki, Ph.D., D.Sc., professor in INCT 11. Prof. Zbigniew Florjańczyk, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology (Chairman) Warsaw University of Technology 29. Halina Polkowska-Motrenko, Ph.D., D.Sc., professor in INCT 12. Prof. Zbigniew Galus, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology University of Warsaw 30. Grażyna Przybytniak, Ph.D., D.Sc., professor 13. Prof. Henryk Górecki, Ph.D., D.Sc. in INCT Wrocław University of Technology Institute of Nuclear Chemistry and Technology 14. Prof. Leon Gradoń, Ph.D., D.Sc. 31. Prof. Janusz Rosiak, Ph.D., D.Sc. Warsaw University of Technology Technical University of Łódź 15. Jan Grodkowski, Ph.D., D.Sc., professor 32. Lech Waliś, Ph.D. in INCT Institute of Nuclear Chemistry and Technology Institute of Nuclear Chemistry and Technology 33. Maria Wojewódzka, Ph.D. 16. Edward Iller, Ph.D., D.Sc., professor in NCBJ Institute of Nuclear Chemistry and Technology National Centre for Nuclear Research 34. Grażyna Zakrzewska-Trznadel, Ph.D., D.Sc., 17. Adrian Jakowiuk, M.Sc. professor in INCT Institute of Nuclear Chemistry and Technology (Vice-chairman) Institute of Nuclear Chemistry and Technology 18. Prof. Marcin Kruszewski, Ph.D., D.Sc. (Vice-chairman) 35. Zbigniew Zimek, Ph.D. Institute of Nuclear Chemistry and Technology Institute of Nuclear Chemistry and Technology 12 MANAGEMENT OF THE INSTITUTE HONORARY MEMBERS OF THE INCT SCIENTIFIC COUNCIL (2011-2015)

1. Prof. Sławomir Siekierski, Ph.D. 3. Prof. Zbigniew Paweł Zagórski, Ph.D., D.Sc. 2. Prof. Irena Szumiel, Ph.D., D.Sc. MANAGEMENT OF THE INSTITUTE 13 ORGANIZATION SCHEME

Scientific DIRECTOR Council

Accountant Deputy Director Deputy Director General of Finances of Maintenance and Marketing

Deputy Director for Research and Development

Laboratory of Nuclear Analytical Methods

Centre for Radiation Research and Technology Stable Isotope Laboratory

Pollution Control Technologies Centre for Radiobiology Laboratory and Biological Dosimetry

Laboratory for Detection of Irradiated Food Centre for Radiochemistry and Nuclear Chemistry Laboratory for Measurements of Technological Doses

Laboratory of Material Research

Laboratory of Nuclear Control Systems and Methods 14 SCIENTIFIC STAFF

SCIENTIFIC STAFF

PROFESSORS

1. Bilewicz Aleksander 13. Migdał Wojciech, professor in INCT radiochemistry, inorganic chemistry chemistry, science of commodies 2. Bobrowski Krzysztof 14. Ostyk-Narbutt Jerzy radiation chemistry, photochemistry, biophysics radiochemistry, coordination chemistry

3. Chmielewski Andrzej G. 15. Pawlukojć Andrzej, professor in INCT chemical and process engineering, nuclear chem- chemistry ical engineering, isotope chemistry 16. Pogocki Dariusz, professor in INCT 4. Chwastowska Jadwiga, professor in INCT radiation chemistry, pulse radiolysis analytical chemistry 17. Polkowska-Motrenko Halina, professor 5. Cieśla Krystyna, professor in INCT in INCT physical chemistry analytical chemistry

6. Dybczyński Rajmund 18. Przybytniak Grażyna, professor in INCT analytical chemistry radiation chemistry 7. Grigoriew Helena, professor in INCT 19. Siekierski Sławomir solid state physics, diffraction research of non- physical chemistry, inorganic chemistry -crystalline matter 20. Szumiel Irena 8. Grodkowski Jan, professor in INCT cellular radiobiology radiation chemistry 21. Trojanowicz Marek 9. Kruszewski Marcin analytical chemistry radiobiology 22. Zagórski Zbigniew 10. Lankoff Anna, professor in INCT physical chemistry, radiation chemistry, electro- biology chemistry 11. Leciejewicz Janusz Tadeusz 23. Zakrzewska-Trznadel Grażyna, professor crystallography, solid state physics, material in INCT science process and chemical engineering 12. Michalik Jacek radiation chemistry, surface chemistry, radical chemistry

SENIOR SCIENTISTS (Ph.D.)

1. Barlak Marek 5. Buczkowski Marek chemistry physics 2. Bartłomiejczyk Teresa 6. Chajduk Ewelina biology chemistry 3. Bojanowska-Czajka Anna 7. Danilczuk Marek chemistry chemistry 4. Brzóska Kamil 8. Deptuła Andrzej biochemistry chemistry SCIENTIFIC STAFF 15

9. Dobrowolski Andrzej 31. Ostapczuk Anna chemistry chemistry 10. Dudek Jakub 32. Ozimiński Wojciech chemistry chemistry 11. Frąckiewicz Kinga 33. Palige Jacek chemistry metallurgy 12. Fuks Leon 34. Pawelec Andrzej chemistry chemical engineering 13. Głuszewski Wojciech 35. Pruszyński Marek chemistry chemistry 14. Gniazdowska Ewa 36. Ptaszek Sylwia chemistry chemical engineering 15. Grądzka Iwona 37. Rafalski Andrzej biology radiation chemistry 16. Harasimowicz Marian 38. Roubinek Otton technical nuclear physics, theory of elementary chemistry particles 39. Sadło Jarosław 17. Herdzik-Koniecko Irena chemistry chemistry 40. Samczyński Zbigniew 18. Kciuk Gabriel analytical chemistry chemistry 41. Sartowska Bożena 19. Kiegiel Katarzyna material engineering chemistry 42. Skwara Witold 20. Kierzek Joachim analytical chemistry physics 43. Sochanowicz Barbara 21. Kornacka Ewa biology chemistry 44. Sommer Sylwester 22. Kunicki-Goldfinger Jerzy radiobiology, cytogenetics conservator/restorer of art 45. Stachowicz Wacław 23. Lewandowska-Siwkiewicz Hanna radiation chemistry, EPR spectroscopy chemistry 46. Starosta Wojciech 24. Łyczko Krzysztof chemistry chemistry 47. Strzelczak Grażyna radiation chemistry 25. Łyczko Monika chemistry 48. Sun Yongxia chemistry 26. Machaj Bronisław radiometry 49. Szreder Tomasz chemistry 27. Majkowska-Pilip Agnieszka chemistry 50. Turek Janusz chemistry 28. Męczyńska-Wielgosz Sylwia chemistry 51. Waliś Lech material science, material engineering 29. Mirkowski Jacek nuclear and medical electronics 52. Warchoł Stanisław solid state physics 30. Nowicki Andrzej organic chemistry and technology, high-tempera- 53. Wierzchnicki Ryszard ture technology chemical engineering 16 SCIENTIFIC STAFF

54. Wiśniowski Paweł 57. Zielińska Barbara radiation chemistry, photochemistry, biophysics chemistry 55. Wojewódzka Maria 58. Zimek Zbigniew radiobiology electronics, accelerator techniques, radiation processing 56. Wójciuk Karolina chemistry CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY

Electron beams (EB) offered by the Centre for Radiation Research and Technology located at the Institute of Nuclear Chemistry and Technology (INCT) are dedicated to basic research, R&D and radiation technology applications. The Centre, in collaboration with the universities from Poland and abroad, apply EB technology for fundamental research on the electron beam-induced chemistry and transformation of materials. Research in the field of radiation chemistry includes studies on the mechanism and kinetics of radiation-induced processes in liquid and solid phases by the pulse radiolysis method. The pulse radiolysis experimental set-up allows direct time-resolved observation of short-lived intermediates (typically within the nanosecond to millisecond time domain), is complemented by steady-state radiolysis, stop-flow absorption spectrofluorimetry and product analysis using chromatographic methods. Studies on radiation-induced intermediates are dedicated to energy and charge transfer processes and radical reactions in model compounds of biological relevance aromatic thioethers, peptides and proteins, as well as observation of atoms, clusters, radicals by electron paramagnetic resonance (EPR) and electron nuclear double resonance (ENDOR), also focused on research problems in nanophase chemistry and radiation-induced cross-linking of selected and/or modified polymers and copolymers. This research has a wide range of potential applications, including creating more environmentally friendly and sustainable packaging, improving product safety, and modifying material properties. Electron accelerators provide streams of electrons to initiate chemical reactions or break of chemical bonds more efficiently than the existing thermal and chemical approaches, helping to reduce energy consumption and decrease the cost of the process. The Centre may offer currently four electron accelerators for study of the effects of accelerated electrons on a wide range of chemical compounds with a focus on electron beam-induced polymerization, polymer modification and controlled degradation of macromolecules. EB technology has a great potential to promote innovation, including new ways to save energy and reduce the use of hazardous substances as well as to enable more eco-friendly manufacturing processes. Advanced EB technology offered by the Centre provides a unique platform with the application for: sterilization medical devices, pharmaceutical materials, food products shelf life extension, polymer advanced materials, air pollution removal technology and others. EB accelerators replace frequently thermal and chemical processes for cleaner, more efficient, lower-cost manufacturing. EB accelerators sterilize products and packaging, improve the performance of plastics and other materials, and eliminate pollution for industries such as pharmaceutical, medical devices, food, and plastics. The Centre offers EB in the energy range from 0.5 to 10 MeV with an average beam power up to 20 kW and three laboratory-size gamma sources with Co-60. Research activity are supported by such unique laboratory equipment as: • nanosecond pulse radiolysis and laser photolysis set-ups, • EPR paramagnetic spectroscopy for solid material investigation, • pilot installation for polymer modification, • laboratory experimental stand for removal of pollutants from gas phase, • laboratory of polymer and non-material characterization, • microbiological laboratory, • dosimetric laboratory, • pilot facility for radiation sterilization and food product processing. The unique technical basis makes it possible to organize a wide internal and international cooperation in the field of radiation chemistry and radiation processing including programmes supported by the European Union and the International Atomic Energy Agency (IAEA). It should be noticed that currently there is no other suitable European experimental basis for study radiation chemistry, physics and radiation processing in a full range of electron energy and beam power. Since 2010, at the INCT on the basis of the Centre for Radiation Research and Technology, an IAEA Collaborating Centre for Radiation Processing and Industrial Dosimetry is function- ing. That is the best example of capability and great potential of concentrated equipment, methods and staff working towards application of innovative radiation technology. CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY 19 OXIDIZING RADICALS AND THEIR REACTIVITY IN IONIC LIQUIDS – BASED ON NTf2 ANION Jan Grodkowski, Rafał Kocia, Jacek Mirkowski, Małgorzata Nyga, Agnieszka Sulich, Tomasz Szreder

− ● ●− Ionic liquids (ILs) belong to quickly expanding N3 + N3 ' N6 (1) field of science. Their properties: negligible vapour In the present paper the mechanism of the ●– pressure, non-flammability, thermal and chemical azide radical anion dimmer N6 formation (1) was resistance, high conductivity, possibility to be re- studied in three different ILs: methyltributylam- used and others make them a very attractive alter- monium N,N-bis(trifluoromethylosulphonyl)imide native to classical solvents [1-4]. Additionally, the (MeBu3NTf2), 1-hexyl-3-methylimidazolium N,N- properties of ILs can be controlled to a large ex- -bis(trifluoromethylosulphonyl)imide (hmimNTf2) tent by variation of both cation or anion [5, 6]. and triethylammonium N,N-bis(trifluoromethylo- The aim of the study is to understand radical-ion sulphonyl)imide (Et3NHNTf2), (Fig.1). All of ILs reactions in selected ILs. We focused on kinetics base on the same anion N,N-bis(trifluoromethylo- and spectral characteristic of oxidizing species sulphonyl)imide which was used to obtain low ●– ●– N6 in these solvents. The N6 radical belongs to melting point of solvents. pseudohalide radicals family and is known as in- The most useful technique to study the chem- termediate in radiation chemistry. This radical is a istry of short-life free radicals is pulse radiolysis. strong one-electron oxidant and can be used in In our research we used 10 ns pulses of 10 MeV studies of electron transfer reactions. Since reac- electrons from a LINAC linear electron accelera- tions in water are very fast and individuals are very tor (LAE 10) with spectrophotometric detection. short-lived, the spectral and kinetic characteriza- Energy from the incident electron beam radiation tion of species participating in reaction (1) in aque- was absorbed in ILs generating a range of ILs ex- ous solutions were investigated before [7, 8]. Equi- cited states (IL*), electrons and ionized species. librium constant values (K) for reaction (1) was The electron deficiency species often called “holes” ● determined to be equal to 0.33 [9] and 200 [10] in [12] react with azide anion forming azide radical N3 water and acetonitrile, respectively. according to reaction (2). Then, the azide radicals Due to high viscosity of ILs radiation-induced react as mentioned above via reaction (1) forming ●– reactions are slowed down in such media. Thus, N6 . ⊕ – ● one can expect different behaviour of certain spe- IL ”hole” + N3 → N3 + IL (2) – cies. For instance, the participation of presolvated Spectrum of the N3 /MeBu3NNTf2 system, record- electron vary with viscosity of medium. In very vis- ed by means of pulse radiolysis, is shown in Fig.2. cose solvents presolvated electrons are more likely Basing on the literature data [7, 8] the band with to react before their solvation and thus influence distinct absorption maxima at 700 nm was assign- ●– radiation yield of radicals species [11]. ed to N6 . Observed increase of absorption of A

C Fig.2. Pulse radiolysis of N2O-saturated solution of tetra- butylammonium azide (0.06 M) in MeBu3NNTf2: (■) 1 μs, (●) 5 μs, (▲) 10 μs, (▼) 40 μs after the pulse; 20 Gy.

− this band with N3 concentration confirmed our D assignment. The calculation of equilibrium constants was carried out basing on the equation: 11 1 1 =+ ×− (3) GG00 GK [N3 ]

Fig.1. Methyltributylammonium cation (a), triethylammo- where: G0 – the radiolytic yield at 700 nm at infi- + − nium cation – Et3NH (b), 1-hexyl-3-methylimidazolium cat- nitely high N3 concentrations, G – the radiolytic + − –● ● ion – hmim (c), N,N-bis(trifluoromethylosulphonyl)imide yield at given N3 concentrations, K = [N6 ]/[N3 ] – anion (d). [N3 ] – the equilibrium constant. 20 CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY

vs. – A plot of 1/G 1/[N3 ] is a straight line. From References the slope of this line, K value can be extracted. [1]. Aparicio S., Atilhan M., Karadas F.: Ind. Eng. Chem. Obtained K values in MeBu3NTf2 and hmimNTf2 Res., 49, 9580-9595 (2010). were determined to be equal to 7 ± 2 and 6 ± 1, [2]. Endres F., El Abedin S.Z.: Phys. Chem. Chem. Phys., respectively. In protic ionic liquids (Et3NHNTf2) we 8, 2101-2116 (2006). ●– [3]. Plechkova N.V., Seddon K.R.: Chem. Soc. Rev., 37, did not observe formation of N6 which is probably ● 123-150 (2008). due to the reaction of N3 with the amine resulting from the radiolysis of ionic liquid, or from con- [4]. Wasserscheid P., Keim W.: Angew. Chem. Int. Ed., 39, 3772-3789 (2000). tamination from the synthesis of IL (Et3NHNTf2). [5]. Earle M.J., Seddon K.R.: Pure Appl. Chem., 72, From the obtained data, it can be observed that 1391-1398 (2000). the K value does not dramatically change in the [6]. Welton T.: Chem. Rev., 99, 2071-2083 (1999). case when methyltributylammonium bis[(trifluoro- [7]. Alfassi Z.B., Prutz W.A., Schuler R.H.: J. Phys. Chem., methyl)sulphonyl]imide (MeBu3NNTf2) is satured 90, 1198-1203 (1986). with water (0.15% mass percent of water). The [8]. Hayon E., Simic M.: J. Am. Chem. Soc., 92, 7486-7487 equilibrium constant K in this case was determined (1970). to be equal to 7. [9]. Butler J., Land E.J., Swallow A.J., Prytz W.: Radiat. Concluding, the low K value can be interpreted Phys. Chem., 23, 265 (1984). in terms of the relatively little difference in free [10]. Workentin M.S., Wagner B.D., Negri F., Zgierski M., ●– Lusztyk J., Siebrand W., Wayner D.D.M.: Phys. energy of formation of the N6 radical as com- . – Chem , 99, 94-101 (1995). pared to the sum of free energy formation of N3 [11]. Wishart J.W., Lall-Ramnarine S.I., Raju R., Scumpia ● and N3 species and may reflect the difficulty in A., Bellevue S., Ragbir R., Engel R.: Radiat. Phys. ●– forming stable bonding in N6 species. Stability of Chem., 72, 99-104 (2005). ●– N6 radical in ionic liquids is much higher as com- [12]. Wishart J.F.: J. Phys. Chem. Lett., 1, 3225-3231 (2010). pared to aqueous solutions.

FREE RADICAL REACTIONS OF NICOTINE Katarzyna Kosno1/, Monika Celuch1/, Jacek Mirkowski1/, Ireneusz Janik2/, Dariusz Pogocki1,3/ 1/ Institute of Nuclear Chemistry and Technology, Warszawa, Poland 2/ Notre Dame Radiation Laboratory, University of Notre Dame, USA 3/ Faculty of Biology and Agriculture, University of Rzeszów, Poland

Nicotine (3-(1-methyl-2-pyrrolidinyl)pyridine), a accompanied by an extensive oxidative stress, where natural alkaloid of main responsibility for tobacco nervous tissue is exposed to the presence of oxygen smoking addiction, has some medical applications. radicals beyond a threshold for proper antioxidant Besides its common usage in nicotine replacement neutralization [2-4], and therapeutic usage of nic-

Fig.1. Acid-base properties of nicotine in aqueous solution at 25oC [6]. therapy, is applied in neurodegenerative diseases otine can be related to its free radical scavenging diagnosis, and for alleviation of some symptoms capacity. and ailments accompanying these diseases [1]. Nicotine molecule is made of two rings – aro- Nicotine can have a potential protective effect on matic pyridine and aliphatic pyrrolidine. In physi- nerve cells. Neurodegenerative diseases are usually ological pH of blood 7.4, ca. 76% (37oC) of nicotine

Fig.2. Alternative pathways of ●OH radical reaction with nicotine. CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY 21

0.1 μs 2 μs 60 μs 155 μs

Fig.3. Transient absorption spectra obtained by ●OH-attack on nicotine recorded 0.1 μs (○), 2 μs (●), 60 μs (■) and 155 μs

(▲) after the pulse in the N2O-saturated 1 mM nicotine solution, at pH 10. Inset: kinetic traces recorded at λ = 330 and 460 nm, respectively. is protonated at pyrrolidine nitrogen [5] (Fig.1). inates coupling with a lone pair and the data from This protonation can influence its reactivity in DFT calculations indicating an increase of BDE radical reactions. for C2’−H bond. Free radical reactions of nicotine in aqueous We have studied the reaction of nicotine and solution can be initiated by water radiolysis [7, 8]. its model compounds with ●OH radicals with a ns Nicotine radical reactions were studied for the pulse-radiolysis technique applying UV-Vis time- first time with pulse radiolysis technique by Wang -resolved detection systems. Pulse radiolysis ex- et al. in 2003 [9]. These authors suggested that nic- periments at the Institute of Nuclear Chemistry otine reacts with hydrated electron, hydrogen atom and Technology (INCT) were performed with a and hydroxyl radical producing anion radical and LAE 10 linear accelerator with typical pulse lengths neutral radicals, respectively. However, their ki- of 4-10 ns [12]. Absorbed dose per pulse was ca. netics data (rate constants) are not consistent with 20 Gy. the results previously obtained by Getoff’s group Pulse radiolysis experiments at the Notre Dame for nicotine molecular components, i.e. pyridine Radiation Laboratory were performed with a Titan and pyrrolidine [10, 11]. Beta Model TBS-8/16-1 electron linear accelera- Combining reaction mechanisms proposed for tor, which provided 4-5 ns pulses of 8 MeV elec- model compounds, three alternative pathways of trons [13]. Absorbed doses per pulse were in the nicotine reaction with hydroxyl radical (Fig.2) can range 4-12 Gy. be taken into account. However, basing on thermo- Reactions with ●OH radicals were studied in dynamics calculation, the most stable product of aqueous solution saturated with N2O, which scav- these reactions are the radicals located at 2’-carbon enges hydrated electrons and nearly doubles the atom as 2’-carbon-hydrogen bond has the lowest amount of ●OH radicals [14]. In the reaction of BDE (bond dissociation energy) due to 2’-radical ●OH radicals with nicotine we obtained transient stabilization by the interactions with π electrons of products absorbing with the maxima at 330 and pyridine ring and the nonbonding electron pair of 460 nm (Fig.3). The build-up kinetics at these two the nitrogen atom. Importantly, protonation elim- maxima are essentially the same, so they probably Table. Rate constants k [dm3mol–1s–1] for the reaction of ●OH radicals with nicotine and its model compounds.

Reagent Nicotine Pyridine Pyrrolidine IChTJ, NDRL Wang et al. [9] IChTJ Getoff et al. [11] Getoff et al. [10] 3.2 × 108 (pH = 1, 4.5 × 108 (pH = 7, 1.4 × 108 (pH = 3, 1.0 × 108 (pH = 2.0-4.5, 9.6 × 109 (pH = 2) λmax = 330 nm) λmax = 460 nm) λmax = 320 nm) λmax = 315 nm) 1.45 × 1010 (pH = 8) 9 9 9 2.7 × 10 (pH = 5.6, 5.3 × 10 (pH = 10, 3.0 × 10 (pH = 10, 9 ● 5.7 × 10 (pH = 6.2, OH λmax = 330 nm) λmax = 320 nm) λmax = 322 nm) λmax = 222.5 nm) 9 3.8 × 10 (pH = 7.4, 2.1 × 1010 (pH = 13.2, λmax = 330 nm) λmax = 230 nm) 6.2 × 109 (pH = 10,

λmax = 330 nm) 22 CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY

0.1 μs 1.5 μs 20.0 μs 45.5 μs 137.6 μs

Fig.4. Transient absorption spectra obtained by ●OH-attack on pyridine recorded 0.1 μs (■), 1.5 μs (●), 20 μs (□), 45.5 μs

(▲) and 137.6 μs (○) after the pulse in the N2O-saturated 1 mM pyridine solution, at pH 10. Inset: kinetic traces recorded at λ = 320 nm.

● Fig.5. Reaction scheme of N3 -induced nicotine 1e-oxidation.

0.03 μs 5.6 μs 36 μs 102 μs 155 μs

● Fig.6. Transient absorption spectra obtained by N3 -attack on nicotine recorded 0.03 μs (■), 5.6 μs (○), 36 μs (●), 102 μs (□) and 155 μs (▲) after the pulse in the N2O-saturated 1 mM nicotine solution containing 10 mM NaN3, at pH 10. Inset: kinetic traces recorded at λ = 330 and 460 nm, respectively. CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY 23 come from the same product. The second-order Our results support the assumption that ●OH rate constants, k(OH+Nic), determined at 330 nm are radicals can react with nicotine following three collected in Table. It can be noticed that the rate different pathways: (i) addition to pyridine ring, constant at pH 7.4 is almost one order of magni- (ii) direct hydrogen abstraction from pyrrolidine tude higher than that obtained by Wang et al. ring, and (iii) one-electron oxidation of nitrogen However, our values are very close to those previ- at pyrrolidine ring. ously measured for pyridine [10, 11], suggesting a close similarity of the reactions pathways. References In order to examine this similarity, we conduct [1]. Pogocki D., Ruman T., Danilczuk M., Danilczuk M., analogous experiments for pyridine obtaining Celuch M., Wałajtys-Rode E.: Eur. J. Pharm., 563, (similarly to the results of Getoff et al. [10, 11]) 18-39 (2007). transient absorption spectra with one distinct max- [2]. Halliwell B., Gutteridge J.M.: Free radicals in biology and medicine. Oxford University Press, Oxford 1999. imum at 320 nm and a broad absorption band in [3]. Andersen J.K.: Nat. Med., 10, Suppl. S18-S25 (2004). the visible range (Fig.4). (The calculated rate con- [4]. Winyard P.G., Blake D.R., Evans C.H.: Free radicals stants, presented in Table, are also very close.) and inflammation. Birkhäuser Verlag, Basel 2000. We conducted similar experiments for aque- [5]. Nielsen H.M., Rassing M.R.: Eur. J. Pharm Sci., 16, ous solutions of pyrrolidine, but in this case we did 151-157 (2002). not observe short-lived transient species absorb- [6]. CRC Handbook of Chemistry and Physics. CRC ing in the examined 280-600 nm wavelength range. Press, 2004. Earlier work of Getoff et al. shows that transient [7]. Baldacchino G., Hickel B.: Water radiolysis under ex- products of ●OH radicals reaction with pyrrolidine treme conditions. Application to the nuclear industry. In: Radiation chemistry. EDP Sciences, France 2008, are characterized by a single absorption maximum pp. 53-54. at about 230 nm [10]. [8]. Buxton G.V.: An overview of the radiation chemistry In order to examine 1e-oxidation pathway of of liquids. In: Radiation chemistry. EDP Sciences, nicotine reaction we studied it using the reaction France 2008, pp. 3-10. ● of nicotine with azide radical (N3 ), which reacts [9]. Li W.Z., Wang S.L., Wang M., Sun X.Y., Ni Y.M.: mainly via electron transfer. It is a weak oxidant Spectrosc. Spect. Anal., 23, 3, 481-484 (2002). not abstracting hydrogen atoms nor forming ad- [10]. Getoff N., Schwörer F.: Int. J. Radiat. Phys. Chem., ducts to π-electron systems. In such process nic- 7, 1, 47-49 (1975). otine radical cations are generated (Fig.5). [11]. Getoff N., Solar S., Sehested K., Holcman J.: Radiat. Phys. Chem., 41, 6, 825-834 (1993). The pulse-radiolysis experiments were conduct- [12]. Bobrowski K.: Nukleonika, 50, 3, 67-76 (2005). ed here in N2O-saturated 1 mM nicotine aqueous [13]. Hug G.L., Wang Y., Schöneich Ch., Jiang P.-Y., Fes- solution containing 10 mM NaN3. The transient senden R.W.: Radiat. Phys. Chem., 54, 559-566 (1999). absorption spectra with two pronounced maxima [14]. Janata E., Schuler R.H.: J. Phys. Chem., 86, 11, at 330 and 460 nm, were obtained (Fig.6). 2078-2084 (1982).

PRELIMINARY STUDIES ON RADIATION DEGRADATION OF AQUEOUS SOLUTION OF LINURON Monika Celuch1/, Anna Bojanowska-Czajka1/, Krzysztof Kulisa1/, Joanna Kisała2/, Katarzyna Kosno1/, Dariusz Pogocki1,2/ 1/ Institute of Nuclear Chemistry and Technology, Warszawa, Poland 2/ Faculty of Biology and Agriculture, University of Rzeszów, Poland

Phenylurea herbicides were introduced in the Linuron is widely used in pre- and postemer- 1950s, and since that time their use has become sig- gence for treatment of both crop and non-crop nificant. Linuron (N-(3,4-dichlorophenyl)-N’-met- cultures. This herbicide is moderately persistent oxy-N’-methylurea) is one of the most commonly in soils, with a field half-life 30 to 70 days, and are used phenylurea herbicides. It has been broadly slightly to moderately soluble in water (81 mg/dm3 used to control weeds by inhibiting photosynthesis. at 25oC). Since linuron can give rise to important Linuron (Fig.1) has been reported to inhibit the residues in soil and in water and simultaneously it is resistant to the standard oxidants such as chlorine and permanganate, there is a strong need for finding new methods and/or developing known ones for effective degradation of linuron. For decomposition of pesticides, some microbiological and advanced oxidation processes (AOPs) are used, Fig.1. Chemical structure of linuron. e.g. O3/UV, O3/H2O2, electro- or photo-Fenton and activity of 5-α-reductase, reduce testosterone pro- others. Some of them were successfully used also duction. Its naturally decayed intermediates (i.e. for linuron degradation [1-13]. chloroaniline) have been suspected as endocrine Mechanisms of pesticides degradation are very disruptors. complex and depend on many environmental fac- 24 CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY tors as pH changes, presence of metal ions, etc. were observed and pH of the stored solution de- Detailed understanding of pesticides decomposi- creased from 10 to 7. HPIC analysis shows sub- tion is very important as some by-products can be stantial amount of acetates and formates (Fig.3). much more toxic than the parent compound. De- tailed describing of mentioned reactions should allow to predict degradation pathway of some molecule and designed structure and in such a way to decrease toxicity of by-products. Ionizing radiation has been applied to the decomposition of different groups of compounds [14, 15]. This seems to be a very effective way of its degradation, especially in the case of particularly oxidation-resistant compounds. In our work linuron (technical grade) was obtained from Zakłady Chemiczne Organika-Sarzyna S.A. (Poland) and the other chemicals were purchased from Sigma-Aldrich with highest analytical grade and, apart from linuron, all were used without further purification. Linuron was recrystallized Fig.3. Concentration of anionic products of linuron degra- from DMSO (dimethyl sulphoxide) befor use. For dation formed as post-radiation effect. pH adjustment, solutions of 70% perchloric acid (HClO4) and 50% sodium hydroxide (NaOH) were The results of our preliminary studies are very used. All experiments were carried out at room interesting and important from both basic and temperature. Experiments were performed using environmental research. Degradation processes a solution of linuron concentration equal to 0.0641 should be examined to detailed described mecha- g/dm3 and pH 10. Specially constructed glass tubes nism of linuron decomposition. Due to the fact were used during saturation of samples with N2O, that very often by-products are more toxic than and following the irradiation in a Co-60 source the parent compound, as many as possible inter- (dose rate – 7.6 kGy/h). In analytical determina- mediates products should be identified. Also the tion of linuron and products of its decomposition influence of some environmental factors (pH, some chromatographic techniques were used: metal ions, inorganic anions, etc.) on the degrada- HPLC (high-performance liquid chromatography) tion process should be examined. technique with spectrophotometric detection (at 254 nm) and ion-chromatography (HPIC – high- References -performance ion chromatography) with conduc- [1]. Farre M.J., Domenech X., Peral J.: Water Res., 40, tometric detection. HPLC analyses were carried 13, 2533-2540 (2006). out just after irradiation and 9 days after irradia- [2]. Farre M.J., Domenech X., Peral J.: J. Hazard. Mater., tion. Results obtained for the samples measured 147, 1-2, 167-174 (2007). just after irradiation show about a 20% decrease [3]. Gatidou G., Iatrou E.: Environ. Sci. Pollut. Res., 18, 6, 949-957 (2011). of linuron concentration for the absorbed dose of [4]. Katsumata H., Kaneco S., Suzuki T., Ohta K., Yobiko 1 kGy (Fig.2). Y.: Chem. Eng. J., 108, 3, 269-276 (2005). [5]. Katsumata H., Kobayashi T., Kaneco S., Suzuki T., Ohta K.: Chem. Eng. J., 166, 2, 468-473 (2011). [6]. Rao Y.F., Chu W.: Chemosphere, 74, 11, 1444-1449 (2009). [7]. Rao Y.F., Chu W.: J. Hazard. Mater., 180, 1-3, 514-523 (2010). [8]. Zouaghi R., Zertal A., David B., Guittonneau S.: Rev. Sci. Eau, 20, 2, 163-172 (2007). [9]. Ghalwa N.A., Hamada M.,. Shawish H.M.A, Shubair O.: Electrochemical degradation of linuron in aque-

ous solution using Pb/PbO2 and C/PbO2 electrodes. Arabian J. Chem. (2011), in press. [10]. Faure V., Boule P.: Pestic. Sci., 51, 4, 413-418 (1997). [11]. Sung M., Huang C.P.: J. Hazard. Mater., 141, 1, 140-147 (2007). [12]. Bourgin M., Violleau F., Debrauwer L., Albet J.: J. Hazard. Mater., 190, 1-3, 60-68 (2011). Fig.2. Yield of radiation-induced degradation of linuron. [13]. Tahmasseb L.A., Nelieu S., Kerhoas L., Einhorn J.: Sci. Total Environ., 291, 1-3, 33-44 (2002). Degradation process is relatively slow and no [14]. Liu S.Y., Chen Y.P., Yu H.Q., Zhang S.J.: Chemo- significant amount of degradation products were sphere, 59, 13-19 (2005). observed. During analysis of samples stored 9 days [15]. Drzewicz P., Trojanowicz M., Zona R., Solar S., at a temperature of about 6oC, some new peaks Geringer P.: Radiat. Phys. Chem., 69, 281-287 (2004). CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY 25 REACTIVITY OF C-CENTRED RADICALS STABILIZED IN ZSM-5 ZEOLITE Marcin Sterniczuk, Jarosław Sadło, Grażyna Strzelczak, Jacek Michalik

Radicals play an important role in catalysis. Their cation interacting with lattice oxygen between two structure and properties are difficult to study be- silica atoms. Instead, signal B we assigned to 13CO cause of their extremely high reactivity. Matrix interacting with oxygen bonded to one only Si isolation technique in halocarbon and noble gas atom. The stability of A and B doublets depends matrices and trapping in zeolites are the methods on sample dehydration temperature, however al- of choice for studying electronic structure and ge- ways signal B is more stable than signal A. In a ometry of radical ions in solids [1-3]. In this paper sample dehydrated above 300oC doublet A disap- we present a study on the reactivity of carbon pears completely at 350 K, while signal B is still paramagnetic centres generated radiolytically in detected at 370 K (Fig.1). In hydrated samples H-ZSM-5 zeolites. We generate free radicals by both signals are much less stable; signal A decays γ-irradiation at liquid nitrogen temperature of at 160 K and B – at 200 K. When H-ZSM-5/13CO zeolites exposed earlier to carbon monoxide and zeolite is exposed at 77 K just after irradiation to follow their reactions by electron paramagnetic 5 Torr of oxygen, the doublets A and B disappear resonance (EPR) spectroscopy gradually increas- completely and a singlet with axial anisotropy: ing temperature. Based on EPR measurements, C(g ) C(g ) we measure their ractivity and postulate the sites II ┴ of their stabilization owing to quantum mechanics computation. The H-ZSM-5 zeolite samples placed in spec- trosil tubes were degassed and next dehydrated at 300oC on vacuum line under the pressure of 10–5 Torr. Carbon monoxides, 12CO and 13CO were adsorbed at room temperature under the pressure range 5-100 Torr. Then the EPR tubings were sealed and irradiated at 77 K in a 60Co γ-source with a dose of 6 kGy. The EPR spectra were recorded with an X-band Bruker ESP 300E spectrometer equipped with a transfer nitrogen dewar. The temperature of the sample during EPR measurments was controlled by a Bruker variable temperature unit in the range 100-380 K. 13 Fig.2. Temperature dependence of H-ZSM-5/ CO+O2. The The EPR spectrum of γ-irradiated H-ZSM-5/ arrow shows the next measuring steps. 13CO recorded at 300 K consists of two doublets: anisotropic doublet A with gx = 2.0005, gy = 2.0010, g┴ = 2.0065, gll = 2.0470 and additional structure gz = 1.9995, Ax = 30.2 mT, Ay = 27.4 mT, Az = 26.0 in the central part is recorded (Fig.2). During mT and isotropic doublet B – giso = 2.0002, Aiso = thermal annealing above 200 K, signals A and B 21.4 mT. We assigned signal A to two paramag- start appearing, reaching the highest intensity netic centre which are characterized by the same around 300 K. However, when the temperature of EPR parameters: the first one – 13CO+● radical EPR measurments decreases again to 100 K, the cation interacting with lattice oxygen between Si doublets disappear. The process is reversible and and Al atoms and the second one – 13CO+● radical

Fig.3. Distribution of unpaired electron spin density on Fig.1. Temperature dependence of H-ZSM-5/13CO spectra. paramagnetic centre A. 26 CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY the 13CO+● doublets are recorded only above 200 tropic singlet of peroxy radical. In the H-Y zeolite, K. A similar effect was observed by Vedrine et al. Vedrine observed only one CO+● centre (centre [4] in zeolite H-Y exposed to 13CO and was explain- A). Our results prove that all the observed CO+● +● ed by coadsorption of O2 molecule on the CO centres in H-ZSM-5 zeolites are able to coadsorb oxygen forming peroxy radicals. To better understand the reactivity between the carbon-centred radicals and molecular oxygen we applied the DFT method. Computation clearly shows how the unpaired electron density is distributed on paramagnetic centre before (Fig.3) and after coadsorption of oxygen (Fig.4). Unpaired electron density before oxygen adsorption was localized principally on the carbon atom. After O2 coadsorption, we are observing a change of electron spin density distribution, the unpaired electron being localized almost only on the oxygen atoms. References [1]. Knight L.B., Jr., Steadman J.: J. Chem. Phys., 77, 1750 (1982). [2]. Garcia H., Roth H.D.: Chem. Rev., 102, 3947 (2002). Fig.4. Distribution of unpaired electron spin density on [3]. Knight L.B., Jr., Gregory B.W., Cobranchi S.T., Wil- coadsorbed complex with oxygen. liams F., Qin X.: J. Am. Chem. Soc., 110, 327 (1988). [4]. Vedrine J.C., Massardier J., Abou-Kais A.: Can. J. centre. This leads to the transfer of unpaired elec- Chem., 54, 1678 (1976). tron from carbon to the oxygen nucleus which is manifested in the EPR spectrum as axially aniso-

MULTIFREQUENCY EPR STUDY ON γ-IRRADIATED BONE SUBSTITUTING BIOMATERIALS Jarosław Sadło, Grażyna Strzelczak, Małgorzata Lewandowska-Szumieł1/, Marcin Sterniczuk, Jacek Michalik 1/ Department of Histology and Embryology, Medical University of Warsaw, Poland

For years, orthopaedic surgeons have been using substituting biomaterials based on hydroxyapatite many synthetic materials (metals, plastics, poly- [3-5]. mers, ceramics, etc.) to replace human tissues in Two types of synthetic bone substituting ma- order to restore their lost functions. The biomaterials – NanoBone® (Artoss GmbH) and HA terial market is expanding rapidly, parallel to the Biocer (CHEMA), a synthetic chemically pure hy- growing demands for bone graft substitute ma- droxyapatite powder purchased from Sigma-Aldrich terials. The substitutes should promote the forma- Co. and powdered defatted human compact bone tion of new natural bone, while the external ma- samples in natural form, obtained from the National terial should be degraded. Therefore, a great Centre of Tissue and Cell Banking (Warszawa, variety of specially synthesized calcium phosphate Poland) were used in this study. materials to be used as bone graft substitute ma- All samples were irradiated at room tempera- terials is proposed [1]. ture, with a dose of 5 kGy in a 60Co gamma source Hydroxyapatite (HA) Ca10(PO4)6(OH)2 is the “Issledovatel”. major mineral phase in natural bone and teeth, so The EPR measurements at X- (9.5 GHz) and synthetic HA is widely used in medicine and den- Q-band (34 GHz) were carried out at room tem- tistry because of its biocompatibility and bioactiv- perature just after the gamma irradiation, one day ity properties. Producers of bone graft substitute and five days later, in order to make sure that all materials often describe their products as chemi- signals derived from the unstable radicals decayed. cally and mineralogically identical to the inorganic The most stable and intense EPR signal in part of bone [2]. both natural bone and synthetic HA is an aniso- In bone which has been exposed to ionizing tropic singlet of an orthorhombic symmetry, with radiation several radicals are induced, which can the following spectroscopic parameters of the g be detected by electron paramagnetic resonance tensor: gx = 2.0030, gy = 1.9973, gz = 2.0017 and

(EPR) spectroscopy. peak-to-peak width ΔHpp = 0.85 mT (Fig.1). EPR In the present study we apply X- and Q-band spectrum of synthetic HA recorded in X-band – EPR spectroscopy to identify paramagnetic centres (Fig.1a) represents CO2 radical anion. The spec- which are responsible for EPR signals that are trum recorded in Q-band (Fig.1b) is much better stable at room temperature in γ-irradiated bone resolved giving evidence that is consists of two CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY 27 assure that the hydroxyapatite used in their product is almost the same as in autologous bone. However, the EPR study of irradiated compact bone and the synthetic graft materials suggests that their microscopic structures are different. NanoBone®

Fig.1. EPR spectra of synthetic hydroxyapatite powder sample γ-irradiated at room temperature: (a) recorded in X-band 1 day after irradiation, (b) recorded in Q-band 1 day after irradiation.

– separate signals: CO2 orthorhombic and isotropic – CO2 with g factor gav = 2.0006 [3, 5-7]. The EPR signals of the irradiated synthetic bone grafts substitute NanoBone® and HA Biocer Fig.2. EPR spectra of NanoBone® powder sample γ-irra- detected in the X-band looks like a broad singlet diated at room temperature: (a) recorded in X-band 1 day with two inflection points. The Q-band spectrum after irradiation, (b) recorded in X-band after 5 days storage, (c) recorded in Q-band 1 day after irradiation. is much better resolved showing clearly the signal anisotropy with the orthorombic g factor of gx = The results presented prove that EPR spec- 2.0041, gy = 2.0036, gz = 2.0018, characteristic of troscopy is a useful tool for studying subtle struc- 3– the CO3 anion radical. tural changes in bone substitute materials. After 5 days of storage, the EPR spectrum was changed in a similar way for both NanoBone® References and HA Biocer samples, showing a weak high- [1]. Dorozhkin S.V.: Biomaterials, 31, 1465-1485 (2010). – [2]. Leventouri Th.: Biomaterials, 27, 3339-3342 (2006). -field component (gll = 1.997) of the CO2 signal (Fig.2). [3]. Strzelczak G., Sadło J., Michalik J.: Nukleonika, 54, The EPR results prove clearly that the long- 247-250 (2009). [4]. Fattibene P., Callens F.: Appl. Radiat. Isot., 68, 2033 -lasting radiation effects associated with carbon- (2010). -centered radicals in commercial bone substitutes [5]. Callens F., Vanhaelewyn G., Matthys P., Boesman E.: are different than those in biological hydroxyapa- Appl. Magn. Reson., 14, 235-254 (1998). tites. It might be related to the different locations [6]. Strzelczak G., Sadlo J., Danilczuk M., Stachowicz W., 2– of the CO3 anions and/or the CO2 molecules in Callens F., Vanhaelewyn G., Goovearts E., Michalik J.: both types of materials. HA Biocer and Nano- Spectrochim. Acta Part A, 67, 1206-1209 (2007). Bone® are commercial synthetic bone substitut- [7]. Ikeya M.: New application of electron spin resonance: ing or reconstructing materials based on hydroxy- dating, dosimetry and microscopy. Eds. M.R. Zimmer- apatite. Producers of both the graft materials man, N. Whitehead. World Scientific, Singapore 1993. 28 CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY SURFACE MODIFICATION OF POLY(ESTERURETHANE) BY RADIATION-INDUCED GRAFTING OF N-ISOPROPYLACRYLAMIDE Marta Walo, Grażyna Przybytniak, Murat Barsbay1/, Pınar Akkas Kavaklı1/, Olgun Guven1/ 1/ Department of Chemistry, Hacettepe University, Ankara, Turkey

It is generally known that the required properties tography (GPC), contact angle measurements (CA) of biomaterials are biocompatibility, sterilizability, and X-ray photoelectron spectroscopy (XPS). adequate mechanical and thermal properties as Chemical structures of non-grafted PUR and well as specific surface characteristic [1]. Among PNIPAAm (poly(N-isopropylacrylamide)) grafted the polymeric biomaterials, polyurethanes (PUR) have attracted a great interest due to their unique chemical and physical properties. Biomedical polyurethanes are widely used in medicine for production of scaffolds in tissue engineering and for manufacturing medical devices, such as vascular grafts, artificial hearts, wound dressings, blood tub- ing, catheters and mammary implants [2]. Poly- urethanes are microphase-separated polymers containing hard and soft segments arranged alternately. Thanks to the possibility to model their properties by selecting various types and molecular weights of the oligodiol, the chemical structure and symmetry of diisocyanate, the hard/soft segment weight ratio, the synthesis method, PUR can be used for specific clinical applications. However, it is diffi- Fig.1. ATR-FTIR spectra of PUR (A) and PUR-g-NIPAAm cult to synthesize polyurethanes with appropriate (B), GY = 22%. bulk and surface properties simultaneously. It is well known that the surface properties of materials PUR were investigated by FTIR spectroscopy in contact with biological systems play a key role (Fig.1). Analysing the carbonyl region of PUR in determining the outcome of biological material and PUR-g-NIPAAm a new C=O stretching band interactions [3]. Therefore, selected functional at about 1656 cm–1 characteristic of PNIPAAm groups must be introduced to surfaces in order to structure appeared. change their properties. There is a multitude of For neat PUR two steps decomposition, it is surface modification methods including chemical revealed in the TGA curves (Fig.2). The first low treatment, immobilizing biological molecules, ra- temperature stage of thermal degradation is as- diation grafting of hydrophilic monomers and gas sociated with scission of the urethane linkages in plasma treatment [4]. Among these methods, radi- hard segments combined with the emission of ation-induced graft polymerization is a well-known carbon dioxide. The second one corresponds to technique for modifying the chemical and physical the soft segment chain cleavages. After NIPAAm properties of polymeric materials without altering grafting, the changes on TGA thermogram were their inherent properties. observed as a newly formed peak at around 400oC The aim of the reported researches was to attributed to the degradation of PNIPAAm. modify the surface of polyurethane by radiation-in- On the basis of GPC results, it was found that duced grafting to improve its hydrophilicity. The the grafting of NIPAAm onto polyurethane sur- samples used for grafting were synthesized by a face causes a shift of the chromatograms to higher two-step polycondensation without any catalyst, molecular weight regions. A new peak appearing solvent and additives. PUR was constructed from in the GPC traces is attributed to the grafted soft segments of oligo(ethylene-buthylene adipate) diol end-capped with molecular mass of 2000 Da and hard segments of isophorone diisocyanate and 1,4-butanediol. The weight ratio between hard and soft segment was 40:60. In this study the mutual radiation grafting of N-isopropylacrylamide (NIPAAm) onto polyurethanes films was performed. At the first stage of investigations, several important factors determining the final effect of graft polymerization were tested, namely: monomer concentration, homopolymer suppressor concentration and dose. Then, non-grafted and grafted polyurethanes with different grafting yield (GY) of 22, 59 and 77% were characterized using the following methods: ATR-FTIR spectroscopy, thermogravimetric analysis (TGA), gel permeation chroma- Fig.2. DTG thermograms of PUR and PUR-g-NIPAAm. CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY 29 dominant participation of C-O and C-C/C-H groups in the PUR surface. Carbonyl groups of the ester units also contribute significantly to the surface structure (25%), contrary to the peak at 288.6 eV attributed to N(H)-C(O)-O whose participation does not exceed 4%. For PUR-g-NIPAAm with GY = 22%, C-O-C(O) and C-N groups con- Table 1. Deconvolution of C1s XPS spectra.

Sample Peak Centre [eV] Ratio [%]

A 288.6 3.9 B 287.0 25.0 PUR C 285.1 15.3

Fig.3. GPC chromatograms of PUR and PUR-g-NIPAAm D 284.0 55.8 in THF (tertrahydrofuran). A 287.9 30.1 PNIPAAm chains, and the intensity of this peak B 286.8 23.2 increases with increasing grafting yield. These re- PUR-g-NIPAAm sults clearly proved formation of the covalent C 285.2 25.2 bonds between the PNIPAAm chains and the poly- D 284.2 21.5 urethane surface (Fig.3). stitute 25% of the C1s bands, whereas before grafting their contribution was about 10% smaller. Additionally, for the grafted surface summary in- put of N(H)-C(O)-O and N-C-C(O) enhances significantly as compared to the untreated PUR (Table 1). Surface hydrophilicity of the PUR film was enhanced by grafting of NIPAAm (Table 2). It was observed that the contact angle measured vs. water diminished to about 67 deg for the sample grafted to GY = 77%. Table 2. Contact angle measurements vs. water at 23oC.

Sample PUR PUR-g-NIPAAm

GY [%] 0 22 59 77 CA [deg] 87.0 71.0 69.0 67.0

The obtained results suggest that the radiation- -induced grafting seems to be a promising method to improve the biocompatibility of polymers for biomedical applications. By introducing specific functional groups to the trunk polymer, surface properties changed significantly. Contact angle, which is an important macroscopic parameter characterizing surface wettability, decreases from 87 to 67 deg confirming increasing hydrophicility of polyurethane surface. References [1]. Chen K., Kuo J., Chen C.: Biomaterials, 21, 161-171 (2000). [2]. Gorna K., Gogolewski S.: Polym. Degrad. Stabil., 79, Fig.4. XPS spectra of C1s for PUR and PUR-g-NIPAAm, 465-474 (2003). GY = 22%. [3]. Gold J.: Eur. Cell. Mater., 10, Suppl. 1 (2005). [4]. Alves P., Coelho J.F.J., Haack J., Rota A., Bruinink A., XPS results confirmed NIPPAm grafting onto Gil M.H.: Eur. Polym. J., 45, 1412-1419 (2009). polyurethane surface (Fig.4). High-resolution C1s region comprising four distinct peaks indicates 30 CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY RADIATION-INDUCED REDUCTION OF CARBON DIOXIDE AS POSSIBLE EXPLANATION OF ABIOTIC FORMATION OF METHANE Ewa Maria Kornacka, Zbigniew Paweł Zagórski

The presence of methane (CH4) and carbon dioxide (CO2) in the solar system, in particular, on the planet Mars is explained by different hypo- theses, especially by biotic formation in the last- -mentioned case. The explanation providing formation of methane as the by-product of life processes is doubtful in the light of few arguments for existence of the present and of any time ago, of life on Mars. In view of justified considerations of ionizing radiation on the surface of Mars, present and actual and consequences of the phenomenon [1, 2], we propose the formation of methane from carbon dioxide in the presence of water by chemical reactions induced by ionizing radiation, abundant Fig.1. EPR spectra of irradiated mixing media CO /H O. on the surface of Mars, due to its weak protection 2 2 by a thin atmosphere, very different from the thick Most atmospheric carbon dioxide on Earth has atmosphere around the Earth. been changed biologically into CaCO3 during the Raw materials for the set of chemical reac- last 600 million years. Solid carbon dioxide is pre- tions, induced by ionizing radiation coming from sent in nature on several planets, also on the sur- the outer space are minerals incorporating water, face of Mars. surrounded by atmosphere rich in carbon dioxide Figure 2 shows the EPR spectra of solid carbon and Martian ice consisting of water and carbon dioxide irradiated by γ-rays at 77 K and measured dioxide mixed ice, covering parts of the surface of also at 77 K after annealing to indicated tempera- Mars, under constant thawing and freezing in cold tures. It turned out that in the sample a contami- regions of Mars. The road map of methane forma- nant of water coming from the moisture was found ● tion is complicated and involves several steps, and three peaks belonging to OH radicals – gzz = through intermediates. 2.055, gxx = 2.029, gyy = 1.995 – were observed at In checking these possibilities, we have started 120 K. The character of the recorded spectra sug- from two materials, resembling those which may gests interaction between the radicals present in be present on Mars. First, it was montmorillonite atmosphere. Peroxy radicals such as HO2, CH3O as a model compound of Martian regolith, contain- and NO2 were measured in free troposphere and ing bound and added water (cf. [3]) and the sec- a atmosphere boundary layer [7]. The radicals are ond was CO2/H2O ice obtained by freezing from a not stable because they quickly disappeared and gaseous mixture. Both materials were gamma-ir- at 120 K their amount is ca. 50%, but at 150 K radiated in ampoules filled with carbon dioxide, they convert to such a different radical which and the gas phase was analysed by gas chromato- shows a spectrum in the form of singlet. graphy on a column in an argon stream. Products were identified as hydrogen formed directly from both forms of water, as it is the common case described in [4, 5] and as methane. Both materials were also investigated in separate experiments after irradiation, by EPR (electron paramagnetic resonance) spectroscopy for identification of intermediates leading to the formation of methane. Gas chromatographic results will be published later. A mixture of CO2/H2O was obtained by flowing of carbon dioxide saturated with aqueous vapour into liquid nitrogen. Resulting solid phase was irradiated to a dose of 20 kGy at 77 K (Fig.1). EPR spectra were measured with a Bruker X-band ESR-300 spectrometer at 77 K using a microwave power of 10 mW. Samples were annealed by warm- Fig.2. EPR spectra of irradiated solid carbon dioxide. ing to required temperatures, as measured by a Three spectra were identified corresponding thermocouple placed in the middle of the samples, to the radicals: hydroxyl radical, carbon dioxide then re-cooled down to 77 K and spectra were re- radical, superoxide radical. At least one uniden- corded [6]. Double integration of the experimental tified species was found whose extreme lines are spectra and the signals were recorded. indicated by the arrows in Fig.3. CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY 31 protons, is signalled as approaching. A mixed character of ionizing radiation leaves open the question of the depth-dose distribution, which is deep in the case of low LET fractions. One should note that it is anyway deeper than in the case of UV+VIS radiation which also can contribute to methane formation, but its action is limited to a thin surface of Mars. Presented hypothesis cannot be a complete and final one, because there are many paths involved in reaching final stable products of radiolysis. Only the primary products, as observed by EPR, are of a zero order considering kinetics and, therefore, are independent of the temperature of irradiated material. However, secondary products of chemi- Fig.3. Isolated EPR spectra of selected radicals. cal changes of the primaries can be temperature Methane formed is a stable compound remain- dependent. ing in the atmosphere, or bound in situ as a clath- Another problem is the total balance of radia- rate if sufficient amount of water is available. tion, in particular the question of the excess of There are assumptions, that methane aqueous oxygen, resulting from the conversion of carbon clathrates exist on Mars. dioxide to methane. One explanation is the assum- Answering the question of quantities of meth- ed formation of hydrogen peroxide, suggested by ane which can be formed in the proposed way, one Houtkooper [11], and listed among other com- has to know the flux of ionizing radiation on the pounds of Mars by Irwin and Schulze-Makuch [12]. surface of Mars. Astonishingly, in spite of several Another one is the decomposition of one of pri- kinds of measurements of the surface of Mars, the maries observed by EPR into molecular oxygen, exposure to ionizing radiation, important in view disappearing in the gaseous sink, surrounding ir- of possible human exploration, has not been meas- radiated clays or mixed ice. ured (or not published to avoid objections to hu- This investigation is supported by European man exploration missions, or even panic). A paper, COST action CM0703 and by the Ministry of which was kept for one year in the editors pro- Science and Higher Education grant. cessing [8], does not mention the dose on the surface of the space ship; another paper [9] mention- References ing the sterilization of the surface of Mars does [1]. Zagórski Z.P.: Nukleonika, 50, Suppl. 2, 59-63 (2005). not give the dose of radiation, etc. There are some [2]. Zagórski Z.P.: Role of radiation chemistry in the clues, as considering the radiation flux on the sur- origin of life, early evolution and in transportation face of Mars, because it must be similar to the flux through cosmic space. Chapter 5. In: Astrobiology: on the surface of any object in the outer space in emergence, search and detection of life. Ed. V.A. Ba- siuk. American Scientific Publishers, 2010, 57 p. the solar system. Recalculation of data in Ref. [10] [3]. Ehlmann B.L. et al.: Nature, 479, 53-60 (2011). suggests that an average dose of 0.1 Gy per day [4]. Zagórski Z.P.: Indian J. Rad. Res., 3, 89-93 (2006). may be liberally assumed. All calculations are es- [5]. Zagórski Z.P.: Origins Life Evol. Biospheres, 36, 3, timates in orders of magnitudes only. 244-246 (2006). The discussed intensity of ionizing radiation [6]. Kornacka E.M., Ambroż H.B., Przybytniak G.K.: reaching Mars is difficult to estimate, because of Radiat. Phys. Chem., 70, 677-686 (2004). highly non-homogeneous character of radiations, [7]. Mihelcic D., Voltz-Thomas A., Patz H.W., Kley D.: J. by both quality measured by LET and distribution Atm. Chem., 11, 271-297 (1990) in time. As the flux of galactic cosmic rays may be [8]. Pálfalvi J.K.: Radiat. Meas., 44, 724-728 (2009). [9]. Dartnell L.R.: Astrobiology, 11, 551-582 (2011). considered stable, more intensive radiation is [10]. Semkova J. et al.: Adv. Space Res., 49, 471-478 reaching Mars during periodical Sun activity. In (2012). particular, that radiation is considered specially [11]. Houtkooper J.M., Schulze-Makuch D.: Int. J. Astro- dangerous for the crew in space. A warning is an- biol., 6, 147-152 (2007). nounced to hide behind the cargo of the space [12]. Irwin L.N., Schulze-Makuch D.: Cosmic biology. ship, after electromagnetic, faster radiation than Springer, New York 2011.

STUDIES OF PHYSICOCHEMICAL PROPERTIES OF GELS BASED ON IRRADIATED WHEAT STARCH Krystyna Cieśla, Wojciech Głuszewski

Starches derived from various plants are an abun- starch, viscosity and stability of gels appear to be dant and cheap raw material with a high potential the crucial factors that affect its possible applica- for application in various food, pharmaceutical tion. This concerns the application of modified and technical industries [1]. Gelling properties of starches as the functional additives in food prod- 32 CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY ucts (gelling, firming or bulking agents, thickeners gelling behaviour of the starch and to the struc- and emulsifiers) or as a component of plastics and ture of the gels. packaging (films and coatings), including active The solid wheat starch of Sigma production packaging and variety of delivering systems (paper, (S-5127) was irradiated with Co-60 gamma radia- textile, chemical, food and pharmaceutical indus- tion in air at ambient temperature in a gamma cell tries). This occurs because the film forming ability “Issledovatel” placed in the Centre for Radiation depends on the properties of the starch gel. Research and Technology, Institute of Nuclear Although potato starch is in Poland largely Chemistry and Technology (INCT). The doses of used for this purposes, the possibility of applica- 5, 10, 20 and 30 kGy were applied with a dose rate tion of other starches seems to be also beneficial. of 0.36 Gys–1. Wheat starch appears as an alternative due to the Gelling behaviour of the starch was examined content of naturally occurring lipids that make it using a procedure described in [4]). This concerns possible to modify the functional properties of determination of the volume of the gel formed starch additives or to obtain products with reduced after heating of 3 ml aliquots of 20% starch sus- hydrophilicity as compared to the starch not con- pensions at selected temperatures (50, 60, 75, 90, taining hydrophobic additives. The gels prepared 120oC) during 40 min, and centrifuged. Then, the basing on wheat starch reveal a lower viscosity as apparent amylose content was evaluated basing a compared to the gels prepared basing on the po- blue value method. A Beckman DU-68 spectro- tato starch. This might be beneficial for some ap- meter was applied for the collection of VIS spec- plications requiring a high content of the solid troscopy data. matter accompanied by low or medium viscosity For examination of the viscoelastic properties (i.e. textile or paper coatings). [7], 20 wt% gels were prepared. Gelatinization was Starch degradation accompanied by oxidation carried out on an oil bath maintained at 140oC (1 h are desirable processes that enable to obtain prod- at a temperature in the range from 70 to 140oC ucts forming gels with reduced viscosity in relation and 30 min at 140oC). The gels were cooled down to those formed by the native starch. Several chem- to 25oC and submitted to examination using a ical and enzymatic methods are involved in modi- Brookfield viscometer DVII+Pro connected to a fication of starch properties leading to obtain on thermostat. Three experimental procedures were an industrial scale appropriate products that can applied: serve for the production of gels with the required • Procedure I: Dependence of the shear stress, viscoelastic properties. Research concerning the torque and viscosity on the applied shear rate development of methods of starch modification (rotation speed) were determined for the gel and testing the new products containing such sample (non-irradiated) maintained at the re- hydrocolloids are being conducted [2]. Ionizing quired temperature. The selected temperatures radiation seems to be a perspective alternative were: 25, 35, 50, 75, 90 and 95oC. The measure- method enabling to reduce the use of toxic and ments were carried out during increase and de- strong chemicals, in relation to chemical methods, crease of the shear rate. These experiments were to reduce the costs in relation to the enzymatic done during increase of temperature followed methods, and easily steering of the process by the by decrease of temperature. way of irradiation parameters. Such methods ap- • Procedure II: Examination of the gels were pear to be perspective also for starch modification, carried out at the selected shear rate during dy- (independently of the present restriction concern- namic heating with an average rate of 3.5 oC/min ing foodstuffs) in regard to the occurring degrada- followed by cooling with an average rate of 1.4 tion and oxidation processes leading to a significant oC/min. The value of shear rate equal to 20.9 s–1 decrease in swelling power and viscosity of gels was selected basing on the results arising from [1, 3, 4]. Accordingly, some trials were done last experiment I. The measurements were perform- years for re-investigation of the radiation processes ed at 25oC and after increasing/decreasing tem- in starches in relation to their possible practical perature with a step of 5 till 95oC. implementation [5]. • Procedure III: Examination of the gels were Our results dealing with gelatinization behav- carried out at the selected shear rate during iour of the irradiated starches have shown a de- prolonged storage at ambient temperature. The crease in the swelling power induced by irradia- minimum value of shear rate 1.1 s–1 (5 RPM) tion accompanied by an increase in the content of was selected for this purpose. water soluble fraction [4]. It was also found that For SEM observation gels containing 12.5% of gamma irradiation performed for the wheat starch dry matter were prepared on the way of heating lead to the improvement of the functional prop- the starch suspensions for 35 min in glass tubes erties of the films prepared basing on this starch placed in a heating chamber stabilized at 100oC. [6]. Wheat starch films have appeared, moreover, With the purpose of attaining freezing, a drop of more elastic as compared to the potato starch films, hot gel was flowed out or made a smear on the although their tensile strength was smaller [6]. frozen metal surface. SEM studies were conducted Accordingly, the present studies dealt with the at depressed temperature (-15oC) at low vacuum influence of irradiation performed for wheat starch using a Quanta 200 Microscope (FEI) installed in on the viscoelastic properties and stability of the the Analytical Centre, Warsaw University of Life formed gels. These properties were related to the Sciences (SGGW). CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY 33 the process increases due to the more advanced gelatinization (Fig.2). Figure 3 present the example of dependence of the shear stress on the shear rate recorded during the increasing or decreasing temperature for the gel prepared using the non-irradiated starch. The curves show hysteresis with the values recorded on the increasing shear rate in most of the cases higher than the values recorded on the decreasing shear rate. As can be expected, decrease in the shear stress (and in viscosity) was observed as related to the increase of temperature. However, higher values of shear stress and viscosity were recorded at a temperature of 95oC than at 90oC. At the same shear rate, all the values of shear stress Fig.1. Dose dependence of the volume of gel formed at 120oC after heating of 3 ml of starch suspension. Decrease in swelling power (Fig.1) accompanied by an increase in the apparent amylose and leaching of the grains during gelatinization (shown by the increasing absorbance of the polyiodine com-

Fig.4. The dependence of the shear stress on temperature, determined (at the shear strain equal to 17.6 s–1) on the basis of the data obtained during heating (data in Fig.3) and during cooling (data not shown) in the frame of experiment I for the gel formed using the non-irradiated starch. were higher during cooling as compared to the Fig.2. Dose dependence of the maximum absorbance of the polyiodine complexes formed by the small molecular frac- values recorded during heating. The dependence tion of the irradiated native potato starched after heating of the shear stress on temperature, determined on at the selected temperatures. the basis of the data obtained in the frame of experiment I shows the significant increase of this plex; Fig.2) are related to the decrease in the mo- parameter during cooling below 35oC (Fig.4). On lecular mass of starch after irradiation. The increas- the contrary, experiment II (dynamic heating and ing amount of the gel formed and the higher ab- cooling) carried out for the residue obtained after sorbances are detected when the temperature of experiment I indicated only small differences of

A B

Fig.3. The dependence of the shear stress on shear rate recorded during the increasing temperature for the gel prepared using the non-irradiated starch: A – 25, 30, 50 and 70oC; B – 90 and 95oC. 34 CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY

A Although the considerably higher values of shear stress were observed during heating of the non-irradiated samples in all the temperature range, the values recorded during cooling at a temperature lower than 80oC became comparable for both samples. The hysteresis in the shear rate – shear stress curves was observed also in the case of the gels obtained basing on the starch irradiated using a 10 kGy dose.

A B

Fig.5. The dependence of the shear stress on the temperature determined at the shear strain equal to 20.9 s–1 during dynamic heating and cooling (experiment II) for the gel formed using the non-irradiated starch (A) and the starch irradiated using a 10 kGy dose (B). the gel shear stress during cooling. Moreover, decrease of this parameter was observed contrary to the increase determined basing data from experiment I. The curve representing dependence of Fig.6. The changes of the shear stress of the gels (formerly processed) during storage at 25oC at the shear strain equal shear stress on the temperature during heating –1 was similar to that shown in Fig.5, with the differ- to 1.1 s : (A) non-irradiated starch, (B) starch irradiated using a 10 kGy dose. ence that the increase in shear stress starts already at a temperature higher than 75oC. The gels with the same “history” prepared bas- Therefore, experiment of the II type was carried ing on the non-irradiated starch and the starch ir- out for both the gels obtained basing on the non- radiated using a 10 kGy dose both have revealed -irradated starch and the starch irradiated using a after the dynamic cooling a relatively low viscosity dose of 10 kGy. The gels obtained basing on the (12.4 and 5.6 cP). However, the viscosity consider- irradiated starch were characterized by the lower ably increased already after 10 min of storage at stress (and consequently viscosity) as compared to room temperature. the gels obtained basing on the non-irradiated It appears that the stability of the parameters starch (Fig.5). In the cases of both samples, the of the cold gels of both types, irradiated and non- increase in the shear stress was observed during -irradiated, might be different. Therefore, the ex- heating at a temperature higher than 85oC. More- periment of the III type was performed after a over, the increase in shear stress was recorded also heating-cooling cycle (Fig.6). It can be stated that during heating in the range of the intermediate the stress in the non-irradiated gels decreases grad- temperature above 35-50oC. The fluent decrease ually during storage with a minimally slow stirring, in shear stress was observed during cooling in the while the stress in the gels irradiated using 10 kGy case of both samples. However, this decrease was dose, after the fast preliminary decrease, stabilizes more evident in the case of the irradiated starch. at a relatively constant level. Table. The shear stress values at a shear rate of 12.1 s–1 and the average values of dynamic viscosity determined for the 20% gels of wheat starch at a temperature of 25oC: directly after preparation (measurement I) and after subsequent 13 h (measurement II). Dose [kGy] Shear stress calculated at shear rate of 12.1 s–1 The average dynamic viscosity I [D cm–1] II [D cm–1] II/I I [P] II [P] II/I 0 10 746 10 937 1.02 986 ± 126 1 050 ± 118 1.06 10 5 756 66 233 1.17 370 ± 29 405 ± 36 1.36 20 3 019 5 643 1.87 181 ± 17 362 ± 29 2.00 CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY 35 Consequently, the studies of the gels stability ones. Beside to viscoelastic properties, the stabil- were continued under static conditions. The meas- ity of these properties of both the type gels de- urements were done according to an experiment- pends strongly on their history and the procedures al procedure (I) at a temperature of 25oC directly applied during examination. Therefore, when the after preparation and after the subsequent 13 h gels were slowly stirred at room temperature (after for the gels prepared using the non-irradiated additional heating-cooling treatment), a stability starch and two irradiated starches (10 and 20 kGy). of the gels formed using the irradiated starch (10 The viscoelastic properties of the gels containing kGy) was higher than the stability of the non-irra- the non-irradiated starch have revealed no essen- diated specimens. On the contrary, the stability of tial differences after 13 h storage as compared the freshly prepared gels left without stirring was to the fresh gels and only negligible differences the lower, the higher was irradiation dose. More- could be detected in the case of the starch irradi- over, the gradual increment in gel strength occurs ated using a 10 kGy dose. On the contrary, the contrary to the stirred gels. The differences in the gels obtained basing on the starch irradiated using gels properties were related to the differences in a 20 kGy dose were characterized after storage by their structure. Dependence of viscoelastic prop- the double value of the preliminary viscosity and erties of the gels on their thermal history is prob- shear stress (Table). ably connected with the increasing amount of the

A B

Fig.7. Examples of SEM images of the wheat starch gels: (A) non-irradiated, (B) irradiated with a 30 kGy dose (magnifi- cation – 1000x). The SEM images of the non-irradiated gels in- apparent amylose leached from the grains during dicate generally a honey-comb structure (Fig.7A), the prolonged thermal treatment. The participa- similarly as in the case of the potato starch gels tion of these formerly leached short molecular [8]. However, a considerable distribution of the products (larger in the case of the irradiated honey-comb cages were observed. After irradia- starch) in further formation of crosslinkages in tion, lengthening of the cages accompanied with the gel might have an additional impact on the the reduction in thickness of the transverse walls faster strengthening during storage of the gels can be noticed (Fig.7B), leading to the gel orien- formed using the non-irradiated starch. tation. The effect is similar to that observed in the References case of potato starch, finally resulting in the increased gel homogeneity. The observed changes [1]. Cieśla K.: Przekształcenia struktury nadcząsteczkowej w polimerach naturalnych inicjowane promieniowa- might be attributed to the radiation-induced weak- niem jonizującym (Transformation of supramolecular ening of the internal forces in gels, indicated by structure initialised in natural polymers by gamma ir- their smaller strength (as shown by the lower values radiation). Institute of Nuclear Chemistry and Tech- of viscoelastic parameters). nology, Warszawa 2009, 223 p. (in Polish). In summary, it can be stated that although ir- [2]. Tomasik P.: Przemysł Spożywczy, 54 (4), 16-18 (2000), radiation induces lowering of the strength of the in Polish. starch gels, the relatively fast dynamic cooling [3]. Raffi J., Agnel J.P., Thiery C.J., Fréjaville C.M., Saint- might result in the similar viscoelastic properties -Lèbe L.J.: Agric. Food Chem., 29, 127-132 (1981). in both the cases: the gels formed using the non- [4]. Cieśla K., Eliasson A.-C.: Acta Alimentaria, 36 (1), -irradiated starch and those formed using the ir- 111-126 (2007). [5]. Chung H.-J., Lee S.-Y., Kim J.-H., Lee J.-W., Buyn radiated starch (10 kGy). Slow cooling, as well as M.-W., Lim S.-T.: J. Cereal Sci., 52, 53-58 (2010). even short storage at room temperature induces, [6]. Cieśla K., Nowicki A., Buczkowski M.: Nukleonika, however, a high increase in the gel strength and 55, 2, 233-242 (2010). this increase is much higher in the case of the non- [7]. Cieśla K. et al.: Wpływ promieniowania gamma na -irradiated species as compared to the irradiated właściwości skrobi: oddziaływania z wodą i z lipidami, 36 CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY

folie skrobiowo-lipidowe (Influence of gamma irra- [8]. Cieśla K., Sartowska B., Królak E., Głuszewski W.: diation on the starch properties: starch interaction Gamma irradiation influence on structure of potato with water and lipids, starch-lipid films). Projekt ba- starch gels studied by SEM. In: Annual Report 2006. dawczy 2 P6T 026 27 Sprawozdanie merytoryczne 2007 Institute of Nuclear Chemistry and Technology, War- (in Polish). szawa 2007, pp. 49-52. CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY

Chemical issues of nuclear power and radiopharmaceutical chemistry – the top two domains of contemporary applied radio- and nuclear chemistry over the world – remained the subject of the research activity of the Centre for Radiochemistry and Nuclear Chemistry in 2011. The main research projects from the Centre were financed from the European Commission (FP7 Euratom, Fission), from the Operational Programme Innovative Economy (PO IG), as well as from the National Science Centre (NCN) and the National Centre for Research and Development (NCBiR). In line with the governmental plans to develop nuclear power programme in Poland, the main efforts of the Centre were focused on the chemical issues of nuclear power. The research teams of three Centre laboratories (Laboratory of Radiochemical Separation Methods, Lab- oratory of Membrane Processes and Technologies, and Laboratory of Sol-Gel Technology) continued their studies on radioactive waste managing, and on special nuclear materials. As a partner in the European Collaborative Project “Actinide recycling by separation and transmutation” (ACSEPT), we carried out studies on solvent extractive separation of americium from highly radioactive nuclear waste by using new selective poly-N-heterocyclic ligands, followed by theoretical investigations of potential reasons of their selectivity, as well as studies on sol-gel producing uranium dioxide matrices for nuclear transmutation of the separated americium (MOX fuels). Further work on new types of MOX nuclear fuels based on uranium oxides and carbides is the subject of a new Collaborative Project “Advanced fuels for generation IV reactors: reprocessing and dissolution” (ASGARD), that starts in 2012 with participation of our Sol-Gel team. Realization of two other European FP7 projects started in 2011. These are: (i) Collaborative Project “Implementing public participation approaches in radioactive waste disposal” (IPPA), aimed at creation of the arena for exchange of opinions and public acceptation of the problems of radioactive waste disposal, and (ii) “New MS linking for an advanced cohesion in Euratom research” (NEWLANCER), aimed at the increase of participation of Polish teams in the coming research Euratom programmes. On the national scale, the Centre coordinated the research project devoted to the possibilities of producing uranium from indigenous resources, and completed participation in the research project on the use of thorium based fuels in nuclear power reactors, both financed from PO IG. We evaluated Polish uranium resources and adapted efficient methods for extracting uranium from these materials. Within the new NCBiR strategic project “Supporting technologies for the development of safe nuclear power” that started in 2011, the Centre coordinates the workpackage entitled “The development of supporting technologies for the management of spent nuclear fuel and radioactive waste”. Within another NCBiR project, a small membrane plant has been designed for managing liquid low-radioactive waste. Within own, Institute statutory research, novel methods were studied for separation of metal ions, based on combination of membrane processes with adsorption (biosorbents), and complex formation with ultrafiltration, considered the basis for further technologies of radioactive waste management. Sol-gel methods have also been elaborated for obtaining novel materials (silica glasses, SYNROC matrices) making it possible to encapsulate and immobilize nuclear waste. Radiopharmaceutical chemistry research, conducted mainly in the Laboratories of Radio- pharmaceuticals Synthesis and Studies, and of Radiochemical Separation Methods, were focused on obtaining novel potential radiopharmaceuticals, both diagnostic and therapeutic, by either labelling novel biological vectors (peptides) with well-known radionuclides (99mTc, 188Re), or labelling of the known vectors with unusual radionuclides therapeutic 123Ra and PET 44Sc, including labelling with the use of functionalized nanozeolites. A number of novel 99mTc-labelled bioconjugates were synthesised and tested as potential receptor-imaging radiopharmaceuticals. A sol-gel method has been elaborated for producing yttrium oxide microspheres as precursors of potential radiopharmaceuticals for anticancer therapy. Apart from the Institute statutory research, the research in this field were funded from eight NCN and NCBiR projects, some of them under international cooperation. The international and national scientific cooperation of the Centre in both main fields of its activity, and the participation of the Centre researchers in international organizations and associations, described in the previous issues of INCT Annual Reports (2009 and 2010), were successfully continued and developed. Two young researchers continue their post-doc contracts at Duke University (NC, USA) and the Institute of Transuranium Elements JRC, Karlsruhe (Germany). One member of the Centre staff defended her PhD thesis. Five medals or other prizes have been awarded to the staff of the Laboratory of Sol-Gel Technology at three international trade shows and exhibitions for their three inventions of new materials. Two PhD students employed at the Centre have been granted with special half-year fellow- ships funded by the Government of Mazovia Province, and one got a European fellowship for a 3-month research stay at the Forschungszentrum Jülich (Germany). On the occasion of the International Year of Chemistry and the International Year of Maria Skłodowska-Curie, numerous staff members of the Centre were very active in organizing performances that popularized nuclear chemistry and its role in developing nuclear power and nuclear medicine, i.e. scientific exhibitions and demonstrations for the public, in particular pupils and students, as well as in presenting invited lectures related to scientific conferences and seminars both in Poland and abroad. The research activity of the Centre staff was complemented by their participation in the realization of the big PO IG project “Centre for Radiochemistry and Nuclear Chemistry – meeting the needs of nuclear power and nuclear medicine”, directed towards modernization of the research infrastructure of the Centre (laboratories and research equipment), funded from the structural funds of EU and of the Government of Poland. CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY 39 ION EXCHANGE EVIDENCE FOR CHEMICAL ISOTOPE EFFECTS OF GALLIUM AND INDIUM IN AQUEOUS HCl SOLUTIONS Irena Herdzik-Koniecko, Sławomir Siekierski, Jerzy Narbutt

Ion exchange chromatography was applied to study It has been found that on the cation exchanger the chemical isotope effects of gallium and indium the light isotope 69Ga was enriched at the front in ligand exchange reactions in aqueous HCl solu- part of the elution band and the heavy isotope tions. Cation and anion exchange resins, strongly 71Ga at the end part (Fig.1), whereas the light 113In acidic Dowex 50W-X8 and strongly basic Dowex isotope was enriched at the end part and the heavy 1-X8, were used as solid phases separating iso- isotope 115In at the front part (Fig.2). The isotope topically enriched chemical forms of the metals. separation factor ε was equal to 3.3 × 10–5 for Ga In order to enhance the isotope separation by in- and 2.0 × 10–4 for In [1]. The picture was found to creasing the path through the beds of ion ex- be reversed in the case of the anion exchange, changers, the merry-go-round elution method was where the heavy gallium isotope was enriched at used, where the band leaving a standard, 1 m long the front part and the heavy indium isotope at the chromatographic column was introduced back on the top of the column after each cycle. The number of cycles varied from 5 to 9, except for Ga on anion exchanger where – due to a large broadening of the band – it was equal to only two. Isotope ratios,

Fig.3. Elution curve and isotope ratio, Ri (▲), of gallium in the anion exchanger/2.5 M HCl system after 2 cycles. Ro denotes the gallium isotope ratio in the feed solution.

end part of the band (Figs.3 and 4), with ε equal –3 –4 Fig.1. Elution curve and isotope ratio, R (▲), of gallium in to ~10 and 1.7 × 10 , respectively [2]. Moreover, i the chromatographic band of gallium, eluted from the cation exchanger/2.5 M HCl system after 7 cycles. Ro denotes the gallium isotope ratio in the feed solution. the anion exchanger column was extremely broad and asymmetric (Fig.3). Ri, the ratios of the mass of the light isotope to Our analysis shows that the opposite isotope that of the heavy isotope (69Ga/71Ga and 113In/115In) effects for the two elements, the neighbours in were determined in selected fractions, i, of the ef- group 13 of the periodic table, can be explained in fluent by means of the inductively coupled plasma terms of the significant difference in their coordi- mass spectrometer (ICP-MS, Elan 6100, Perkin El- nation chemistries, which is a manifestation of the so-called secondary periodicity observed in numerous properties of group 13 elements [3]. In fact, stability constants of chloride complexes, low for 2+ 2+ [Ga(H2O)5Cl] and high for [In(H2O)5Cl] , dif-

Fig.2. Elution curve and isotope ratio, Ri (▲), of indium in the cation exchanger/0.5 M HCl system after 9 cycles. Ro denotes the indium isotope ratio in the feed solution.

mer Sciex). In the feed solution the isotope ratios, Fig.4. Elution curve and isotope ratio, Ri (▲), of indium in Ro, were equal to 1.50677 for gallium and 0.04482 the anion exchanger/1 M HCl system after 5 cycles. Ro de- for indium. notes the indium isotope ratio in the feed solution. 40 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY fer by about three orders of magnitude [4]. Gallium of the Ga3+–Cl– bond is somewhat smaller than and indium also differ in the coordination number the average energy of the Ga–ligand bonds in the 2+ and in the structure of their highest chloride com- [Ga(H2O)5Cl] complex which predominates in plexes: tetrahedral for gallium and octahedral for the aqueous phase [4]. Therefore, according to indium. Analysis of the numerical values of the sta- the theory, the light isotope ought to be enriched bility constants of the Ga and In chlorides leads to in the resin and at the end part of the elution 3+ the conclusion that the Ga –OH2 bond is slightly band. Really, Fig.3 shows that the light isotope stronger than the Ga3+–Cl– bond, whereas for the 69Ga is enriched at the diffuse end part and the indium complexes the bond strength is reversed heavy isotope 71Ga at the less diffuse front part of and the difference of bonds energies is much great- the band. The very large width of the elution band 3+ er. Therefore, the energy of the Ga –OH2 bond (only two cycles of the merry-go-round method 3+ in hexahydrate [Ga(H2O)6] (which because of its could be performed) points to particularly slow +3 charge prevails in the resin phase) is greater changes between tetrahedral and octahedral spe- – + than the average energy of the Ga–ligand bonds cies: [GaCl4] ↔ [Ga(H2O)4Cl2] ; that accompany 2+ in the [Ga(H2O)5Cl] complex (which prevails in the sorption/desorption processes of gallium on the the 2.5 M HCl solution [4]). The above assumption anion exchanger, as confirmed by kinetic studies permits to expect, in accordance with the Bigelei- [6]. The asymmetric shape of the band (very long sen-Mayer theory [5], the enrichment of the heavy tail) seems to be due to particularly slow change 71Ga isotope in the resin phase, i.e. at the end part from tetrahedral to octahedral coordination upon of the band, in agreement with the experiment desorption. The great change of the coordination (Fig.1). Small difference in the bond energies, the is probably the main reason of the high value of ε, – –3 fact that only one Cl anion is replaced by the H2O equal to about 10 , though the asymmetry of the 3+ molecule upon [Ga(H2O)6] adsorption, and prac- band makes this value only approximate. tically no change in the coordination geometry, Contrary to gallium, the merry-go-round me- 2+ 3+ from [Ga(H2O)5Cl] to [Ga(H2O)6] species point thod consisting of 5 cycles was successfully applied to the small value of the isotope separation coef- for indium on the anion exchanger, for which the ficient for Ga (ε = 3.3 × 10–5). band profile at 1 M HCl shows a sharp front and 3+ On the contrary, much weaker the In –OH2 slightly broadened end boundary (Fig.4). Owing than the In3+–Cl– bond permits to expect the en- to the charge, the main species in the resin is 115 3– richment of the heavy In isotope in the aqueous [InCl6] with admixture of the lower charged i.e. 2– phase, at the front part of the band eluted by [In(H2O)Cl5] , while the more hydrated com- 0.5 M HCl; opposite to gallium but also in agree- plexes with weaker In–ligand bonds predominate ment with the experiment (Fig.2). The isotope sep- in the aqueous phase (see above). Therefore, ac- aration factor for indium, ε = 2.0 × 10–4, one order cording to the theory and contrary to gallium, the of magnitude greater than that for gallium, points heavy isotope ought to be enriched in the resin to much greater difference in the energy between and at the end part of the elution band. Indeed, 3+ – 3+ 115 the In –Cl and In –OH2 bonds than the respec- the experiment shows that In is enriched at the tive difference for gallium, which is consistent with end part of the band, whereas 113In is enriched at the reported stability constants [4]. The other fac- the narrow front part (Fig.4). The band is broader tor contributing to the higher ε value for indium than those eluted from the cation exchanger, but than for gallium is the greater change in the coor- sharper than that for gallium. This picture can be dination sphere of the former, accompanying ad- attributed to the quite different composition of sorption process. Because the indium complexes indium complexes predominating in both phases, + predominating in 0.5 M HCl are [In(H2O)4Cl2] but to the same octahedral coordination of the – –4 and [In(H2O)3Cl3], hence two or even three Cl species. The ε value, equal to 1.7 × 10 , a little bit ions have to be replaced by H2O molecules upon lower than that for indium in the cation exchange 3+ [In(H2O)6] adsorption, whereas in the case of system, reflects some smaller number of exchanged – gallium, only one Cl ion is replaced by H2O mol- ligands, accompanying sorption/desorption in the ecule (see above). present system, at the same difference in the energy The end boundary of the gallium elution band, between the In-ligand bonds. The broadened end somewhat more broadened than the front bound- boundary of the band means that the conversion 3– ary (Fig.1), implies slightly slower substitution of of [InCl6] into the eluted, partly hydrated forms, – 3+ H2O by Cl , that accompanies [Ga(H2O)6] ad- is slightly slower than the reverse process. – sorption, than substitution of Cl by H2O, that ac- It is interesting to notice that the observed en- 2+ companies [Ga(H2O)5Cl] desorption. On the richment of the front part of the elution band of contrary, the indium elution band shows a sharp indium in the light isotope and the end part in the end and broadened front boundary (Fig.2), which heavy isotope in the anion exchanger/Cl– system – suggests faster substitution of H2O by Cl (desorp- shows the same pattern as that of gallium in the tion) than the reverse substitution. anion exchanger/NCS– system [7]. The reason is The picture observed in the case of anion ex- that both metals form rather strong complexes, of change systems is fully consistent with that ob- similar strength, in the respective solutions – ind- served for cation exchanger, but with the opposite ium with Cl– ions [4] whereas gallium with NCS– directions of the isotope effects. The anionic ions [8]. – [GaCl4] complex is probably the only form ad- In conclusion, we state that the opposite direc- sorbed on the anion exchange resin, and the energy tions and various magnitudes of the chemical iso- CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY 41 tope effects for gallium and indium, observed in References separation systems consisting of ion exchange re- [1]. Dembiński W., Herdzik I., Skwara W., Bulska E., Wy- sins and aqueous HCl solutions, can be explained, socka A.I.: Nukleonika., 51, 217-220 (2006). in accordance with the Bigeleisen-Mayer theory, [2]. Herdzik I., Dembiński W., Skwara W., Bulska E., Wy- in terms of the differences in coordination chem- socka A.: Gallium and indium isotope effects in the istry of chloride complexes of these two elements. Dowex 1-X8/HCl system. In: INCT Annual Report These differences appear in the composition and 2006. Institute of Nuclear Chemistry and Technology, coordination geometry of the separated complexes, Warszawa 2007, pp. 81-82. 3+ [3]. Siekierski S., Burgess J.: Concise chemistry of the ele- as well as in the strength of the M –OH2 and 3+ – ments. Horwood Publishing, Chichester 2002, pp. 90-91. M –Cl bonds. In particular, the processes of gal- [4]. Wood S.A., Samson I.M.: Ore Geol. Rev.., 28, 57-102 lium sorption/desorption in the system anion ex- (2006). changer/HCl are accompanied by the mutual con- [5]. Bigeleisen J., Mayer M.: J. Chem. Phys., 15, 261-267 version of tetrahedral and octahedral gallium (1947). chlorides. This great difference between the two [6]. Herdzik I., Narbutt J.: Kinetics of ion exchange of gal- forms results in the high value of isotope separa- lium and indium ions in the system aqueous HCl solution factor, but the slow kinetics of these processes tion/anion exchange resin (Dowex 1-X8). In: INCT makes the elution band of gallium very broad and Annual Report 2008. Institute of Nuclear Chemistry asymmetric. and Technology, Warszawa 2009, pp. 86-88. [7]. Machlan L.A., Gramlich J.W.: Anal. Chem., 60, 37-39 The different pattern of isotope enrichment for (1988). gallium and indium, the neighbouring elements in [8]. Das R.C., Dash A.C., Mishra J.P.: J. Inorg. Nucl. Chem., group 13, is an example of the secondary periodic- 30, 2417-2423 (1968). ity present in numerous chemical properties of these elements.

NEW METHOD FOR DISSOLUTION OF THORIUM OXIDE Krzysztof Łyczko, Monika Łyczko, Irena Herdzik-Koniecko, Barbara Zielińska

Recently, the interest revived in the thorium-uran- under reflux condition [3]. As a result of this re- ium fuel cycle, in which – as a result of irradiation action, we obtain an easily soluble in aqueous by neutrons – thorium-232 (a fertile material) is media a thorium trifluoromethanesulphonate (tri- converted into uranium-233 (a fissile material). flate) salt. With the appropriate concentration of For nuclear power reactors that use thorium oxide, acid this dissolution process can be shortened to it is necessary to develop a method of thorium re- several or tens of minutes. It turned out that add- covering from spent fuel. However, the problem ing a small amount of water to the concentrated of dissolving ThO2 becomes the goal not only for triflic acid significantly accelerates the dissolution the nuclear issues, but also for the processing of process. The synthesis of thorium triflate in the ores containing thorium oxide. reaction of triflic acid with thorium nitrate [4] or It is known that thorium oxide is chemically an with thorium hydroxide [5] was described earlier. inert compound. In aqueous solution it dissolves The method presented herein has many ad- in concentrated nitric acid only in the presence of vantages. It is achieved in a very simple system small amounts of fluoride ions. The most common without necessity of adding to the solution other method of dissolving of ThO2 is to treat it with the inconvenient compounds such as hydrofluoric acid so-called THOREX solution, containing 13 M and aluminium nitrate. Furthermore, in a small HNO3, 0.02-0.05 M HF and 0.1 M Al(NO3)3 [1]. In volume of solution, a large amount of ThO2 can this system, hydrofluoric acid becomes a catalyst be dissolved. The approach described may be im- of the reaction, and aluminium nitrate protects portant in the processing of nuclear fuel based on against the corrosive action of HF, preventing the thorium oxide and in processing of ores contain- precipitation of thorium fluoride as well. Another ing ThO2. It can become a competitive method way of obtaining thorium compounds easily sol- compared to that currently used, applying a mix- uble in aqueous solutions is sintering thorium ture of mineral acids HNO3 and HF. oxide with ammonium sulphate at temperatures This work was financed by the Operational o of 250, 365 or 450 C, which gives (NH4)4Th(SO4)4, Programme Innovative Economy and supported (NH4)2Th(SO4)3, or Th(SO4)2, respectively [2]. by the European Regional Development Fund Hydrated Th4+ ions exist in aqueous solutions only (project POIG 01.03.01-00-076/08-00 “Analysis of at low pH. For concentrated thorium solutions, thorium use in nuclear power plant”). the hydrolysis is considerable even at pH 1. There- fore, when dissolving ThO2 and other thorium References compounds in aqueous media very low pH value [1]. Takeuchi T., Hanson C.K., Wadsworth M.E.: J. Inorg. should be maintained. Nucl. Chem., 33, 1089-1098 (1971). We have found another simple route for con- [2]. Chaudhury S., Keskar M., Patil A.V., Mudher K.D.S., version of thorium oxide into a soluble form dur- Venugopal V.: Radiochem. Acta, 94, 357-361 (2006). ing its heating in the concentrated aqueous solu- [3]. Łyczko K., Łyczko M., Herdzik I., Zielińska B.: Method tion of trifluoromethanesulphonic (triflic) acid of dissolution of thorium oxide. Polish Patent Applica- 42 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY

tion No. P-390844 (2010); European Patent Applica- [5]. Walker M.: Process for the preparation of aryl ketones tion No. 11460009.1-2111 (2011). generating reduced amounts of toxic byproducts. US [4]. Bouby M., Billard I., MacCordick J.: J. Alloys Comp., Patent No. 6362375 (2002). 271-273, 206-210 (1998).

LABELLING OF DOTATATE WITH CYCLOTRON PRODUCED 44Sc Seweryn Krajewski, Izabela Cydzik1/, Kamel Abbas1/, Antonio Bulgheroni1/, Aleksander Bilewicz, Agnieszka Majkowska-Pilip, Federica Simonell1/ 1/ European Commission Joint Research Centre, Institute for Health and Consumer Protection, Ispra, Italy

177Lu- and 90Y-DOTATATEs have been intro- MeV. The activity of the samples was measured duced by the European Association of Nuclear by high resolution γ-ray spectrometry. Medicine into the Investigational Medicinal Prod- For labelling experiments, 5-10 mg of the 44 ucts List, since both radiopharmaceuticals are high- CaCO3 were irradiated for approximately 1 h by ly promising agents for peptide receptor radionu- a proton beam of 9 MeV on the target and apply- clide therapy. They are used in treatment of inop- ing the proton current of 5-15 μA. Afterwards, the erable and metastasized neuroendocrine tumours, target material was dissolved in 1 ml of 0.1 M HCl which overexpress somatostatin receptors [1, 2]. and diluted with 1 ml of water. Then, the solution 68Ga-DOTATATE is used to visualize such tumours was passed through a commercially available col- and plan targeted radionuclide therapy. However, umn (d = 0.8 cm, h = 4.0 cm) filled with chelating it demonstrates a number of pharmacokinetic draw- ion exchange resin Chelex 100. After adsorption backs, which could be avoided by using the longer- of 44Sc, the column was washed with 30 ml of 0.01 44 44 -lived Sc (τ1/2 = 3.92 h) as a prospective radionu- M HCl and the effluent containing enriched Ca clide for PET (positron emission tomography) was collected for target recovery. The scandium imaging. 44Sc has better nuclear properties than radionuclides were eluted with 1 M HCl in 0.5 ml 68Ga and, contrary to Ga3+, forms complexes of fractions. structure similar to those of Y3+ and Lu3+ [3]. 44Sc-DOTATATE radiobioconjugate was syn- Scandium-44 can be obtained from a 44Ti/44Sc thesized using 10, 25 and 38 nmol of the peptide in generator, but the cost of 44Ti production is very sodium acetate buffer of pH = 6. The solution high [4]. Alternatively, it can be produced in small was heated for 30 min at 95oC. Product formation medical cyclotrons by the 44Ca(p,n)44Sc nuclear and reaction yield were estimated by instant thin- reaction. The aim of our study was to optimize the -layer chromatography. The 0.1 M citric buffer 44 44 parameters for CaCO3 irradiation, in order to was used as the eluent. Free Sc moved with the maximize the production of 44Sc with minimal im- front boundary of the solution whereas the label- purities of 44mSc and to develop a simple proce- led bioconjugate stayed at the starting point. The dure of 44Sc separation from the calcium target 10 cm ITLC strip was cut in the middle and each for labelling the DOTATATE. part was measured with a γ-spectrometer. 44 Highly enriched CaCO3 (Isoflex, Russia) was The volume of the collected effluent was de- used as a target material. Irradiations were per- creased to less than 1 ml in a drier heated at 140oC. formed using the Scanditronix MC 40 cyclotron of Next, 200 μl of concentrated ammonia was added the European Commission Joint Research Centre to the solution, which was then heated at 170oC to 44 44 (Ispra, Italy). In order to optimize the yield of Sc decompose NH4Cl and to obtain pure Ca(OH)2. 44 44 44 formed in the Ca(p,n) Sc reaction, CaCO3 tar- The recovered target was irradiated for 1 h with a gets of 2 mg in the form of dry powder were irradi- proton beam of 9 MeV and a current of 10 μA. ated by protons in the energy range from 5.5 to 23 Next, the separation and labelling procedures were Table 1. Activity of 44Sc and 44mSc as a function of the proton energy on the target. The optimum proton beam energy is marked in bold.

Proton energy [MeV] Proton energy on target [MeV] 44Sc [kBq] 44mSc [kBq] 44mSc [%] 19.0 5.57 25.8 0.02 0.081 19.5 7.28 4 240 0.94 0.022 20.0 7.88 4 350 2.6 0.060 20.5 8.89 27 000 43 0.159 21.0 9.83 31 000 57.8 0.186 21.5 10.7 9 370 23 0.245 23.0 13.2 13 600 76 0.559 26.0 17.5 4 600 40 0.869 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY 43 repeated, but instead of sodium acetate buffer, Table 2. Labelling yield as a function of the amount of the ammonia acetate buffer was used. DOTATATE used in the reaction. The analysis of the results obtained from optimization studies shows that in the proton energy Amount of peptide [nmol] Yield of labelling [%] range of 9-10 MeV on the target, the amount of 31 98.2 44Sc reaches a maximum (Table 1) with a minimum 25 99.5 production of 44mSc impurity that is estimated to (0.16%). The 44Sc activity obtained after irradia- 10 98.3 tion of a 5 mg target was around 40 MBq for 1 h irradiation and a 10 μA proton current. The activ- First experiments on the recovery of the calc- ity can be easily increased by prolonging the irradia- ium target showed that up to 50% of 44Ca could be tion time, using higher beam current and amount recovered. The work was performed on small of the target material. amounts of the target (5 mg), which could strongly influence the final efficiency. This issue requires further studies. The recovered 44Ca target was irradiated again, 44Sc was separated from the target on the Chelex 100 column and 25 nmol of DOTA- TATE was labelled with a yield of 99.5%. Irradiations of 44Ca provide an opportunity to produce GBq activity levels of 44Sc. The proposed separation process of 44Sc from the calcium target is simple and fast. The obtained 44Sc can be used, instead of 68Ga, in PET imaging and in planning 177 44 peptide receptor radionuclide therapy with Lu- Fig. Elution curve of Sc with 1 M HCl from column filled 90 44 with Chelex 100 resin. and Y-DOTATATEs. CaCO3 is expensive, but the production cost of 44Sc-DOTATATE can be The separation on the Chelex 100 resin is very reduced by target recovery. efficient. More than 60% of 44Sc activity was eluted with 1 M HCl in three initial 0.5 ml fractions References (Fig.). The content of Ca2+ in 44Sc was less than 1 [1]. Kwekkeboom D.J., Teunissen J.J., Bakker W.H., Kooij ppm, which was measured with ICP-MS (induc- P.P., de Herder W.W., Feelders R.A., van Eijck C.H., tively coupled plasma mass spectroscopy). Esser J.-P., Kam B.L., Krenning E.P.: J. Clin. Oncol., We obtained a high yield of labelling DOTA- 23, 2754-2762 (2005). TATE with 44Sc. The labelling yield exceeded 98% [2]. Kunikowska J., Królicki L., Hubalewska-Dydejczyk A., Mikołajczak R., Sowa-Staszczak A., Pawlak D.: Eur. J. for all amounts of the bioconjugate (Table 2), 44 Nucl. Med. Mol. Imag., 38, 1788-1797 (2011). which shows that very pure and n.c.a. Sc was ob- [3]. Majkowska-Pilip A., Bilewicz A.: J. Inorg. Biochem., tained. When the yield of reaction is not high 105, 313-320 (2011). enough, the labelled peptide can be purified on a [4]. Zhernosekov K., Bunka M., Hohn A., Schibli R., Türler Sep-Pak® C-18 column. A.: J. Labelled Compd. Radiopharm., 54, S239 (2011).

99mTc-LABELLED VASOPRESSIN ANALOGUE 2 4 9 d(CH2)5[D-Tyr(Et ),Ile ,Eda ]AVP AS A POTENTIAL RADIOPHARMACEUTICAL FOR SMALL-CELL LUNG CANCER (SCLC) IMAGING Ewa Gniazdowska, Przemysław Koźmiński, Krzysztof Bańkowski1/ 1/ Pharmaceutical Research Institute, Warszawa, Poland

The aim of the work was to synthesize and investi- predominantly antidiuretic and blood pressure ac- 2 4 gate the conjugate of the d(CH2)5[D-Tyr(Et ),Ile , tivities, vasopressin demonstrates a variety of Eda9]AVP (AVP(an)) peptide, the analogue of neurological effects on central nervous system vasopressin, with a mixed-ligands “4+1” technet- (CNS). It is involved, via different receptor sub- ium(III) complex. types, in higher brain functions, including cogni- Vasopressin (arginine vasopressin, (Arg8)-Vaso- tive abilities and emotionality. In the recent years, pressin, AVP) is a cyclic peptide (disulphide bond interest increased in the role of vasopressin in its between Cys1 and Cys6) containing nine amino participation in such diseases as schizophrenia acid residue (Cys1-Tyr 2-Phe3-Gln4-Asn5-Cys6-Pro7- and autism [1]. The half-live of the vasopressin -Arg8-Gly9). AVP is a peptide hormone found in peptide in vivo is about 15-20 min [2]. The over- most mammals, including humans. AVP regulates expression of vasopressin receptor V2 has been body retention of water, being released when the found on small-cell lung cancer (SCLC) [3-5]. body is dehydrated (antiduretic action of AVP, Physicochemical properties of the 99mTc-labelled mediated via V2 type receptors). In addition to its vasopressin peptide were already studied [6]. 44 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY The AVP analogue, AVP(an), is one of the thesized according to the procedures described in several effective antagonists (Fig.1A) of the anti- Refs. [6, 8-11]. diuretic (V2-receptor) responses to arginine vaso- MS of CN-AVP(an), (m/z): calcd – 1231.61, found pressin [7]. – 616.1 [M+H]+, 1254.3 [M+Na]+. The “4+1” mixed-ligand technetium complex MS of Re(NS3)(CN-(AVP(an)), (m/z): calcd – consists of central metal ion Tc(III) coordinated 1612.1, found – 806.8 [M+H]+, 1634.5 [M+Na]+. by a tetradentate tripodal chelator tris(2-mercapto- The 99mTc-labelled AVP(an) conjugate was via 99m ethyl)-amine, NS3, and a monodentate isocyanide formed in two-step synthesis, the Tc-EDTA ligand previously coupled with the selected bio- intermediate complex [6, 8, 9, 11], with a final molecule (Fig.1B). The identity of the 99mTc-la- yield of 95%.

A O B N O H O N NH2 O O O N H H H H R N N N N N N H H S O O O N N M C peptide N N S O N S O

M=99mTc, Re S S 2 4 9 99m Fig.1. (A) d(CH2)5[D-Tyr(Et ),Ile ,Eda ]AVP, (AVP(an)); (B) Tc-labelled peptides using the “4+1” approach. belled AVP(an) was corroborated by investiga- The HPLC chromatograms of the compounds tion of an analogous rhenium compound. Re(NS3)(CN-AVP(an)), RT = 15.9 min, and 99m The analogue AVP(an), was a gift from Prof. Tc(NS3)(CN-AVP(an)), RT = 16.3, min are Maurice Manning from the University of Toledo shown in Fig.2. (Ohio, USA). The log P value of -0.44 ± 0.03 for the 99mTc-la- The compounds: tetradentate NS3 ligand belled AVP(an) was found (the value may be cor- (tris(2-mercaptoethyl)-amine; 2,2’,2’’-nitrilotri- rected by introduction a hydrophilic group, R, at ethanethiol, R=H), aliphatic linker CN-BFCA the periphery of the NS3 ligand). 99m (BFCA – bifunctional coupling agent) – mono- The conjugate Tc(NS3)(CN-AVP(an)) exhi- dentate isocyanide ligand (isocyanobutyric succin- bits high stability. Figure 3 shows the percentage imidyl ester), CN-AVP(an) – the isocyanide linker of intact conjugate in the challenge experiments CN-BFCA coupled with AVP(an) and the “cold with an excess (10 mM) of histidine or cysteine rhenium precursor” Re(NS3)(PMe2Ph) were syn- during incubation of the isolated conjugate at 37oC. After 24 h of incubation, the obtained HPLC chromatograms have shown the existence of one radioactive species in the solution, of the retention time characteristic of the complex studied. The HPLC chromatograms obtained after in- 99m cubation of Tc(NS3)(CN-AVP(an)) conjugate 99m Tc(NS3)(CN-AVP(an)) in human or rat serum are shown in Fig.4. The labeling mixture, g detection conjugate studied is also very stable in human and rat serum, on the contrary to the 99mTc-labelled arginine vasopressin peptide. The biomolecule AVP(an), the antagonist of the V2 vasopressin receptor, does not undergo enzymatic biodegrada- tion in vivo, even in rat serum.

100 99m Tc(NS3)(CN-AVP(an)) purified, g detection

75 )(CN-AVP(an)) 3

50 Re(NS3)(CN-AVP(an)) UV-Vis detection, 220 nm Tc(NS

99m in 10 mM histidine solution

0 0 5 10 15 20 25 30 25 in 10 mM cysteine solution min 99m

Fig.2. The HPLC chromatograms of the Tc/Re com- % of intact plexes prepared in this study (analytical Phenomenex col- 0 0 4 8 12162024 umn – Jupiter Proteo, 4 μm, 90 Å, 250 × 4.6 mm; under condition: solvent A – water with 0.1% TFA (v/v), solvent time of incubation [h] B – acetonitrile with 0.1% TFA (v/v); gradient elution – Fig.3. Histidine and cysteine challenge experiments: the 99m 0-20 min 20 to 80% solvent B, 10 min 80% solvent B; percentage of intact Tc(NS3)(CN-AVP(an)) complex re- 1 ml/min, γ-detection). maining after various incubation times at 37oC. CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY 45

after 15 min of incubation cpm cpm after 15 min of incubation

after 90 min of incubation after 90 min of incubation

0 0

0 5 10 15 20 25 0 5 10 15 20 25 min min 99m o Fig.4. HPLC chromatograms of Tc(NS3)(CN-AVP(an)) conjugate after incubation at 37 C in human (A) and rat (B) serum (analyses carried out under the conditions described above).

In conclusion, one can say that the novel [6]. Gniazdowska E., Kozminski P., Bankowski K., Pietzsch conjugate of the vasopressin peptide analogue H.-J.: Vasopressin peptide (AVP) labelled with a “4+1” 2 4 9 mixed-ligand technetium complex. In: INCT Annual d(CH2)5[D-Tyr(Et ),Ile ,Eda ]AVP with the “4+1” mixed-ligands technetium(III) complex can be Report 2008. Institute of Nuclear Chemistry and Technology, Warszawa 2009, pp. 77-81. considered promising diagnostic radiopharmaceu- [7]. Manning M., Przybylski J., Grzonka Z., Nawrocka tical for patients suffering from small-cell lung E., Lammek B., Misicka A., Ling Ling Cheng: J. cancer. Med. Chem., 35, 3895-3904 (1992) and references cited therein. References [8]. Seifert S., Kuenstler J.-U., Schiller E., Pietzsch H.-J., [1]. Frank E., Landgraf R.: Best Pract. Res. Clin. Anaes- Pawelke B., Bergmann R., Spies H.: Bioconjugate thesiol., 22, 265-273 (2008). Chem., 15, 856-863 (2004). [2]. Guyton A.C., Hall J.E.: Text book of medical physi- [9]. Kunstler J.-U., Seidel G., Bergmann R., Gniazdo- ology. 10th ed. Saunders W.B., Philadelphia, PA 2000. wska E., Walther M., Schiller E., Decristoforo C., [3]. Pequeux C., Breton C., Hendrick J.-C., Martens Stephan H., Haubner R., Steinbach J., Pietzsch H.-J.: M.-T.H., Winkler R., Legros J.-J.: Cancer Res., 62, J. Med. Chem., 45, 3645-3655 (2010). 4623-4629 (2002). [10]. Spies H., Glaser M., Pietzsch H.-J., Hahn F.E., Luegger [4]. North W.G., Fay M.J., Longo K.A., Jiniin Du: Cancer T.: Inorg. Chim. Acta, 240, 465-478 (1995). Res., 58. 1866-1871 (1998). [11]. Kuenstler J.-U., Veerenda B., Figueroa S.D., Sieckman [5]. Pequeux C., Keegan B.P., Hagelstein M.-T., Geenen G.L., Rold T.L., Hoffman T.J., Smith C.J., Pietzsch V., Legros J.-J., North W.G.: Endocr. Relat. Cancer, H.-J.: Bioconjugate Chem., 18, 1651-1661 (2007). 11, 871-885 (2004).

THE CONCEPT OF A HYBRID SYSTEM FOR TREATMENT OF LIQUID LOW- AND MEDIUM-LEVEL RADIOACTIVE WASTE Grażyna Zakrzewska-Trznadel, Agnieszka Miśkiewicz, Agnieszka Jaworska-Sobczak, Marian Harasimowicz

Radioactive wastes in Poland arise from research tion in the volume of liquid containing small con- reactors and from various applications of radioiso- centrations of radionuclides. Various methods for topes in industry, medicine and science. The waste concentrating radioactive waste have been studied from around the country is collected, processed and developed at the Institute of Nuclear Chem- and prepared for disposal at the Radioactive Waste istry and Technology (INCT), including membrane Management Plant at Świerk (Poland). At present, processes. Reverse osmosis (RO) has been imple- only the institutional radioactive waste is treated mented at the Radioactive Waste Management and conditioned there, however, the development Plant. Other methods such as ultrafiltration (UF), of the Programme of Polish Nuclear Energy will membrane distillation (MD) and adsorption pro- imply necessary activities concerning the future cesses were studied within the scope of national strategy of radioactive waste management. and international projects. The current work pre- The first step in the processing of low- and sents the results of development studies per- medium-level liquid radioactive waste is a reduc- formed at the INCT, aiming at implementation of 46 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY these methods at nuclear centres that produce portion of the radioactivity load can be removed liquid wastes, as well as on the plans devoted to in the precipitation process with ferric hydroxide longer term issues of low-level waste treatment or ferrocyanides. Pretreated waste can be cleaned from the future nuclear power industry in Poland. with UF or RO membranes, depending on the Implementation of liquid-radioactive-waste management is difficult and requires effective methods, including separation processes of high selectivity. To obtain the desired effects, several consecutive steps of treatment using various separation methods should be performed. More frequently, the use of hybrid systems which combine two or more processes is considered to treat the waste material. These systems, enabling higher decontamination factors, can also be considered as selective methods for various types of metal ions, allowing their recovery. Hybrid arrangements are Fig. The scheme of the system for radioactive waste treat- effective and flexible; they are useful in solving ment. complex technical problems encountered in the economy and environmental protection. waste composition. UF is generally applied for The concept of small hybrid systems for low- colloidal solutions; however real waste containing 2+ + and medium-level liquid radioactive waste treat- small cations like Co or Cs can be treated in the ment based on membrane processes was develop- UF process enhanced by complexing agents (sol- ed in the scope of the project No. R05-05806/2009 uble polymers, cheap biopolymers), or dispersed financed from the National Centre for Research sorbents like activated carbon (SUF). After the and Development (NCBiR). A variety of methods basic stage of processing, the final polishing of – such as microfiltration (MF), chemical precipi- permeate takes place in an MD module or in tation, ultrafiltration, seeded ultrafiltration (SUF), standard ion exchange columns. The effluent from nanofiltration (NF) and reverse osmosis, as a main this stage is relatively pure water (below clearance unit of processing – were tested at the INCT with limits: 10 Bq/L) that can be discharged to the sew- institutional radioactive wastes collected from the age system or used as process water, e.g. for clean- Radioactive Waste Management Plant. As a final ing the membrane modules or other components step in the decontamination, the use of hydro- of the plant. Further concentration of retentate phobic microfiltration membranes was proposed from the membrane basic system occurs in the as part of the membrane distillation unit to com- concentration stage composed alternatively of plete the entire scheme. The output streams from high-pressure desalination RO elements or of an the plant are: clean water that can be discharged additional MD module. to the communal sewage system, and the concen- Such a system is very flexible and universal. trate of radioactive compounds, ready for immo- The module design makes it possible developing bilization – the last stage of waste conditioning. the capacity according to specific conditions and The hybrid system for the treatment of liquid actual needs, and an easy up-scaling. It is possible low- and medium-level radioactive waste originat- to redesign some components if the composition ed from nuclear applications (institutional waste) of the waste is stable enough and the rest of ap- was composed of four stages: pretreatment, basic paratuses guarantee the target goals: a clear efflu- stage, final polishing and concentration stage ent from the plant and a concentrate appropriate (Fig.). Radioactive aqueous waste enters the pre- for cementation and disposal. The whole installa- treatment stage where it is prepared before the tion can be a very useful tool for testing different basic stage of processing, which is composed of options of treatment depending on the waste com- RO or UF membrane modules. In the pretreat- position. ment stage, all suspended matter is removed by The research has been supported by the Na- depth filters. The organic compounds and oxidiz- tional Centre for Research and Development ing agents like chlorine are retained by sintered or (NCBiR) – research grant No. R05-05806/2009. granulated activated carbon filters. A large pro- CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY 47 STUDIES ON THE LEACHING OF URANIUM FROM LOWER TRIASSIC PERIBALTIC SANDSTONES Grażyna Zakrzewska-Trznadel, Katarzyna Kiegiel, Kinga Frąckiewicz, Dorota Gajda, Ewelina Chajduk, Iwona Bartosiewicz, Jadwiga Chwastowska, Stanisław Wołkowicz1/, Jerzy B. Miecznik1/, Ryszard Strzelecki1/ 1/ Polish Geological Institute – National Research Institute, Warszawa, Poland

Nuclear power is one of the branches of power in- centration in sand stones from Peribaltic Synec- dustry which, despite a temporary slowdown caused lise shows a big diversity of uranium concentration by an accident in Fukushima, will be fast develop- in the vertical profile: from 4.8 to 1316 ppm. In the ing (reported by Cap Gemini). The alternative to ores, uranium usually was accompanied by other nuclear power for Europe is its dependence on valuable metals, e.g. V, Mo, Th, La, Cu or Co, that gas import from Russia [1]. can be recovered in technological process to im- The inevitable development of nuclear power prove the economy of the whole venture. The implicates the interest in evaluation of domestic exemplary results of chemical analysis of Peri- resources and possibilities of uranium exploita- baltic sandstones are presented in Table. tion [2] for production of nuclear fuel for Polish The first stage of uranium extraction from the reactors. The project entitled “Analysis of the sandstones is leaching by acidic or alkaline solu- possibility of uranium supply from domestic re- tions. It is well established that many factors such sources”, developed by the Institute of Nuclear as temperature, pressure, leaching mode (acidic or Chemistry and Technology (INCT) and Polish alkaline), and the concentration of reagent exert a Geological Institute, makes an effort to evaluate significant effect on the efficiency of extraction of the possibility of uranium production from indig- uranium and other metals from uranium ores. The enous resources.The main objectives of the pro- influence of all these factors on the leaching effi- ject are: ciency was examined. Prior to the leaching, the • to assess the possibility of exploitation of uran- samples of the ores were crushed and ground. The ium resources in Poland, experiments were performed in a round bottom • to work out methods for uranium extraction glass flask equipped with a reflux condenser and a from the ores and production of the yellow cake magnetic stirrer (Star FishTM, Multi-experiment o – U3O8. work station) at a temperature of 80 C under am- According to the assessments done by the Polish bient pressure. The samples of grain size in the Geological Institute, apart from the well-known range of 0÷0.2 mm were tested. The oxidizing resources in Sudetes exploited in 1948-1973, there agent (MnO2 or 30% H2O2) was added to oxidize are other deposits of uranium on the territory of all uranium to U(VI). The post-leaching solution Poland: in the Lower Ordovician Dictyonema was separated from the leached ore by filtering shale of Podlasie Depression (North-East Poland) and successive washing with distilled water. A with the metal concentration of 75-250 ppm, and sample of the solution was drawn for ICP-MS the most prospective uranium mineralization – analysis [4] to estimate the leaching efficiency. the Lower and Middle Triassic rocks of the central The experiments performed with 10% H2SO4 parts of Peribaltic Syneclise [3]. The ore material lixiviant at 80oC showed the efficiency of uranium originating from these two resources was selected extraction on the level of 63÷80%. The results are for laboratory studies carried out in the scope of shown in Fig.1. Very interesting results were ob- the present project. The analysis of uranium contained when alkaline lixiviants (5% Na2CO3/5% Table.The content of selected metals in uranium ore samples.

Sandstones Sample Deposit notation notation U Th Cu Co La V Yb Ni Fe [ppm] [ppm] [ppm] [ppm] [ppm] [ppm] [ppm] [ppm] [ppm] 21/10/138 Ptaszków IG-1 1 120 4.0 42 127 14 142 0.8 21 8 080 21/10/140 Ptaszków IG-1 1 316 5.1 28 81 47 625 1.7 41 12 680 21/10/141 Ptaszków IG-1 1 144 14 47 117 51 717 2.5 52 21 590 21/10/142 Ptaszków IG-1 670 4.8 32 57 29 770 1.6 26 8 500 21/10/148 Ptaszków IG-1 526 10 46 71 43 232 2.3 36 28 270 21/10/149 Ptaszków IG-1 159 3.3 20 7.4 18 370 0.7 18 8 400 21/10/160 Krynica Morska 565 4.3 59 96 14 371 2.0 45 16 000 21/10/161 Krynica Morska 355 4.1 78 65 2 100 25 158 2.1 3 280 21/10/166 Krynica Morska 260 5.3 33 35 33 230 2.9 29 7 500 21/10/169 Krynica Morska 457 7.8 65 97 33 83 5.3 53 20 780 48 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY

100 100 21/10/138 21/10/142 21/10/142 80 80 21/10/160 21/10/160 ciency ciency ﬁ 60 ﬁ 60

40 40

% leaching ef 20 % leaching ef 20

0 0 U Th La V Yb Cu U Th La V Yb Cu metal metal

Fig.1. Efficiency of acid leaching (10% H2SO4) of sand- Fig.3. Efficiency of alkaline leaching (8% NaOH/18% stones from Peribaltic Syneclise. Na2CO3) of sandstones from Peribaltic Syneclise.

NaHCO3 and 8% NaOH/18% Na2CO3) were used of reagents, leaching mode, temperature, and par- as leaching solution (Figs.2 and 3). These experi- ticle size of ground ores. The effect of these fac- ments show that the alkaline leaching is more se- tors was tested as well. lective than acidic leaching. In the post-leaching It is expected that the present project will pro- solutions only uranium, vanadium, and copper vide the data answering the question whether in- were detected. digenous resources can be considered as a poten- 100 tial reserve of uranium for Polish nuclear reactors 21/10/138 in the future. 80 21/10/142 The studies were supported by PO IG 21/10/160 01.01.02-14-094-09-00 research grant “Analysis of 60 ciency

ﬁ the possibility of uranium supply from domestic resources”. 40 References 20 [1]. Ciepiela D.: Energetykę jądrową na świecie czeka świe- % leaching ef tlana przyszłość (Nuclear power in the world waiting 0 for a bright future). http://www.elektrownia-jadrowa. U Th La V Yb Cu pl/energetyke-jadrowa-na-swiecie-czeka-swietlana- metal -przyszlosc-html (2011), in Polish.

Fig.2. Efficiency of alkaline leaching (5% Na2CO3/5% [2]. International status and prospects of nuclear power, NaHCO3) of sandstones from Peribaltic Syneclise. 2010 edition. International Atomic Energy Agency, Vienna 2011. http://www.iaea.org/books. When 5% Na2CO3/5% NaHCO3 was used as the [3]. Miecznik J.B., Strzelecki R., Wołkowicz S.: Prz. Geol., leaching solution, the yield of recovery of uranium 59, 10, 688-697 (2011), in Polish. was low (20÷52%) (Fig.2). However, the leaching [4]. Chajduk E., Kalbarczyk P., Dudek J., Polkowska-Mo- trenko H.: Isotope ratio measurements for uranium by with 8% NaOH/18% Na2CO3 was very satisfactory. The almost complete extraction of uranium was quadrupole-based inductively coupled plasma mass observed in that case (Fig.3). spectrometry. In: INCT Annual Report 2010. Institute The efficiency of uranium leaching also de- of Nuclear Chemistry and Technology, Warszawa 2011, pp. 77-78. pends on other factors such as the concentration

SYNTHESIS OF URANIUM DIOXIDE MICROSPHERES BY WATER AND NITRATE EXTRACTION FROM URANYL-ASCORBATE SOLS Marcin Brykała, Andrzej Deptuła, Wiesława Łada, Tadeusz Olczak, Danuta Wawszczak, Tomasz Smoliński

A new method for the synthesis of uranium dioxide time and destruction of the microspheres during microspheres has been developed. It is a variant thermal treatment owing to highly reactive com- + of our patented complex sol-gel process (CSGP) ponents in the gels (ascorbic acid – ASC, NH4 , – which has been used to synthesize high-quality NO3 ). We, therefore, modified the gelation step by powders of a wide variety of complex oxides and simultaneously extracting water and nitrates using oxide compounds. In the new method, uranyl ni- Primene JMT (commercial name of aliphatic trate-ascorbate sols (alkalized by aqueous ammo- amines, principally C18H37N2). We observed more nia) were emulsified in 2-ethylhexanol-1 contain- than one order of magnitude decrease in gelation ing SPAN 80. Drops of emulsion were gelled by time, and the microspheres remained intact dur- extraction of water by solvent. The technique ex- ing heating, even when using relatively high (10 hibited two serious disadvantages: long gelation oC/min) heating rates. The final thermal treat- CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY 49 ment step was reduction at 1100oC in a gas mix- and the most popular method for fabrication of ture atmosphere containing hydrogen. Because of uranium-containing spherical particles is the sol- the presence of ascorbic acid in the gels, the sinter- -gel process. It is a chemical method which mainly ability of the spherical powders was higher than that involves the gelation of droplets of sol to the de- of routinely synthesized uranium dioxide powder. sired fuel material into gel microsphere. After- Uranium dioxide is the principal compound wards, the gels are washed, dried and thermally used as nuclear fuel, either in the natural form or treated to obtain high density microspheres [1, 2]. enriched in 235U. For the present generation of At the Institute of Nuclear Chemistry and nuclear reactors, uranium dioxide powder is syn- Technology (INCT), a new method of synthesis of thesized by various routes (e.g. thermal decompo- uranium dioxides has been elaborated, by a new sition and reduction of U(VI) to U(IV) of simple variant of the sol-gel method – complex sol-gel uranium substrates, such as uranium trioxides, process (CSGP) [3, 4]. The main modification step ammonium poliuranates or uranyl nitrate). If en- is the formation of uranyl-nitrate-ascorbate sols riched UF6 is used, then the defluorinating step is from components alkalized by aqueous ammonia. necessary, followed by further processing to UO2. By applying of IChTJ process [5], final products Finally, UO2 powders are pressed to pellets and are obtained in the shape of medium-sized spheri- after sintering loaded into fuel rods. cal particles with a diameter below 100 μm [6]. Nuclear fuels of spherical shape are proposed According to our best knowledge, CSGP has for IV generations of power nuclear reactors (e.g. never been applied for the preparation of uranium high temperature gas cooled reactors). The main dioxide [7]. It is important to recognize that the sols and gels are not in thermodynamic equilibrium, and their properties depend critically on the preparation conditions. Consequently, the effects of changes in the conditions were difficult to predict, and studies were conducted for the development of the best parameters requested for these complexes. The following reagents were used: uranyl nitrate (Chemapol Praha), ascorbic acid pharmaceutical grade (Takeda Europe GmBH), 2-ethylhexanol-1 (Acros Organics, 99%), SPAN-80 (Fluka), and Primene JMT (Fluka). Gels and products were characterized by the following methods: thermogravimetric analysis (TG) and differential thermal analysis (DTA) with a Hungarian MON Deri- vatograph, scanning electron microscope (SEM) observation with a Zeiss DSM 942 and Jeol JSM64-90LV. The CSGP and IChTJ processes applied to the synthesis of spherical particles of uranium dioxide consist of following steps which are shown in Fig.1. The first step of the method consists in the formation of complex solution – uranyl-nitrate-ascorbate sol (mole ratio U/ASC = 1) by addition of a very strong complexing agent – ascorbic acid – this is the salient feature of CSGP process. Afterwards, partial hydrolysis by addition of ammonia solution to a certain pH value before precipitation (approx. pH ~ 4) is carried out. The results of potentiometric titration with ammonium hydroxide, of various ascorbate-uranyl sols (0.001 M) obtained

Fig.1. Flow chart of preparation of uranium dioxide in the form of microspheres (< 100 μm) by CSGP and IChTJ Fig.2. Potentiometric titration of 0.001 M UO2(NO3)2 with processes. ammonia (0.1 M); MR – mole ratio. 50 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY from uranyl nitrate, are shown in Fig.2. In the sample without ascorbic acid, we can observe a small plateau in the pH region of ~6 (mole ratio NH4OH/U = 3), connected with polymerization of uranyl ion to polynuclear ions, followed by a definite increase in pH (inflection point at approx. mole ratio = 3.5), representing formation of ammonium polyuranates in the solution. These effects are considerably disappearing with an increase in ASC concentration, which confirms strong complexing ability of this reagent. Evidently, a value of inflection points is proportionally higher with an increase in the mole ratio ASC/U. The next step, which influences obtaining of the desired shape of final product, is the gelation of complex sol. The sols can be gelled: into irregular agglomerates by evaporation of water; to spherical particles, like kernels (Ø > 200 μm) by internal gelation; and to medium sized spherical particles (Ø < 100 μm) by modified external gelation – IChTJ process (Fig.1). The products, after Fig.4. Thermal analysis (TG, DTA) of ascorbate-uranyl gels. this part of method, are shown in Fig.3. droxide groups, but it is also connected to the decomposition of U-ASC-NO3-NH4OH gel when one of the components – ammonium nitrate – de- composes with explosion. This means that thermal treatment requests special procedures to avoid ex- plosions. The simplest way was the application of low heating rate (1-2 oC/min) to a temperature of 250oC, when the decomposition of ammonium nitrate occurs. Unfortunately, despite this procedure, the spherical particles are chipped (Fig.5A). Consequently, a new method of gelation sols to spherical particles has been elaborated. This procedure consists of the following steps: 1 M uranyl-nitrate-ascorbate sols (alkalized with aqueous ammonia) were emulsified in 2-ethylhexanol-1 Fig.3. SEM of spherical particles of ascorbate-uranyl gel. (2EH) containing SPAN 80. The gelation step was modified by simultaneously extracting of water by The final step of the combination of CSGP and 2EH and nitrates using Primene JMT. The volume IChTJ processes is a non-destructive thermal of used Primene JMT is 2% of the 2EH volume. treatment with reduction U(VI) to U(IV). The We observed that the microspheres remained in- uranyl-nitrate-ascorbate gels were annealed ac- tact during heating, even when using relatively cording to the temperatures indicated by the re- high (10 oC/min) heating rates (Fig.5B). These sults of thermal analysis – TG, DTA (Fig.4). positive results are the effect of lower concentra- The first weight loss of all obtained gels, at tion of nitrates in U-ASC-NO3-NH4OH, and con- temperatures of 100-300oC, is connected to evap- sequently much less content of potentially explo- oration of molecular water and splitting the hy- sive ammonium nitrate.

Fig.5. SEM of triuranium octoxide in the shape of spherical particles obtained by: A – IChTJ process, B – double extraction process. CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY 51 For both curves, the next weight loss, with broad References o exothermic effect at 400-600 C, is connected with [1]. Sood D.D.: J. Sol-Gel Sci. Technol., 59, 404 (2011). the combustion of ASC and the products of its de- [2]. Vaidya V.N.: J. Sol-Gel Sci. Technol., 46, 369 (2008). composition. After that, the weight is stable and [3]. Deptuła A., Brykała M., Łada W., Wawszczak D., Ol- represents the formation of triuranium octoxide czak T., Chmielewski A.G.: Method for obtaining uranium dioxide in the form of spherical and irregular (U3O8). The obtained triuranium octoxide was then re- grains. Polish Patent Aplication No. P-389385 (2009); duced to uranium dioxide in the 5% hydrogen and UE Patent No. 101884385-1218 (2010); Russian Fed- eration Patent Application No. 2010 136670; Republic 95% nitrogen atmosphere at a temperature of o of Belarus Patent Application No. 2010 1305; Ukrain- 900 C. ian Patent Application No. 2010 10756. In conclusion, a new technique of gelation of [4]. Deptuła A., Brykała M., Łada W., Olczak T., Waw- uranyl sols obtained from uranyl nitrate has been szczak D., Modolo G., Daniels H., Chmielewski A.G.: elaborated. This modification (simultaneous ex- Synthesis of uranium dioxides by complex sol-gel pro- traction of water and nitrate anions) eliminates cesses (CSGP). In: Proceedings of the 3rd Interna- the serious disadvantage – the destruction of mi- tional Conference on Uranium, 40th Annual Hydro- crospheres during thermal treatment, which is metallurgy Meeting, Saskatoon, Saskatchewan, Canada. connected with violent decomposition of ammo- Vol.II. 2010, pp. 145-154. nium nitrates formed in time of alkalization of [5]. Deptuła A., Hahn H., Rebandel J., Drozda W., Kali- nowski B.: Sposób wytwarzania sferycznych ziaren uranyl-nitrate-ascorbate sol by ammonium hy- tlenków metali (Method for preparing spherical grains droxide. After that, even relatively high heating of metal oxides). Polish Patent No. 83484, (1977). o rates (10 C/min) can be used. [6]. Deptuła A., Brykała M., Łada W., Olczak T., Sarto- It is necessary to underline that the prepara- wska B., Chmielewski A.G.: Fusion Eng. Des., 84, 681 tion of uranyl gels from uranyl nitrate by extrac- (2009). tion of nitrates without addition of ascorbic acid is [7]. Deptuła A., Łada W., Olczak T., Lanagan M.T., Dorris not possible. S.E., Goretta K.C., Poeppel R.B.: Sposób wytwarzania The work has been carried out within the Col- nadprzewodników wysokotemperaturowych (Method laborative Project ACSEPT (Actinide Recycling for preparing of high temperature superconductors). Polish Patent No. 172618 (1997). by Separation and Transmutation), contract No. FP7-CP-2007-211267.

SYNTHESIS OF PEROVSKITE BY COMPLEX SOL-GEL PROCESS FOR NUCLEAR WASTE IMMOBILIZATION Tomasz Smoliński, Andrzej Deptuła, Tadeusz Olczak, Wiesława Łada, Danuta Wawszczak, Marcin Brykała, Fabio Zaza1/, Andrzej G. Chmielewski 1/ Italian National Agency for New Technologies, Energy and Environment (ENEA), CR Casaccia, Rome, Italy

Synroc is a kind of “synthetic rock” which has its synthesis in solid-state reaction. Radioactive been invented by Ringwood in 1978 [1, 2]. It has waste elements are added into the obtained ma- been regarded as the second generation of high trixes. After that, the material is pressed and sin- level waste (HLW) immobilization forms in the tered. An alternative solution for synthesis of the world. Because of higher leaching resistance and various Synroc materials seems to be the sol-gel better durability, it can be a better solution for im- method. This method allows for the direct incor- mobilizing nuclear waste [3, 4]. Basically, Synroc poration of radioactive elements into the mineral materials are a ceramic made from several natural structure during its formation [3]. The homogene- minerals which incorporate nearly all of the ele- ous distribution of the components reduces the ments present in high level radioactive waste into their crystal structures [4]. This advanced ceramics comprises geochemically stable natural titanate minerals which occur naturally in the earth’s crust [5-7]. Crystal structures of these materials allow to incorporate almost all of the elements present in high level radioactive waste. Synroc can take many forms which depend on the type and form of waste [5-7]. Synroc C consist of the following materials: perovskite (CaTiO3), zirconolite (CaZrTi2O7) and hollandite (BaAl2Ti6O16). Long-lived actinides such as plutonium are immobilized in perovskite and zirconolite. Perovskite immobilizes also strontium and barium. In hollandite is immobilized caesium, potassium, rubidium and barium. The most common method of production of Synroc is Fig.1. Flow chart for preparation of Sr-doped perovskite. 52 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY sintering temperature and increases the product dechlorination step [8, 9]. During the dechlorina- resistance to leaching of radioactive elements. tion step, we observed decomposition and vigor- In this work, our patented complex sol-gel ous evolution of gas, due to oxidation of the ASC process (CSGP) [8, 9] was used to synthesize the by the nitrates. The resulting sols were nearly perovskite capable of incorporating significant transparent, pale yellow in colour, and stable. This amounts of high level nuclear waste. The goal of sol was used to produce perovskite of various this work was limited to incorporating strontium composition. into titania ceramic, and studing the course of re- Thermal treatments were conducted in air. action and characterizing the final product. Gels and final powders were characterized by The flow-chart of the preparation of Sr-doped thermogravimetric analysis (TGA) and differential (mole 10%) titanate gels is shown in Fig.1. Com- thermal analysis (DTA). All the resulting products via mercial TiCl4 was introduced pumping into were analysed by X-ray diffraction (XRD) as well.

o Fig.2. Thermal analysis of gel powders dried at 105 C: (1) CaTiO3, (2) CaTiO3 + ASC, (3) CaTiO3 + 10% Sr, (4) CaTiO3 + 10% Sr + ASC. concentrated HCl. The titanium concentration The thermal decomposition of gels dried under was ca. 4 mol/L. The main preparation step con- vacuum at 80oC is illustrated in Fig.2. For all four sisted of chloride elimination [8] by distillation gels, the loss of mass, Δm, became significant with nitric acid, addition of hydroxides of Ca and above 120oC. TGA traces revealed systematic es- Sr (mole 10%), evaporation of water and hydro- cape of volatile substance without clearly defined chloric acid from sols to dry substance, grinding, thermal effects. Distinct exothermic effects have and thermal treatment to titanates of Ca and Sr. been observed above 500oC, which was connected There were synthesized four samples: CaTiO3 to the formation of crystalline phase of perovskite. (P1), CaTiO3 + ASC (P2), CaTiO3 + 10% Sr (P3), In the samples prepared with ASC addition (P2, CaTiO3 + 10% Sr + ASC (P4). P4) this temperature was lower. To prevent precipitation we added ascorbic The samples P1 and P2 treated at 450oC were acid (ASC) to samples P2 and P4 before the essentially amorphous. The samples containing

Fig.3. XRD patterns of titania gels cacined for 2 h at various temperatures. CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY 53

Table. The samples analysed by XRD.

Structure order/ Samples T [oC] Chemical nature Lattice systems Size [nm] disorder

P1 1200 CaTiO3 crystalline orthorhombic 27.7

P2 1200 CaTiO3 (with ASC) crystalline orthorhombic 21.8

P3 1200 Sr0.1Ca0.9TiO3 crystalline orthorhombic 22.4

P4 1200 Sr0.1Ca0.9TiO3 (with ASC) crystalline orthorhombic 22.4

P1 700 CaTiO3 crystalline orthorhombic 27.6

P2 700 CaTiO3 (with ASC) crystalline orthorhombic 25.9

P3 700 Sr0.1Ca0.9TiO3 crystalline orthorhombic 20.7

P4 700 Sr0.1Ca0.9TiO3 (with ASC) crystalline orthorhombic 23.0

P1 450 CaTiO3 amorphous - -

P2 450 CaTiO3 (with ASC) amorphous - -

P3 450 Sr0.1Ca0.9TiO3 amorphous - -

P4 450 Sr0.1Ca0.9TiO3 (with ASC) amorphous - - strontium, small bands (presumably of non-react- that powders will be easy tractable by pressing and ed substrates) are observed. The samples calcined sintering. at 700oC were fully crystalline and had a perfect The complex sol-gel process for synthesizing of orthorhombic structure (Fig.3). This temperature Synroc material seems to be advantageous in com- is significantly lower than that reported when parison to conventional methods. Consequently, solid state reaction had been used [2]. The aver- we are going to synthesize other Synroc materials age crystallite sizes of our samples is between 20 containing various HLW (e.g. Cs, Co, and U or ac- to 28 nm (Table). Crystalline structure of synthe- tinide surrogates e.g. Nd). We expect their increased sized perovskites is shown in Fig.4. resistance to radionuclide leaching and improved The Synroc materials – perovskite CaTiO3 also durability. Sr Ca TiO , were synthesized directly by using 0.1 0.9 3 References [1]. Ringwood A.E., Kesson S.E., Ware N.G., Hibberson W., Major A.: Nature, 278, 219-223 (1979). [2]. Ringwood A.E.: Am. Sci., 70, 2, 201-207 (1982). [3]. Ringwood A.E., Oversby V.M., Kesson S.E., Sinclair W., Ware N., Hibberson W., Major A.: Nucl. Chem. Waste Manage., 2, 4, 287-305 (1981). [4]. Ringwood A.E., Kessom S.E., Ware N.G., Hibberson W.O., Major A.: Geochem. J., 13, 141-165 (1979). [5]. Ojovan M.I., Lee W.E.: An introduction to nuclear waste immobilization. Vol.1. Elsevier, London 2005, 316 p. [6]. Woignier T., Reynes J., Phalippou J., Dussossoy J.L.: J. Sol-Gel Sci. Technol., 19, 833-837 (2000). [7]. Clarke D.R.: Ann. Rev. Mater. Sci., 13, 191-218 (1983). [8]. Deptula A., Lada W., Olczak T., Lanagan M.T., Dorris S.E., Goretta K.C., Poeppel R.B.: Sposób wytwarzania nadprzewodników wysokotemperaturowych (Method for preparing high-temperature superconductors). Polish Fig.4. Crystalline structure: (1) Ca or Sr, (2) Ti, (3) O. Patent No. 172618 (1997). [9]. Deptuła A., Olczak T., Łada W., Sartowska B., Chmie- the complex sol-gel process. The gels prepared lewski A.G., Casadio S., Alvani C., Croce F., Goretta from stable, transparent titanium-nitrate sols with K.C., Di Bartolomeo A.: Fabrication of spherical and ASC addition, formed crystalline titanate phases irregularly shaped powders of Li and Ba titanates from at lower temperatures than did gels without this titanium tetrachloride by inorganic sol-gel process. In: additive. The added strontium is homogeneously Advances in Science and Technology 30, 10th Interna- tional Ceramic Congress – Part A. Techna Srl, 2003, distributed in the crystalline structures. The very pp. 441-452. small crystallite size (20-28 nm) allows us to assume CENTRE FOR RADIOBIOLOGY AND BIOLOGICAL DOSIMETRY

The Centre continued and completed the projects that were carried out in 2010. Studies carried out in 2011 concentrated on two main topics: validation, adaptation and implementation of various biodosimetric methods and biological effects of nanoparticles. The biodosimetric methods can be divided into two categories: the first category is for radiation dose estimation in a multiparametric triage test for nuclear and radiological mass-casualty incidents (supported by the European Union Structural Funds and Ministry of Regional De- velopment, Poland, project No. POIG.01.03.01-14-054/09). The second category of methods is that of cytogenetic methods and the work has been carried out in a close international cooperation in the frame of the European Union MULTIBIODOSE (241536 FP7-SECURITY SEC-2009-4.3-02 Bio-dosimetric tools to manage radiological casualties) programme. It comprises, among others, validation of automating the scoring and implementation of telescoring of the standard biodosimetric cytogenetic methods (dicentric assay, micronucleus test) as well as optimization and validation of the γ-H2AX assay as a rapid triage device for a mass casualty scenario. The participation involves cooperation with other European laboratories, exchange of samples and microscopic preparations in order to unify the procedures and training. Our contributions to the POIG.01.03.01-14-054/09 and MULTIBIODOSE programmes were presented at the 1st International Nuclear Energy Congress (Warszawa), the 19th Nuclear Medical Defence Conference (Monachium) and the XIV International Congress of Radia- tion Research (Warszawa). As both programmes are targeted at testing large groups of potential victims, time is an important factor and the speed of analysis counts more than accuracy. Hence the necessity to establish automated, high-throughput, cytogenetic biodosimetry methods to process a large number of samples for conducting the assays using peripheral blood from exposed individuals according to internationally accepted protocols (i.e. within days following radiation exposures). The Centre is being prepared to participate in triage tests with the use of various methodo- logical approaches. An automated metaphase finder and micronucleus finder is presently used for validation of the biodosimetric methods. The nanoparticle project is carried out in the frame of the Polish Norwegian Research Fund (PNRF-122-AI-1/07) in cooperation with several laboratories (Norwegian Institute of Air Image analysis system METAFER 4, Metasystems with a Research, Norwegian Institute of Public Health, Zeiss fluorescent microscope at the Centre for Radiobiology National Institute of Public Health – National and Biological Dosimetry. Institute of Hygiene, Warsaw University of Life Sciences). During 2011, we studied the effects of DNA damage induced by treatment with uncoated silver nanoparticles (Ag NP) 20 nm or 200 nm particles and titanium dioxide nanoparticles (TiO2 NP) 21 nm in three human cell lines: hepatocellular liver carcinoma HepG2, colorectal adenocarcinoma HT29 and lung carcinoma A549. It was also presented at the Annual Meeting of the Polish Biochemical Society in Kraków. In cooperation with the Jena University, in the frame of the Ministry of Science and Higher Education grant DPN/N23/NIEMCY/2009, we continued the study of the role of conjugated linoleic acids (CLA) in the cellular response to X-rays. We have previously found that the X-irradiated colon cancer HT-29 cells become markedly radiosensitized in result of culture in a CLA complemented medium and this is accompanied by an impaired repair of DNA double strand breaks. These data were further completed by determination of the formation and decay of the γ-H2AX “repair foci”, examination of the extent of chromosome fragmentation with the use of the premature chromosome condensation (PCC) method and recently, by analysis of lipid raft properties. These results were presented at the Annual Meeting of the Polish Bio- chemical Society and at the XIV International Congress of Radiation Research (Warszawa). Three PhD theses were defended in 2011 by the Centre’s PhD students. During 2011, 12 papers were published and 26 posters and lectures presented at meetings in Poland or abroad, and also at the 14th International Congress of Radiation Research that took place in Warsza- wa (28th August-1st September). The congress was organized by the Polish Radiation Re- search Society under the auspices of the Polish Presidency of the European Union Council. Anna Lankoff and Marcin Kruszewski worked in the Organizing Committee, Irena Szumiel – in the Scientific Committee. Most of the younger members of the Centre also participated as volunteers in various organizational tasks during the sessions and symposia. CENTRE FOR RADIOBIOLOGY AND BIOLOGICAL DOSIMETRY 57 OPTIMIZATION OF A FINGER-PRICK BLOOD COLLECTION METHOD FOR THE γ-H2AX ASSAY: POTENTIAL APPLICATION IN POPULATION TRIAGE Maria Wojewódzka, Anna Lankoff, Marcin Kruszewski

Accurate methods for measuring the biological ef- temperature. Slides were mounted with DAPI Vec- fects of radiation are critical for estimating the tashield and analysed with an automated image health risk from radiation exposure. Foci of γ-H2AX acquisition and analysis system Metafer (Meta- which form in response to radiation-induced DNA systems, Germany). double strand breaks and can be quantified by im- Our results revealed that the number of γ-H2AX munofluorescence microscopy or flow cytometry foci was linearly related to the radiation dose. The have been considered for application in population number of radiation-induced γ-H2AX foci obtain- triage [1-3]. However, application of this method ed for samples incubated at 37oC for 30 min was as a triage tool in large-scale radiological accidents comparable to that for samples incubated at 0oC demands immediate blood collection and high for 24 h followed by 30 min incubation at 37oC throughput sample processing and analysis. Since (Figs.1 and 2). This result points to the possibility the γ-H2AX foci scoring assay seems to be the of sample storage in situations when very high most sensitive to ionizing radiation, the aim of our study was to optimize a finger-prick blood collection method for the automated γ-H2AX assay in relation to various blood storage conditions. Peripheral whole blood was collected from five healthy volunteers. For each donor, blood samples were irradiated with 250 kV X-rays (0, 0.2, 0.4, 0.6, 0.8, 1, 1.5, 2, 3, 4 Gy). After irradiation, one set of samples was incubated at 37oC for 30 min. Three other sets of samples were incubated at 0 and 37oC for 24 h, followed by 30 min incubation at 37oC. Blood samples (50 μl) were mixed with 900 μl of medium and loaded into eppendorf tubes contain- Fig.2. Dose response curve for radiation-induced γ-H2AX ing 100 μl of Histopaque 1077. The samples were foci in human peripheral blood lymphocytes incubated at spun two times at 2000 g for 3 min. The cells were 0oC for 24 h followed by 30 min incubation at 37oC. spotted onto slides with a cytospin at 490 g for 10 min, fixed in paraformaldehyde for 30 min and numbers of samples have to be analysed in the permeabilized/blocked in KCMT buffer (120 mM frame of a triage procedure. The number of radi- KCl, 20 mM NaCl, 10 mM Triton, 1 mM EDTA) ation-induced γ-H2AX foci obtained for samples containing 2% BSA and 10% low fat milk for 1 h at incubated at 37oC for 24 h decreased significantly, irrespective of the radiation dose (not shown). Also, we observed that the inter-individual variation in the number of spontaneous γ-H2AX foci (2-7 per cell) was related to various blood storage conditions. To conclude, our finger-prick blood collection method for the γ-H2AX assay allows to obtain reproducible and quantitative results using small aliquots of blood and appears to have a potential use for rapid population triage in case of a large-scale radiological event. References [1]. Rothkam K., Horn S.: Ann. Ist. Super. Sanita, 45, Fig.1. Dose response curve for radiation-induced γ-H2AX 265-271 (2009). foci in human peripheral blood lymphocytes incubated at [2]. Horn S., Barnard S., Rothkamm K.: PLoS ONE, 6, 37oC for 30 min. e25113 (2011). room temperature. The cells were incubated with [3]. Roch-Lefevre S., Mandina T., Voisin P., Gaëtan G., Mesa J.E., Valente M., Bonnesoeur P., García O., Voisin monoclonal γ-H2AX antibody for 1 h, washed in P., Roy L.: Radiat. Res., 174, 185-194 (2010). PBS and incubated with FITC-conjugated goat anti-mouse secondary antibody for 45 min at room 58 CENTRE FOR RADIOBIOLOGY AND BIOLOGICAL DOSIMETRY CLONOGENIC ABILITY DOES NOT CORRESPOND TO DNA DAMAGE INDUCED IN HUMAN CELLS TREATED IN VITRO WITH SILVER AND TITANIUM DIOXIDE NANOPARTICLES Iwona Grądzka, Teresa Bartłomiejczyk, Teresa Iwaneńko, Maria Wojewódzka, Anna Lankoff, Maria Dusinska1/, Gunnar Brunborg2/, Irena Szumiel, Marcin Kruszewski 1/ Norwegian Institute of Air Research, Oslo, Norway 2/ Norwegian Institute of Public Health, Oslo, Norway

Due to their antibacterial properties, silver nano- Titania NP were the least damaging in all cell lines. particles (Ag NP) have been integrated into hun- Interestingly, there were no increases in the fre- dreds of consumer products. They have also found quencies of histone γ-H2AX foci and micronuclei numerous technical and medical applications. It is generally agreed that the oxidative stress is the A main cause of the Ag NP-induced effects at the cellular level, such as genotoxicity and mutagenic- ity, disturbed mitochondrial respiration, impaired proliferation and apoptotic death. These effects may be the potential cause of toxicity of Ag NP and are sufficient to raise concern for the human health and the environment [1]. Although Ag NP and TiO2 NP (titanium dioxide nanoparticles) belong to the NP most often studied, the mechanisms of their biological effects are still not fully understood. Moreover, there are numerous discrepancies in the reports on the extent of DNA damage induced by Ag NP in various mammalian cells in in vitro studies [2]. Some of these discrepancies may be due to the different properties of Ag NP preparations, such as their size, since they are prepared B according to different protocols, uncoated or coated with polymers such as polyvinylpyrrolidone, polyethylenimine or starch. Additionally, different treatment protocols involve preliminary NP dispersion, e.g. in either a BSA (bovine serum albumin) or an FCS (foetal calf serum) containing medium. Finally, cell type may affect the resulting extent of genotoxic damage. There are relatively few data on NP genotoxicity and no attempt has been made to directly relate DNA damage to clonogenicity loss. Therefore, we undertook studies of the effects of DNA damage induced by treatment with un- Fig. DNA damage (single stand breaks, SSB, and base coated Ag NP 20 nm or 200 nm particles and TiO damage recognized by FPG in cells treated with Ag NP or 2 Ag 200 nm particles and TiO NP for 2 h at concentrations NP 21 nm in three human cell lines: hepatocellu- 2 indicated: A – A549 cells, B – HepG2 cells; asterisks mark lar liver carcinoma HepG2, colorectal adenocarci- the statistically significant difference from control (Student’s noma HT29 and lung carcinoma A549. The end- t-test). -points examined were DNA breakage estimated by the comet assay and oxidative base damage as compared to those in the untreated cells. This recognized by formamido-pyrimidine glycosylase means that the DNA damage types do not include (FPG) and estimated with the FPG + comet assay, double strand breaks (DSB). The reported experi- frequencies of histone γ-H2AX foci and micronu- ments provided no data that would directly cor- clei, apoptosis and clonogenic survival. Each cell relate DNA damage induced by Ag NP or TiO2 NP line had a different pattern of DNA breakage and to early apoptosis or loss of clonogenic ability. base damage vs. NP concentration and time of treatment. References Figure illustrates the sensitivity difference to [1]. AshaRani P.V., Hande M.P., Valiyaveettil S.: BMC applied NP treatment between the resistant A549 Cell Biol., 10, 65 (2009). cells and the sensitive HepG2 cells. However, after [2]. Karlsson H.L.: Anal. Bioanal. Chem., 398, 651-666 24 h treatment, these differences became smaller. (2010). CENTRE FOR RADIOBIOLOGY AND BIOLOGICAL DOSIMETRY 59 COMPARISON OF FREQUENCIES OF DICENTRIC CHROMOSOMES AND HISTONE γ-H2AX FOCI IN HUMAN LYMPHOCYTES X-IRRADIATED AT 4, 20 AND 37OC Anna Lankoff, Sylwester Sommer, Iwona Buraczewska, Teresa Bartłomiejczyk, Teresa Iwaneńko, Halina Lisowska1/, Aneta Węgierek-Ciuk1/, Irena Szumiel, Iwona Wewiór, Anna Banasik-Nowak1/ 1/ Department of Radiobiology and Immunology, Jan Kochanowski University, Kielce, Poland

In the frame of experiments aimed at validation, 20oC: y = 0.008 + 0.028 · D + 0.027 · D2 adaptation and implementation of various biodosi- 37oC: y = 0.008 + 0.025 · D + 0.038 · D2 metric methods we carried out a comparison of Looking for the significance of differences between frequencies of dicentric chromosomes and histone aberration frequencies after irradiation at various γ+H2AX foci in human lymphocytes X-irradiated temperatures, we analysed the variance values at at 4, 20 and 37oC. The effect of temperature at experimental points for the respective doses (not which human lymphocytes are X-irradiated on di- shown). No differences were found between tem- centric chromosome frequency was first described peratures 4 and 20oC, as well as 20 and 37oC. Sta- by Bajerska and Liniecki [1] and recently further tistically significant differences between irradia- examined [2]. As it may affect the cytogenetic tion temperatures 4 and 37oC were found at doses evaluation of ionizing radiation dose, the tempera- 2, 2.5 and 3 Gy (Fig.). Also, aberration distribu- ture effect is both of practical and basic science tion for each dose and irradiation temperature interest. was analysed to see whether it deviates from the The experiments were carried out on blood normal Poisson distribution. To this end, disper- taken three times from four healthy male donors. sion indices (variance-to-mean ratios) were calcu- Mononuclear cells were isolated from the periph- lated and used to calculate the u function, i.e. nor- eral blood samples, suspended in the RPMI 1640 malized dispersion index [5]. Their values (not medium supplemented with foetal calf serum, an- shown) are between the -1.96 to +1.96 limits, indi- tibiotics, L-glutamine and phytohaemagglutinin at cating no deviation from the Poisson distribution. three temperatures mentioned above. After 30 min Further, the flow cytometric determination of incubation at the three temperatures, all samples γ-H2AX foci was carried out at 1 and 24 h after were irradiated with 0, 0.5, 1, 1.5, 2, 2.5 and 3 Gy irradiation at the respective temperatures. The of γ 60Co (Siemens Theratron Elite 80) at a dose dose-effect curves obtained were described by the rate of 1.1 Gy/min. Standard procedures were ap- following linear equations: plied for the chromosomal microscopic prepara- 4oC: y = 9.052 + 9.789 · D tions [3] and cell samples for the flow cytometric 20oC: y = 7.857 + 5.925 · D determination of histone γ-H2AX foci [4]. 37oC: y = 6.926 + 5.702 · D Figure shows the three dose-effect curves for Variance analysis showed no differences in the dicentric chromosomes in peripheral blood lym- total histone γ-H2AX fluorescence at 1 h after ir- phocytes γ-irradiated at three different tempera- radiation between the same doses and temperatures of exposure to γ rays, in contrast with the data for dicentric chromosomes. The total histone γ-H2AX fluorescence at 24 h after irradiation was lower from that at 1 h independently of the exposure temperature. Fluorescence decrease (FD) was calculated as FD = (F1 – F24) · 100/F1 where F1 – fluorescence measured at 1 h post irradiation [%], F24 – fluorescence measured at 24 h post irradiation [%]. FD was about 90%, i.e. close to the control values, notwithstanding the dose (F = 0.949, p = 0.458) or temperature at which irradiation was carried out (F = 1.612, p = 0.121). On the one hand, the presented results point Fig. Dose-effect curves for dicentric chromosomes irradiat- to a lack of effect of the exposure temperature on ed at three different temperatures, as indicated; each point the initial double strand break level, as measured by represents mean value with standard deviation indicated. the γ-H2AX foci fluorescence. On the other hand, Asterisks mark statistically significant differences between the altered, temperature-dependent frequency of irradiation temperatures 4 and 37oC at doses 2, 2.5 and 3 Gy (p < 0.05). dicentric chromosomes may be taken as indication that the exposure temperature affects the fidelity tures; each point represents mean value from 12 of double strand break rejoining. results (4 donors x 3 replicates). The dose-effect curves were described by the following linear-quad- References ratic equations (D – dose): [1]. Bajerska A., Liniecki J.: Int. J. Radiat. Biol., 16, 483-493 4oC: y = 0.002 + 0.024 · D + 0.024 · D2 (1969). 60 CENTRE FOR RADIOBIOLOGY AND BIOLOGICAL DOSIMETRY

[2]. Brzozowska K., Johannes C., Obe G., Hentschel R., [4]. Jucha A., Węgierek-Ciuk A., Koza Z., Lisowska H., Morand J., Moss R., Wittig A., Sauerwein W., Liniecki Wójcik A., Wojewódzka M., Lankoff A.: Mutat. Res., J., Szumiel I.,Wojcik A.: Int. J. Radiat. Biol., 85, 891-899 696, 16-20 (2010). (2009). [5]. Radhakrishna C.R., Chakravarti I.M.: Biometrics, 12, [3]. Sommer S., Buraczewska I., Wojewodzka M., Boużyk 264-282 (1956). E., Szumiel I., Wojcik A.: Int. J. Radiat. Biol., 81, 741-749 (2005).

THE EFFECT OF CONJUGATED LINOLEIC ACID (CLA) SUPPLEMENTATION ON LIPID RAFT PROPERTIES AND RADIOSENSITIVITY OF HUMAN COLON CANCER HT-29 CELLS Iwona Grądzka, Barbara Sochanowicz, Kamil Brzóska, Grzegorz Wójciuk, Christian Degen1/, Gerhard Jahreis1/, Irena Szumiel 1/ Institute of Nutrition, Friedrich Schiller University of Jena, Germany

Ionizing radiation-generated reactive oxygen spe- leic acid (c9,t11-CLA) which is the main isomer in cies activate epidermal growth factor receptor a mixture of CLA, derivatives of linoleic acid (LA, (EGFR) in the plasma membrane. Instead of be- C18:2, cis-9, cis-12), with two double bonds sepa- ing degraded upon internalization (as it takes place rated from each other by one single bond. CLA after the ligand binding), thus activated EGFR are natural components of diary products and meat migrates to the nucleus in vesicles formed of cave- of ruminants. C9,t11-CLA sensitizes human colon olin-enriched lipid rafts. Translocation of the re- cancer HT-29 cells to X-radiation (dose modifica- ceptor is required for activation of DNA-depend- tion factor, D0 control/ D0 CLA = 1.55). The in- ent protein kinase (DNA-PK) – the key enzyme crease in radiosensitivity is not due to changes in of the non-homologous end joining (NHEJ), the cell cycle progression or a decrease in DNA repair-

Fig.1. Distribution of EGFR and cav-1 among cellular membrane fractions. HT-29 cells were cultured without or with 70 μM c9,t11-CLA for 22 h, then irradiated with a dose of 5 Gy. Fifteen minutes after irradiation, membrane vesicles were prepared according to a detergent-free method [1] and fractionated by flotation through OptiPrep gradients. 100 μl aliquots of each fraction were subjected to Western blot analysis. A representative experiment of the three performed is shown. Abbreviations for the experimental groups are in the text. major double strand DNA break (DSB) repair -related gene expression (not shown), but is asso- system in mammals. We examined the radiosensi- ciated with a transcription-independent decrease in tizing properties of 9cis,11trans-conjugated lino- DNA-PK activity that results in transient accumu- CENTRE FOR RADIOBIOLOGY AND BIOLOGICAL DOSIMETRY 61 lation of DSB during repair. The latter, however, is not followed by a significant increase in chromosomal aberration frequencies (not shown). Here, we report that c9,t11-CLA influences the distribution of EGFR, cav-1 (caveolin-1) and cholesterol in cellular membrane fractions. Fractions of cellular membranes from HT-29 cells, obtained with the use of a detergent-free method [1], were analysed in terms of the content of EGFR, cav-1 and cholesterol. Localization of EGFR and cav-1 in the membrane fractions, visualized by Western blotting, is shown in Fig.1, while Fig.2 presents the graphs of distribution of both proteins and cholesterol, normalized to protein content. Generally, in preparations from c9,t11-CLA supplemented cells (CLA, X+CLA) the distributions of all the three membrane components were shifted towards lighter (top) fractions compared to the distributions in the corresponding control preparations (C, X). This appears reasonable, as the CLA isomer incorpo- rated into cellular lipids, increasing the overall content of unsaturated fatty acids (not shown), which must affect the density of the membrane vesicles. Previously, it was established, that in the Fig.2. Distribution of EGFR, cav-1 and cholesterol in frac- density gradient preparations from mammalian tions of cell membranes. The charts are based on the data cells the EGFR-enriched fractions designated the presented in Fig.1: the Western blots were scanned and position of lipid rafts [1]. In this position, covered quantified using ImageJ software; the values were normal- by fractions 8-14 in our experiments (Fig.2), a co- ized to total protein content of each fraction and presented -occurrence of EGFR and cav-1 was observed in as a percentage of all fractions. In addition, cholesterol control (C) but not in c9,t11-CLA supplemented content in each fraction was measured and the distribution of cholesterol/protein ratio was added to the charts. The (CLA) cells. X-irradiation (X) did not essentially data for EGFR, cav-1 and cholesterol are from the same change the relative distribution of the proteins, but experiment – a representative of three experiments per- again, in X-irradiated and CLA-supplemented cells formed. (X+CLA), cav-1 was displaced from the EGFR-enriched region. Interestingly, the distributions of crease in DNA-PK activity in response to ionizing cav-1 and cholesterol in the preparations from radiation, thus influencing the cellular radiation non-supplemented cells (C, X) did not correlate sensitivity. with one-another, whereas they nearly overlapped in the preparations from c9,t11-CLA supplement- References ed cells (CLA, X+CLA). [1]. Macdonald J.L., Pike L.J.: J. Lipid Res., 46, 1061-1067 In conclusion, CLA supplementation of cell (2005). culture medium for 24 h changes the pattern of [2]. Dittmann K., Mayer C., Fehrenbacher B., Schaller M., cholesterol and EGFR distribution in the lipid Raju U., Milas L., Chen D.J., Kehlbach R., Rodemann H.P.: J. Biol. Chem., 280, 31182-31189 (2005). rafts of HT-29 cells. This is accompanied by a de- [3]. Dittmann K., Mayer C., Fehrenbacher B., Schaller creased nuclear translocation of EGFR (not shown). M., Kehlbach R., Rodemann H.P.: FEBS Lett., 584, As reported by Dittmann et al. [2, 3], the EGFR 3878-3884 (2010). import to the nuclei is indispensable for the in- LABORATORY OF NUCLEAR ANALYTICAL METHODS

The Laboratory of Nuclear Analytical Methods was created on the basis of the former Department of Analytical Chemistry in 2009. The research programme of the Laboratory has been focused on the development of nuclear and nuclear-related analytical methods for the application in a nuclear chemical engineering, radiobiological and environmental problems associated with the use of nuclear power (as well as other specific fields of high technology). New procedures of chemical analysis for various types of materials are also being developed. The main areas of activity of the Laboratory include inorganic trace analysis as well as analytical and radiochemical separation methods. The Laboratory cooperates with the centres and laboratories of the INCT and provides analytical services for them as well as for outside institutions. The Laboratory has been also involved in the preparation and certification of new certified reference materials (CRMs) for inorganic trace analysis and is a provider of proficiency testing schemes on radionuclides and trace elements determination in food and environmental samples. The main analytical techniques employed in the Laboratory comprise: neutron activation analysis with the use of a nuclear reactor (instrumental and radiochemical modes), inductively coupled plasma mass spectrometry (together with laser ablation and HPLC), atomic absorption spectrometry, HPLC including ion chromatography, as well as gamma-ray spectrometry and alpha- and beta-counting. In 2011, the research projects carried out in the Laboratory were concerned with: • chemical aspects of nuclear power, • radiopharmaceuticals and health protection, • nuclear and related analytical techniques for environment protection. In 2011, the Laboratory participated together with the Centre of Radiochemistry and Nuclear Chemistry in two Operational Programme Innovative Economy (PO IG) projects. The project on the use of thorium-based fuels in nuclear power reactors was coordinated by the Institute of Atomic Energy POLATOM. The second project on the possibilities of producing uranium from indigenous resources, and to the safety of nuclear power, including radiation protection of humans and environment was coordinated by the INCT and the Polish Geological Institute – National Research Institute was the partner. In 2011, the Laboratory has started participation in the strategic research project from the National Centre for Research and Development (NCBiR), Poland No. SP/J/3/143045/11 on bioleaching of uranium mine waste heaps. The project is coordinated by the Faculty of Biology, University of Warsaw. Laboratory of Nuclear Analytical Methods is a provider of proficiency tests. Two main proficiency testing schemes are conducted: (i) on the determination of man-made radionuclides and (ii) trace elements in waters, food and environmental samples. In 2011, proficiency test on the determination of Am-241, H-3, Pu-239 and Ra-226 in water, food and environmental samples was conducted on the request of the National Atomic Energy Agency, Poland for laboratories forming radiation monitoring network in Poland. Proficiency testing scheme PLANTS 11: Determination of As, Cd, Cr, Cu, Hg, Pb, Se and Zn in dry edible mushroom powder was provided for laboratories analysing food and environmental samples. All proficiency tests are provided following requirements of ISO/IEC 17043:2010 and IUPAC Inter- national Harmonized Protocol (2006). 64 LABORATORY OF NUCLEAR ANALYTICAL METHODS RADIOLYTIC DECOMPOSITION OF DICLOFENAC – ANALYTICAL, TOXICOLOGICAL AND PULSE RADIOLYSIS STUDIES Anna Bojanowska-Czajka, Gabriel Kciuk, Magdalena Gumiela1/, Grzegorz Nałęcz-Jawecki2/, Krzysztof Bobrowski, Marek Trojanowicz 1/ Department of Chemistry, University of Warsaw, Poland 2/ Department of Environmental Health Sciences, Medical University of Warsaw, Poland

With commonly observed in recent decades an in- load in comparison to municipal sources [7]. Many crease of the use of human and veterinary phar- pharmaceuticals are excreted mainly as metabo- maceuticals one can observe also an increase of lites and hence their presence in the aquatic envi- the presence of their residues in the environment. ronment. A significant element of these environ- This fact together with a finding of synthetic phar- mental processes is also indirect potable water maceuticals in finished drinking water causes an reuse. Wastewater treatment plant discharge is di- increasing concern about potential environmental rected to surface waters, and in some cases efflu- and health harmful effects. The most commonly ent dominated surface waters are used for drink- accepted form of toxicity associated with environ- ing treatment facilities. mental pharmaceutical residues is endocrine dis- Besides increasing consumption of pharmaceu- ruption, which means the disruption of chemical ticals, a significant factor contributing to their pres- signalling mechanisms controlling cellular devel- ence in the environment is the limited efficiency opment. of their decomposition in wastewater treatment First reports about detecting pharmaceuticals plants, and in drinking water treatment plants. This in environmental samples were published in the concerns such methods as UV irradiation, oxidation early 1970s [1], and in 1965 it was observed for the with free chlorine, or even ozonation [8]. Concen- fist time that residues of steroid hormones are not tration of some pharmaceuticals detected in efflu- completely decomposed by wastewater treatment ents (antibiotics, non-steroidal anti-inflammatory [2]. Since then a fast increase of interest in differ- drugs or steroid hormones) may reach even frac- ent aspects of the presence of pharmaceutical resi- tions of mg/L [9]. This is then reflected by concen- dues in environmental waters is observed. Number trations of pharmaceuticals and their metabolites of papers published annually was about 500 in in worldwide tap water, which are found in some 2000, while it reached a level of about 3000 in 2010 cases in the level exceeding 1 μg/L (iodinated [3]. In a recent decade this problem was a subject X-ray contrast medium diatrizoate, analgesics of several published books, e.g. [4], and numerous AMIDOPH, ibuprofen) [10]. Hence, strong at- valuable review articles in scientific journals, e.g. tention is focused in recent years on the develop- [3, 5]. ment of radical methods of decomposition, de- Pharmaceuticals are a very large and diverse scribed as advances oxidation processes. Especially group of chemicals consisting of both human and efficient process is radiolytic decomposition by veterinary medicinial compounds. It is assumed the use of ionizing radiation (gamma or beam of that it consists of about 4500 species, including accelerated electrons), where, as a result of water pharmaceuticals which are in various stages of in- radiolysis taking place during irradiation of aque- vestigation. Research studies concerning their pres- ous solutions, radicals of oxidative and reductive ence in the environment and their removal from properties are formed. These processes were al- waters and wastes published so far, deal with about ready examined for satisfactory decomposition of 160 human and veterinary pharmaceuticals and β-blockers [11], and antibiotics nitroimidazoles [12]. about 30 by-products [5]. The main groups of phar- Very recently, when the present studies were in maceuticals, which are detected in the aqueous en- progress, the first paper was published on radio- vironment include anti-inflammatory drugs (anal- lytic decomposition of diclofenac [13], which as a gestics), steroids and related hormones, antibiotics, widely used analgesic and a non-steroidal anti-in- β-blockers and lipid regulators. Some of them are flammatory drug, is a subject of wide studies in consumed annually even in tens or hundreds of terms of its occurrence in waters and its removal tons. For instance, non-steroidal anti-inflammatory in wastewater treatment [14]. drug paracetamol – 622 t in Germany in 2001, ibu- Frequent occurrence of pharmaceuticals in the profen – 345 t in Germany in 2001, diclofenac aquatic environment, and also in finished drinking (DCF) – 86 t in Germany in 2001, and naproxen – water, is a source of concern about their impact 35 t in England in 2001 [6]. on public health, although commonly encountered As the main source of wide presence of pharma- opinion in the literature is that our current knowl- ceuticals in the environment is considered munici- edge what is the effect of human exposure to low- pal water discharge, of which many residual drugs -dose mixture of pharmaceuticals is none. One can are not removed by current wastewater processes. find opinions about no appreciable risk to human Another contributing sources are industries, farms at detected concentrations of pharmaceutical resi- and hospitals, although as it was demonstrated re- dues [15], but due to consuming contaminated cently by studies carried out in Norway, the point drinking water over a lifetime, chronic toxic ef- sources discharges from hospitals typically make a fects cannot be excluded because of lack of chronic small contribution to the overall pharmaceutical ecotoxicity data [16]. This creates both demand for LABORATORY OF NUCLEAR ANALYTICAL METHODS 65 wide monitoring of presence of pharmaceuticals dative and reductive conditions due to different in waters and wastes, and search for more efficient reactivity of different radicals. This was shown re- and cost-effective methods of their removal. cently, e.g. for the decomposition of pesticide car- In the coarse of this study aqueous solutions of bendazim [17]. As it is shown in Fig.1, while the DCF were gamma-irradiated using a 60Co source decomposition of DCF in 50 mg/L DCF in aerated Gamma Chamber with a dose-rate of 8.0 kGy/h. Using chromatographic methods several factors 100 affecting efficiency of radiolytic decomposition of DCF and formation of products of radiolysis were 80 examined. The reversed-phase HPLC determinations of DCF were carried out using a Shimadzu 60 chromatograph with a diode array UV/Vis detector, a Luna ODS2, a 5 μm 250 × 4.6 mm analytical column and a guard column from Phenomenex 40 (Torrance, CA, USA). The following conditions were employed for determination of DCF: iso- 20 Yield of decomposition % cratic elution with eluent consisted of 50 mM phosphate buffer of pH 7.0, methanol and ace- 0 tonirile (58:21:21 v/v), flow-rate – 1.0 mL/min, sample injection volume 20 – μL. The determina- 012345 tions were carried out without additional precon- Dose, kGy centration, and limit of detection for DCF was Fig.1. Effect of dose on yield of radiolytic decomposition evaluated as 0.13 mg/L. The ion-chromatographic of diclofenac in 50 mg/L aqueous solutions gamma-irradi- determinations of chloride were performed using ated in different conditions: (■) aerated solution, (●) solution saturated with N O, (▲) solution of pH 7.0, contain- a chromatograph Dionex model 2000i/sp, equip- 2 ing 0.52 mM tert-butanol and saturated with argon. ped with an ASRS I electrochemical anion self- -regenerating suppressor, a conductivity detector, aqueous solution requires a dose of 4.0 kGy, in the an AG9HC guard column, and an AS9HC analyti- process carried out with scavenging of solvated cal anion exchange column from Dionex. Mobile electron by saturation of irradiated solution with phase of the system was sodium carbonate and N2O, the required dose drops down to 1 kGy. The sodium bicarbonate with a flow rate of 1 mL/min. deaeration of irradiated solution by saturation with Studies in this stage of the project included ex- argon and irradiation in the presence of tert-buta- perimental determination of the yield of radiolytic nol decreases the yield of DCF irradiation only in decomposition of DCF in various conditions of the range of doses from 0.5 to 3 kGy, whereas above irradiation where different products of water ra- 3 kGy has no effect. Such studies were not report- diolysis predominate. They also included effect of ed in recently published work [13], and they evi- the presence of selected scavengers of radicals dently show the predomination of oxidative decom- commonly occurring in natural waters, and also ef- position of DCF by gamma irradiation. fect of matrices of different natural waters on the The presence of such ●OH radical scavengers efficiency of radiolytic decomposition. In numer- as nitrate, carbonate or humic acid at 50 mg/L ous reported investigations of radiolytic decompo- level does not affect decomposition of DCF at an sition of different organic pollutants it was shown initial level of 50 mg/L (Fig.2), which is in good that the yield of decomposition is different in oxi- agreement with reported data [13]. It was ob-

A 100 B 15 14 13 80 12 11 10 60 9 8 7 40 - 6 50 ppm NO3 2- 5 50 ppm CO3 2- 4 50 ppm NO2- 100 ppm CO 3 20 3 3 2-

Yield of decomposition % Yield 50 ppm CO 50 ppm humic acid Chloride concentration, ppm 3 2 2- 100 ppm CO3 1 50 ppm humic acid) 0 0 012345 012345 Dose, kGy Dose, kGy Fig.2. Effect of the presence of selected scavengers of radicals on (A) yield of decomposition of diclofenac in aerated aqueous solutions at initial concentration 50 mg/L, and (B) release of chloride during irradiation at different doses. 66 LABORATORY OF NUCLEAR ANALYTICAL METHODS A diolytic decomposition of organic pollutants was reported also earlier, e.g. in radiolysis of pesticide atrazine [18]. Humic acid as effective scavenger of hydroxyl radicals may favour reaction of solvated electron, which in the case of some transient products formed during radiolysis of DCF may lead to more effective release of chloride. B 100 The effectiveness of DCF decomposition carried out in complex matrix of river water is illus- 80 trated by chromatograms shown in Fig.3A. Irra- diation of river water spiked with 50 mg/L DCF with a 0.2 kGy dose leads to a 24% decrease of 60 DCF concentration. In the same figure it is shown a chromatogram recorded for a Vistula river water sample without irradiation, which indicates the 40 presence of 0.29 mg/L DCF. As it is shown in Fig.3B, the yield of irradiation is similar for dis-

Yield of decomposition % 20 50 ppm DCF in distiled water tilled and river waters, but evidently larger in tap 50 ppm DCF in tap water water, and these data require further investiga- 50 ppm DCF in river water tions. 0 The goal of this work was also investigation of 012345the radiation-induced degradation pathway. The Dose, kGy knowledge regarding kinetic parameters of reac- – Fig.3. Effect of different water matrices on yield of radio- tions of parathion with radical species (e aq and lytic decomposition of diclofenac with initial concentration ●OH) will be useful in ascertaining the degrada- 50 mg/L: A – HPLC chromatograms recorded for Vistula tion reaction pathways. The radiolysis of water river water spiked with 50 mg/L DCF and irradiated with and aqueous solution is based on the ionization of 0.2 kGy dose (a), and for non-spiked Vistula river water water molecules, because in dilute solution, when prior to the irradiation (b); B – yield of radiolytic decom- –3 position of DCF in aerated solutions of 50 mg/L in distilled concentration ≤ 0.1 mol dm the ionized molecules water (■), tap water (●), and Vistula river water (▲). are essentially those of the solvent: ● ● – + H2O => OH + H + e aq + H3O + H2O2 served, however, only in this study that in the pres- In this stage of the project the reaction between ence of 50 mg/L of humic acid in irradiated solu- diclofenac and hydroxyl radical (●OH), was studied tion a much more effectively inorganic chloride by the puls radiolysis method. A comparison be- are released from transient products of DCF ir- tween the obtained data and the data concerning radiation in comparison to other examined condi- radical reactions of dichloro-derivatives aromatics tions of irradiation (Fig.2B). A favourable effect compounds available in the literature will give ad- of the presence of humic acid on the yield of ra- ditional information about the nature of occurring 3.24 12 k = 1.24 × 1010 mol-1s-1dm3 3 ]

-1 10 [s 6 8 2.43 10 ×

] × 10 6 –1 k obs 4

cm 2 1.62 –1 0

J 0.0 0.2 0.4 0.6 0.8 1.0 3 concentrationconcentration [mM] a Ab [dm 0.81 ε Bc Cd

G × D

0.00 325 390 455 520 585 Wavelength [nm] Fig.4. Absorption spectra recorded in pulse radiolysis system for 0.1 mM aqueous solution of diclofenac of pH 7.0 saturated with N2O at different time delays: (a) 0.12 ms, (b) 0.8 ms, (c) 16 ms and (d) 500 ms. Inset shows the Stern-Volmer plot of the absorption growth at 370 nm. LABORATORY OF NUCLEAR ANALYTICAL METHODS 67 radical reactions. The reaction of ●OH radical irradiated solutions. This allows the determination with diclofenac water solution (at pH 5.6) was of authentic environmental impact of applied pro- carried out in solution saturated with N2O – a cesses with the use of different test organisms. It well-known electron scavenger. was not reposted so far for radiolytic decomposi- The main absorption spectrum constitutes of O three bands seen on the spectra recorded during oxidation of DCF by ●OH radical. The first – most Cl OH O intensive absorption band, is located at λmax = 370 NH nm, it grows up within < 0.8 μs time domain (Fig.4, OH curve b), with rate k = (1.30 ± 0.06) × 107 s–1, and Cl OH 4 –1 Cl decay with rate k = (6.4 ± 0.5) × 10 s . The sec- NH O ond absorption band is located at a shorter wave- + HO OH length, and also is built up within microsecond Cl Cl time domain (Fig.4, curve b). The location of the NH second band is changing with time, it starts at λ max HO = 335 nm (Fig.4, curve a), after 0.8 μs is moved to Cl λmax = 325 nm (Fig.4, curve b), and after 6 μs is Fig.5. Formation of diclofenac adduct(s). seen as a shoulder of absorption band located at a wavelength below λ = 320 nm (start of measure- tion of DCF. In this study three different tests ment). This observation clearly indicates that at were employed, which are widely used in environ- this region more than one species is responsible mental toxicity studies. Microtox is based on the for absorption, and therefore its interpretation is use of the bioluminescent marine bacterium Vibrio ambiguous. fisheri as the test organism, Spirotox is a test un- The absorption spectra recorded 0.8 μs after dertaken with a very large ciliated protozoan Spi- electron pulse comprises additional shoulder-shape rostomum ambiguum, while Thamnotoxkit is a bio- absorption (Fig.4, curve b), and with elapsed time assay using larvae of the freshwater anostracen Thamnocephalus platyurus it reveals absorption band located at λmax = 430 crustacean hatched from nm (Fig.4, curve c and d). The absorption record- cysts. The toxicity studies were conducted for 50 ed after the end of OH-radical reaction with DCF mg/L DCF solutions irradiated in aerated solution (Fig.4, curve b) can be attributed to the primary with doses up to 5 kGy. With all employed tests a product(s) of oxidation diclofenac by ●OH radi- certain increase of toxicity was observed for the cals. Probably it is an adduct(s) of ●OH to aro- applied doses in the range 0.5-0.8 kGy, where as it matic rings of DCF (Fig.5). was shown above about 50-60% of DCF is decom- The overall rate constant of the ●OH radical re- posed (Fig.6). This indicates a larger toxicity of action with DCF deducted from the Stern-Volmer formed transient products from the decomposed plot of absorption build-up at λmax = 370 nm is DCF. At a 3.5 kGy dose, where complete decom- equal to k = 1.24 ± 0.02 × 1010 dm3 mol–1 s–1 (inset position of DCF was observed (Fig.1), a 33% de-

10 10 10 9 A 9 B Microtox C 8 8 Spirotox 8 7 7 Thamnotoxkit

6 6 6

5 5 TU 50 TU 50 4 4 TU 50 4

3 3

2 2 2

1 1

0 0 0 012345 012345 012345 Dose, kGy Dose, kGy Dose, kGy Fig.6. Toxicity changes observed with different toxicity tests at different applied doses for irradiation of 50 mg/L aerated solution of diclofenac: A – Microtox, B – Spirotox, C – Thamnotoxkit. in Fig.4). In a longer time scale the decay of ab- crease of Microtox toxicity was observed, while sorptions band λmax = 370 nm is observed, which is practically no changes of toxicity with two other associated with the decay or transformations of employed tests was found in comparison to initial primary products. The absorption of transient values prior to irradiation. This means a very low products of DCF oxidation recorded 0.5 ms after toxicity of DCF for the organisms employed in electron pulse (Fig.4, curve d) reveals absorption those two tests, and also a differentiated environ- at λmax = 430 nm and a shoulder at shorter wave- mental impact of DCF residual in waters and lengths. wastes. A very important supplement to analytical investigation of the efficiency of radiolytic decom- References position of organic pollutants for environmental [1]. Tabak H.H., Brunch R.L.: Devel. Ind. Microbiol., 11, protection is the monitoring of toxicity changes of 367-376 (1970). 68 LABORATORY OF NUCLEAR ANALYTICAL METHODS

[2]. Stumm-Zollinger E., Fair G.M.: J. Water Pollut. [12]. Sanchez-Polo M., Lopez-Penalver J., Prados-Joya G., Control Fed., 37, 1506-1510 (1965). Ferro-Garcia M.A., Rivera-Ytrilla J.: Water Res., 43, [3]. Fatta-Kassinos D., Meric S., Nikolaou A.: Anal. Bio- 4028-4036 (2009). anal. Chem., 399, 251-275 (2011). [13]. Liu Q., Luo X., Zheng Z., Zheng B., Zhang J., Zhao [4]. Kümmerer K.: Pharmaceuticals in the environment: Y., Yang X., Wang L.: Environ. Sci. Pollut. Res., 18, sources, fate, effects and risks. Springer-Verlag 2008. 1243-1252 (2011). [5]. Mompelat S., Le Bot B., Thomas O.: Environ. Int., [14]. Zhang Y., Geissen S.-U., Gal C.: Chemosphere, 73, 35, 803-814 (2009). 1151-1161 (2008). [6]. Fent K., Weston A.A., Caminada D.: Aquat. Toxicol., [15]. Schulman L.J., Sargent E.V., Numann B.D., Faria E.C., 76, 122-159 (2006). Dolan D.G., Wargo J.P.: Hum. Ecol. Risk Assess., 8, [7]. Langford K.H., Thomas K.V.: Environ. Int., 35, 766-770 657-687 (2002). (2009). [16]. Carlsson C., Johansson A.K., Alvan G., Bewrgman [8]. Snyder S.A.: Ozone Sci. Technol., 30, 65-69 (2008). K., Kuhler T.: Sci. Total Environ., 364, 67-87 (2006). [9]. Ikehata K., Naghashkhar N.J., El-Din M.G.: Ozone [17]. Bojanowska-Czajka A., Nichipor H., Drzewicz P., Sci. Eng., 28, 353-414 (2006). Szostek B., Gałęzowska A., Męczyńska S., Kruszew- [10]. Jones O.A., Lester J.N., Voulvoulis N.: Trends Bio- ski M., Zimek Z., Nałęcz-Jawecki G., Trojanowicz M.: technol., 23, 163-167 (2005). J. Radioanal. Nucl. Chem., 289, 303-314 (2011). [11]. Song W., Cooper W.J., Mezyk S.P., Greaves J., Peake [18]. Basfar A.A., Mohammed K.A., Al-Abduly A.J., Al-Sha- B.M.: Environ. Sci. Technol., 42, 1256-1261 (2008). hrani A.A.: Ecotox. Environ. Safe., 72, 948-953 (2009).

ELABORATION OF OPTIMAL CONDITIONS OF GEOLOGICAL MATERIALS ANALYSIS FOR URANIUM DETERMINATION Iwona Bartosiewicz, Ewelina Chajduk, Marta Pyszynska, Jadwiga Chwastowska, Halina Polkowska-Motrenko

The plans of building a nuclear power plant in 550oC) when alkali fusion is applied. This stage pro- Poland resulted from the fact that it is the most ef- longs the time of analysis. When the acid miner- fective way to cover the growing demand for elec- alization method is applied, hydrofluoric acid has tricity. Because of this the problem of perspective to be added to the digestion mixture to remove domestic uranium deposits has become very actual. silicon present in the sample. However, some ele- The purpose of our work was the elaboration ments like Al, Fe, alkaline earths and rare earth of optimal conditions of analysis of geological ma- elements form low soluble fluorides and such ele- terials for uranium content. Dictyonema shales ments as U, Th, lanthanides form stable fluoride and sandstones were chosen for the analysis. These complexes, what can cause losses of the deter- materials are known as uranium-bearing [1, 2] mined elements. In order to avoid these effects, and differ significantly in composition. Inductively boric acid is usually added to complex remaining coupled plasma mass spectrometry was used for HF and to enable dissolution of the precipitated the analysis [3-5]. fluorides [8-10]. In this work, the influence of dif- The methods of digestion are essential for the ferent methods of digestion of geological samples analysis of geological materials. Two methods of on the results of the determination of elements digestion were taken into consideration: alkali fu- was studied. The following methods of digestion sion [6] and mineralization in a microwave diges- were examined: tion system with using suitable mineral acids [3, 7]. a) fusion with Na2O2 [11] in zirconium crucibles; In the case of high content of organic substances, b) mineralization in a closed microwave digestion especially in shales (20-30%), a stage of prelimi- system (Anton Paar Multiwave 3000) of 250 mg nary roasting before fusion is necessary (4.5 h at sample in a mixture of HNO3 + HF; Table 1. Results of ICP-MS determination of U, Th, La, Yb in dictyonema shales using different digestion methods. Removing of F– in microwave digestion system Fusion Evaporation Sample Element Mineralization 12 mL 0.5 g 1 g with Na2O2 with H3BO3 4% H3BO3 H3BO3 H3BO3 U 41 8 35 41 26 43 Th 12 0.14 7.3 15 7 11 1 La 40 0.28 29 43 18 43 Yb 4.0 0.21 3.5 3.7 2.5 3.3 U 100 40 83 103 80 100 Th 13 1.8 11 16 11 13 2 La 41 0.8 25 48 28 43 Yb 4.0 0.9 3.5 4.2 3.1 3.4 LABORATORY OF NUCLEAR ANALYTICAL METHODS 69 c) mineralization as described in point b) follow- Table 2. Working parameters for ICP-MS analysis. ed by removing of fluoride ions by evaporation RF power: 1000 W with H3BO3 solution on a hot plate; d) mineralization as described in point b) follow- Plasma gas: 13.0 L min–1 ed by removing of fluoride ions applying two- Auxiliary gas: 1.2 L min–1

-step procedure with solid H3BO3 or 4% H3BO3 –1 solution added in the second step. Mass spectrometer Nebulizer gas: 0.92 L min The obtained results of the inductively coupled ELAN DRC II Lens voltage: 6.75 V plasma mass spectrometry (ICP-MS) analysis of Detector mode: dual two different samples of dictyonema shales are shown in Table 1. Cones: Ni The obtained results show that the use of two- Working mode: standard -step process (mineralization + removing fluorides in a microwave digestion system using 4% H3BO3) (daily performance solutions of concentration of 1 ensures complete recovery of elements which form ng mL–1 – Perkin Elmer). The optimal conditions stable fluoride complexes. It reduces significantly of analysis by the ICP-MS method (Table 2) were also the analysis time and can be recognized as an established by checking the effect of the following optimal mineralization procedure. parameters: RF power, nebulizer gas flow and lens Sandstones contain as a rule high content of silica voltage. and not so high of organic substances. In that case After sample decomposition, the obtained solu- the digestion by fusion is preferred. The following tions were diluted with 0.7% HNO3 and In was trace elements were determined: U, Th, Cu, Co, added as an internal standard prior to the analysis. Mn, Zn, La, V, Yb, Mo, Ni and Sb by the ICP-MS The following nuclides: 238U, 232Th, 63Cu, 59Co, method. 55Mn, 66Zn, 139La, 51V, 174Yb, 98Mo, 60Ni, 121Sb and Elaborated procedures of analysis 57Fe were selected since they are free from inter- Geological materials are heterogeneous, there- ference and are sufficiently abundant for quanti- fore much affords were made to get a representa- tative measurement by ICP-MS. tive sample. The analysed samples was homoge- Expanded uncertainty – U (k = 2) was evaluated nized by milling in an agate ball mill (dictyonema as 5-15%. shales) and in tungsten carbide ring mill (sand- The elaborated methods were applied to the stones) to obtain the grain size less than 0.2 mm. analysis of 50 samples of dictyonema shales and Then, the obtained fraction was carefully mixed. 50 samples of sandstones. The examples of results Analysis of dictyonema shales of analysis are presented in Table 3. 0.25 g of a sample was weighed directly to a di- The uranium content range was from 41 to 215 gestion vessel, a mixture of 6 mL of HNO3 + 2 mL ppm and 5 to 1316 ppm for shales and for sand- of HF was added and the vessels were capped. The stones, respectively. Beside uranium, V, Ni, Cu, digestion programme for geological materials was Mo, Mn were also determined, as they can be im- applied. Then, the vessels were left for cooling and portant for technology. From the obtained data, a opened. Twelve mL of 4% H3BO3 solution was big diversity of uranium as well as other elements added and the second step of digestion was com- o Table 3. Results of analysis of some geological material pleted (50 bar, 220 C, 45 min). The obtained solu- samples [mg kg–1]. tion was transferred into a 50 mL PFA volumetric flask and submitted to analysis by the ICP-MS method. Dictyonema shales Sandstone Analysis of sandstones Element 0.5 g of a sample was weighed to zirconium Sample code crucibles, 2 g of Na2O2 was added and carefully 3 8 141 160 mixed. The fusion process was carried out in an oven at a temperature of 550oC during 1 h. The U 41 142 1144 565 alloy was dissolved in water, then HNO3 concd. Th 12 15 14 4.3 was added to attain 5 M, and the mixture was heated at a temperature of about 80oC to obtain clear Cu 244 208 47 59 solution. The obtained solution was transferred to Co 13 20 117 96 a 250 mL volumetric flask and adjusted with water to 250 mL. Mn 94 50 890 640 Blanks were prepared in the same way as the Zn 240 4830 999 45 samples. After suitable dilution, the samples were La 40 45 51 14 analysed by the ICP-MS method. Conditions of determination by ICP-MS V 1730 1650 717 371 The instrument used was ELAN DRC II Yb 4.0 3.7 2.5 2.0 (Perkin Elmer) with a crossflow nebulizer with a Scott double-pass spray chamber and Ni cones. Mo 68 270 < 5 < 5 Optimization of experimental parameters of an Ni 247 287 52 45 ICP-MS spectrometer was performed with respect to the maximal ion intensity of chosen elements Sb 7.0 18 0.3 0.2 70 LABORATORY OF NUCLEAR ANALYTICAL METHODS concentration is observed. Bigger diversity is ob- [6]. Galindo C., Mougin L., Nourreddine A.: Appl. Radiat. served in the case of sandstones samples. Isot., 65, 9-16, (2007). [7]. Chen M., Ma L.Q.: Soil Sci. Soc. Am. J., 65, 491-499 References (2001). [8]. Krachler M., Mohlb C., Emons H., Shotyk W.: Spectro- [1]. Bareja E.: Kwart. Geol., 21, 4, 705-714 (1977), in chim. Acta Part B, 57, 1277-1289 (2002). Polish. [9]. Swami K., Judd C.D., Orsini J.,· Yang K.X., Husain L.: [2]. Bareja E.: Kwart. Geol., 28, 2, 353-366 (1984) , in Fresenius J. Anal. Chem., 369, 63-70 (2001). Polish. [10]. Ivanova Ju., Djingova R., Korhammer S., Markert B.: [3]. Krachler M., Mohl C., Emons H., Cozzi G., Barbante Talanta, 54, 567-574 (2001). C., Cescon P., Shotyk W.: J. Anal. At. Spectrom., 17, [11]. Choy C.C., Korfiatis G.P., Meng X.: J. Hazard. Mater., 844-855 (2002). 136, 53-60 (2006). [4]. Balcerzak M.: Anal. Sci., 18, 737-750 (2002). [5]. Celo V., Dabek-Zlotorzynska E., Mathieu D., Okon- kaia I.: Open Chem. Biomed. Meth. J., 3, 143-152 (2010). LABORATORY OF MATERIAL RESEARCH

Activities of the Laboratory are concentrated on: • studies of coordination polymers built of s block metals and azine carboxylate ligands, • synthesis of nanoscale porous metal organic framework materials (nanoMOFs) using particle track membranes as template, • synthesis of functional materials – silver modified cotton and cellulose fibers using radiation beam techniques, • modification of surface layer of engineering materials by implantation of lanthanide elements and nitrogen atoms using high intensity plasma pulses, • characterization of art objects. The design and construction of coordination polymers have been studied intensively in recent years, as evidenced by the very rapid growth of publications. Particularly, the porous coordination polymers or the so-called metal organic framework materials (MOFs) are of great interest due to their potential applications for gas storage, gas separation, catalysis, sensors, etc. Despite of many achievements in the field, new rational and effective methods for assembling coordination polymers with specific or desired structure are still awaited. Our in- terests are focused on light s block metals coordination polymers with carboxylic ligands with carboxylic and/or nitrogen functionality. In the last year the crystal structures of seven new lithium coordination polymers with azine dicarboxylic acids have been solved and published. For many potential MOF applications, it is essential to obtain them on the nanometer length scale (nanoMOFs). Nanoscopic dimensions are essential for many applications, particularly, for biomedical applications, like drug carriers and diagnostic agents. They also find applications in the field of catalysis, to obtain materials with better kinetic properties due to higher ratio of surface to bulk atoms, and for surface sensors development by integrating nanoscale materials on the surface. For the synthesis of nanoMOFs, we have applied the so-called template synthesis method using particle track membranes. The possibility of HKUST-1 MOF nanocrystals synthesis in the pores of track-etched membranes has been demonstrated. The results were presented at the NUTECH 2011 conference and the paper concerning the results should appear in the conference materials in “Nukleonika”. The production of the track-etched membranes is well-known in membrane science and described in the literature. However, the increasing interest of polymer track-etched membranes with nano-channels still exists and is related to development and creation of nanoporous materials with unique properties. New achievements concerning membranes with diode-like pores and membranes with highly asymmetrical nanopores have been obtained in the course of the last years in the Flerov Laboratory of Nuclear Reactions, Joint Institute for Nuclear Research (Dubna, Russia). Their structural properties have been documented in the course of joint research work of the Flerov Laboratory of Nuclear Reactions and the Laboratory of Material Research. In the cooperation with the National Nuclear Research Centre at Świerk (Poland) studies on the modification of surface properties of AISI 316L stainless steel with REE (Ce+La) using high intensity pulsed plasma beams (HIPPB) have been carried out. The results of this work show that improvement by alloying AISI 316L stainless steel with REE (Ce+La) leads to the formation of a remelted and enriched with active elements near surface layer, and that the obtained modified surface layers show marked improvement of tribological properties as compared to initial material. The research on radiation enhanced synthesis of silver nanoparticles on a number of polymeric matrices like cellulose and cotton fibres as well as powdered silica contained materials have been continued. The silver ions deposited from a solution of silver salts were reduced using accelerator electron beam. The materials obtained have been characterized using scanning electron microscope with back-scattered electrons detector (SEM-BSE), energy dispersive X-ray (EDX), X-ray diffraction (XRD), electron paramagnetic resonance spectroscopy (EPR). Their thermal properties have been determined using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) methods and their antibacterial and antifungal properties have been determined as well. The results were presented recently at the 27th Miller Conference on Radiation Chemistry, International Meeting on Radiation Processing (IMRP 2011), 12th Tihany Symposium on Radiation Chemistry, International Conference on Develop- ment and Applications of Nuclear Technologies NUTECH 2011. Nuclear analytical techniques have been applied in the Laboratory for many years for examination, characterization and analysis of cultural heritage artefacts or art objects and their component materials. The unique properties of this technique like high sensitivity, reproducibility, non-destructive and non-invasive character are crucial for an enhencement of our knowledge concerning their elaboration, their evolution and degradation during time. They provide a basis for their restoration and conservation. Recently, studies on the basic attributes and limitations of INAA technique for the analysis of alabaster sculptures has been completed in the Laboratory. LABORATORY OF MATERIAL RESEARCH 73 STRUCTURAL STUDIES IN Li(I) ION COORDINATION CHEMISTRY Wojciech Starosta, Janusz Leciejewicz

An analysis of the crystal structures of Li(I) ion the carboxylate group and the pyridazine ring is complexes with diazine carboxylate ligands deter- 43.4(2)o. The pyridazine ring is almost planar with mined up to now in the course of the present project r.m.s. of 0.0148(2) Å. Both ligand’s heterocyclic N reveals a number of interesting features which are atoms remain coordination inactive. The Li(I) ion briefly summarized below: is coordinated by the bridging carboxylato O1 and • Li(I) ions show an evident preference to adopt O1(ii) atoms, a bridging carboxylato O2(i) donated distorted trigonal bipyramidal coordination ge- by the adjacent dimer and the aqua O3 atom re- ometry with coordination number five. Among sulting in a distorted tetrahedral coordination. 17 symmetry independent Li(I) ions, which were Carboxylato O2 atoms bridge the dimers into mol- observed in the crystal structures of 11 complexes ecular layers which are approximately parallel to [1-11], 12 ions show this coordination mode, 4 the crystal bc plane. The structure of a layer can be ions distorted tetrahedral environment with co- visualized as composed of corrugated loops with ordination number four. In only one complex four equal sides and the dimers at their apices. [2] octahedral coordination with six coordinat- Hydrophobic parts of pairs of pyridazine rings are ed atoms has been observed. directed inside the loop with closest distance of • Apart from one structure [5], the others show 4.91(1) Å between ring centres while heterocyclic more or less complicated polymeric molecular N atoms are directed outside and participate in a patterns, irrespectively whether the ligand is network of hydrogen bonds. The latter consist of mono- or multicarboxylate. coordinated water molecules acting as donors and • In three complexes [1, 6, 7] centrosymmetric moieties have been found as building blocks of the structures. • Water molecules are active in 11 structures as coordinating and bridging agents. Only in two structures [9, 10] solvation water molecules have been also detected. The structure of one complex [7] does not contain water molecules, but besides the N,O bonding groups, nitrate groups act as coordinating and bridging. • In all compounds systems of hydrogen bonds are responsible for the stability of their structures. Short hydrogen bonds linking protonated and deprotonated carboxylic groups of the same Fig.2. The packing of layers composed of dimeric units ligand molecule are observed in the structures viewed along the c axis. of three compounds [3, 4, 9]. In two more complexes short bonds with the hy- the pyridazine N atoms in an adjacent layer as ac- drogen atom located at an inversion centre are ceptors. They form centrosymmetric rings which observed. They act as bridging to form catenat- give rise to a three-dimensional structure (Fig.2). 2O;O’ ed [2] and layered [11] molecular patterns. Part 07. Poly[(μ2-nitrato-κ )(μ2-pyrimidi- 2O;O’ Part 06. Poly[aqua(μ3-(pyridazine-4-carboxy- num-2-carboxylato-κ )lithium] [7] lato-κ2O:O:O’)lithium] [6] The structure of the title compound contains The structural unit of the title compound is a Li(I) ions, each coordinated by two ligand carboxy- centrosymmetric dimer composed of two Li(I) lato and two nitrato O atoms at the apices of a bridged by a bidentate carboxylate O1 atom, each distorted trigonal bipyramid. Its base is composed

Fig.1. A dimeric structural unit of the title compound with atom labelling scheme and 50% probability displacement ellipsoids. Symmetry code: (ii) -x, -y+1, -z. donated by one of two symmetry related ligands Fig.3. A fragment of the structure with atom labelling (Fig.1). The ligand carboxylate group C7/O1/O2 scheme. Non-hydrogen atoms are shown as 50% displace- (ii) (iii) makes with the O1/Li1/O1 Li plane a dihedral ment ellipsoids. Symmetry code: (ii) -x+1, -y+1, -z+1; (iii) angle of 10.9(1)o, while the dihedral angle between -x+3/2, y+1/2, z. 74 LABORATORY OF MATERIAL RESEARCH of coplanar carboxylato O1, nitrato O11 and O12(ii) 1 and 0.0069(1) Å for ring 3; carboxylate groups atoms (Fig.3). The Li1 ion is shifted by 0.0548(2) C17/O11/O12 and C37/O31/O32 make with rele- Å above this plane. The carboxylato O2(iii) is at the vant rings dihedral angles of 11.2(1)o and 11.0(1)o, apex of the pyramid. Li-O bond distances fall in respectively. The nitrate anion is planar (r.m.s. the range from 1.967(3) to 2.019(3) Å, commonly observed in the structures of Li(I) complexes with

Fig.5. A dimeric structural unit with atom labelling scheme and 50% probability displacement ellipsoids. Symmetry code: (i) -x+2, -y, -z+2; (ii) x, y+1, z; (iii) x, y+1, z. 0.0002(1) Å). Its O1 atom acts as bidentate and bridges Li1 and Li3 ions, while the O2 atom chelates the Li2 ion. Nitrato O3 atom is coordination inactive. Li1 and Li1(i) ions bridged by biden- Fig.4. Packing of molecular layers viewed along the a axis. tate carboxylate O11 and O11(i) form a core of a carboxylate ligands. The Li1-N1 bond distance of centrosymmetric cluster composed of Li1 and Li3 2.467(3) Å as too long was not allowed in coordi- ions bridged by bidentate nitrato O1 atom, Li1 nation of the Li1 ion. The pyrimidine ring is planar and Li2 bridged by the aqua O4 atom, Li2 and Li3 with r.m.s. of 0.0074(1) Å. A hydrogen atom at- bridged by the aqua O5 atom. The clusters bridged tached to the hetero-ring N2 atom, clearly visible via nitrato O1 and O2 atoms, form molecular colon the Fourier map, maintains the charge balance. umns along the crystal [010] direction (Fig.6) which It links the N2 atom with the carboxylate O(i) atom are held together by a network of hydrogen bonds via a hydrogen bond of 2.5762(17) Å. Bond dis- in which aqua O4 and O5 molecules are as donors tances and bond angles within the pyrimidine ring and carboxylate O31 and O32 atoms as acceptors. do not differ from those reported earlier in the π-π type interactions between methylpyrazine rings structures of other metal complexes with the title belonging to adjacent columns are also observed ligand. The C7/O1/O2 carboxylate group makes as indicated by the distances between the centroids with ring a dihedral angle of 14.81(2)o. Two Li(I) of slightly shifted each to the other hetero-rings ions, one coordinated by the carboxylato O1 atom, which amount to 3.694(3) and 3.796 Å. the other by the second carboxylato O2 atom of the same ligand form molecular ribbons composed of dimeric units (Fig.4). The latter bridged by nitrato O11 and O12(ii) atoms give rise to molecular layers. Part 08. Poly(di-μ2-aqua-μ2-(-5-methylpyrazine- -2-carboxylato)-(5-methylpyrazine-2-carboxylato)-μ3-nitrato-trilithium] [8] The asymmetric unit of the title compound contains three Li(I) ions, two 5-methylpyrazine-2-carboxylate anions, two water molecules and a nitrate anion (Fig.5). The coordination environment of the Li1 ion is composed of N11, O11(i), O1, O4 and O11 atoms. The latter three form a base of a distorted trigonal bipyramid, N11, O11(i) atoms are at its apices. Li1 ion is 0.0097(2) Å out of the basal plane. The Li2 ion is coordinated by water O4, O5, carboxylate O12(i) and nitrate O2(iii) atoms which form a distorted tetrahedral coordination environment. The same distorted tetrahedral coordination geometry shows the Li3 ion sorrouded by N31, O31, O1 and O5 atoms. Both methylpyrazine Fig.6. The alignment of the polyhedra columns in the unit rings are planar with r.m.s. of 0.0074(1) Å for ring cell. LABORATORY OF MATERIAL RESEARCH 75 catena Part 09. -Poly[[[aqualithium]-μ3-car- carboxylate groups C27/O21/O22 and C28/O23/O24 boxy-pyrazine-2-carboxylato-κ4O2,N1:O3,N4] with the pyrazine ring 2 amount to 15.4(2)o and monohydrate] [9] 4.3(1)o, respectively. Solvation and coordinated The asymmetric cell of the title compound con- water molecules participate in a network of hy- tains two symmetry independent Li(I) ions, two drogen bonds which bridges the ribbons. They act ligand molecules, two coordinated and two solva- as donors, the carboxylato O atoms as acceptors. catena tion water molecules (Fig.7). Li(I) ions and the Part 10. -Poly[[μ2-aqua-diaquabis(μ2- ligands form two parallel molecular chains propa- -pyradizine-3,6-dicarboxylato) tetralithium] gating in the crystal b direction (Fig.8). In each, monohydrate] [10] the Li ion shows a distorted trigonal bipyramidal The title compound is a polymeric complex with four symmetry independent Li ions in the asymmetric cell. Two of them show distorted trigonal bipyramidal geometry, the two other exhibit distorted tetrahedral coordination environment. The asymmetric cell contains also two symmetry independent pyridazine-3,6-dicarboxylate ligand molecules (PY1 and PY2), three coordinated water molecules and a solvation water molecule (Fig.9).

Fig.7. Two structural units of the title compound with atom labelling scheme and 50% probability displacement ellipsoids. Symmetry code: (iii) -x+1, y-1/2, -z; (iv) -x, y+1/2, -z+3/2. coordination mode. The Li1 ion is 0.017(1) Å out of the basal plane composed of carboxylato O11, O14(i) and aqua O15 atoms; hetero N11 and N12(i) atoms are at axial positions. The equatorial plane in the case of the Li2 ion consists of carboxylate O21, O24(ii) and water O25 atoms; hetero N21 and N22(ii) form the apices. The Li2 ion is 0.012(1) Å out of the basal plane. The observed Li-O and Li-N bond distances are characteristic of Li(I) complexes with diazine carboxylate ligands. Each ligand uses both its N,O chelating sites to bridge Li(I) ions. The second carboxylato O atoms do not participate in coordination but remain protonated to main- tain the charge balance. In both ligands these pro- Fig.9. The structural unit of the title compound with atom tons are active in short intra-molecular hydrogen labelling scheme and 50% probability displacement ellip- bonds of 2.393(3) Å and 2.416(3) Å. Bond lengths soids. Symmetry code: (i) -x+2, -y, -z+2; (ii) -x+2, -y+1, and bond angles within both pyrazine rings do not -z+2; (iii) -x+2, -y, -z+3; (iv) -x+2, -y+1, -z+1. differ from those reported in the structures of two modifications of the parent acid. Pyrazine rings are The equatorial plane of Li1 coordination poly- planar with r.m.s. of 0.0040(2) Å and 0.0094(2) Å, hedron is composed of O11, N21, O24(iii) atoms; for ligand 1 and 2, respectively. The carboxylate the Li1 ion is 0.0285(2) Å out of the plane, O21 groups C17/O11/O12 and C8/O13/O14 make with and N11 atoms are at axial positions. Li2 ion is the pyrazine ring 1 dihedral angles of 4.8(1)o and shifted by 0.0186(2) Å from the basal plane com- 3.8(1)o, respectively. Dihedral angles made by the posed of O12(i), O23, N12 atoms; O13 and N22 atoms make the apices. Li3 ion is coordinated by O21, O22(iv), O31, O42(i) atoms at the apices of a distorted tetrahedron while the coordination tetrahedron of the Li4 ion is composed of O13(ii), O14, O41, O42 atoms. Both pyridazine rings are planar with r.m.s. of 0.0154(2) Å and 0.0123(2) Å for the ring PY1 and PY2, respectively. Carboxy- late C17/O11/O12 and C18/O13/O14 groups make with the hetero-ring PY1 dihedral angles of 14.3(1)o and 22.2(2)o, respectively. Dihedral angles formed with the hetero-ring 2 by carboxylate groups C27/O21/O22 and C28/O23/O24 amount to 3.8(1)o Fig.8. Packing diagram of the structure viewed along the b and 17.2(2)o, respectively. The Li1 and Li2 ions axis. bridged by hetero-ring N atoms donated by both 76 LABORATORY OF MATERIAL RESEARCH ligands along the Li1-N11-N12-Li2-N22-N21-Li1 zine-2,6-dicarboxylate ligand molecule and a co- pathway form a dimeric moiety. The C27/O21/O22 ordinated water molecule (Fig.11). The coordina- and C27(iv)/O21(iv)/O22(iv) groups acting as biden- tion environment of the Li1 ion is composed of five atoms: ligand carboxylate O1, O1(i), hetero- ring N1, aqua O3 and O3(iii) atoms. Coplanar Li1, N1, O3 and O3(iii) form the base of a distorted trigonal bipyramid, with O1 and O1(i) atoms at its apices. The observed Li-O and Li-N bond distances are typical for Li(I) complexes with diazine carboxylate ligands. The aqua O3 atom bridges Li1 with Li1(ii) ion to form molecular ribbons which propagate in the crystal c direction (Fig.12). The

Fig.10. Packing diagram of the structure viewed along the b axis. tate bridge the Li3 and Li3(iv) ions to form a loop which joins a dimer with an adjacent from one side via O21 and O21(iv) atoms since the latter are also bonded to the Li1 and Li1(iv) ions, respectively. A similar loop bridges the dimers from the other side as the bidentate O13 atom links the Li2 and Li4(ii) ions. A molecular ribbon propagating along the crystal c direction can be visualized The ribbons bridged by carboxylate and coordinated water O atoms form molecular layers which are parallel to the crystal bc plane and stacked along the a direction (Fig.10). The bridging of ribbons proceeds via carboxylato O12 and O24 atoms: O12 atom is coordinated to the Li2(i) atom in an adjacent ribbon while the Li2 ion – by the O12(i) atom from the same ribbon. The O24 atom is chelated to the Li1(iii) ion in the other adjacent ribbon, while the O24(iii) atom is coordinated to the Li1 ion. In addition, pairs of ribbons are bridged by coordinated aqua O42 atoms via Li4-O42-Li3(i) and Li3-O42(i)-Li4(i) links. An extended system of hydrogen bonds in Fig.12. The alignment of the ribbons viewed along the a which coordinated water molecules are donors and axis. carboxylato O atoms in adjacent layers act as acceptors, maintains the stability of the structure. carboxylato O1 atom remains protonated and Two intra-molecular hydrogen bonds are also ob- mantains the charge balance. This proton, located served. at an inversion centre, forms a short centrosym- Part 11. catena-Poly[[(6-carboxypyrazine-2- metric O1-H1… O1(iv) hydrogen bond of 2.455(3) -carboxylato)lithium]-μ-aqua] [11] Å which links adjacent ribbons to form molecular The asymmetric unit of the title compound layers. The pyrazine ring is planar with r.m.s of consists of a Li(I) ion, a singly deprotonated pyra- 0.0024(1) Å. The C7/O1/O2 and C7(i)/O1(i)/O2(i) carboxylic groups make with it dihedral angles of 3.0(1)o. Bond distances and bond angles within the ligand molecule do not differ from those reported in the structure of pyrazine-2,6-dicarboxylic acid dihydrate. The layers are held together by weak hydrogen bonds in which the coordinated water molecules act as donors and carboxylate O atoms and hetero-ring N atoms from adjacent layers are as acceptors. References [1]. Starosta W., Leciejewicz J.: Acta Crystallogr., E66, m744-m745 (2010). [2]. Starosta W., Leciejewicz J.: Acta Crystallogr., E66, Fig.11. The asymmetric unit of the title compound with atom m1362-m1363 (2010). labelling scheme and 50% probability displacement ellip- [3]. Starosta W., Leciejewicz J.: Acta Crystallogr., E66, soids. Symmetry code: (i) x, -y+3/2, z; (ii) x+1, y, z; (iii) x-1, m1561-m1562 (2010). y, z; (iv) -x+1, -y+1, -z; (v) -x+1, y-1/2, -z; (vi) x, -y+1/2, z; [4]. Starosta W., Leciejewicz J.: Acta Crystallogr., E67, (vii) x-1, y+1/2, -z; (viii) -x+2, -y+1, -z. m50-m51 (2011). LABORATORY OF MATERIAL RESEARCH 77

[5]. Starosta W., Leciejewicz J.: Acta Crystallogr., E67, [9]. Starosta W., Leciejewicz J.: Acta Crystallogr., E67, m202 (2011). m1133 (2011). [6]. Starosta W., Leciejewicz J.: Acta Crystallogr., E67, [10]. Starosta W., Leciejewicz J.: Acta Crystallogr., E67, m425 (2011). m1455-m1456 (2011). [7]. Starosta W., Leciejewicz J.: Acta Crystallogr., E67, [11]. Starosta W., Leciejewicz J.: Acta Crystallogr., E67, m818 (2011). m1708-m1709 (2011). [8]. Starosta W., Leciejewicz J.: Acta Crystallogr., E67, m1000-m1001 (2011).

NANOPORES WITH CONTROLLED PROFILES IN TRACK-ETCHED MEMBRANES Bożena Sartowska, Oleg Orelovitch1/, Adam Presz2/, Irina Blonskaya1/, Pavel Apel1/ 1/ Flerov Laboratory of Nuclear Reactions, Joint Institute for Nuclear Research, Dubna, Russia 2/ Institute of High Pressure Physics, Polish Academy of Sciences, Warszawa, Poland

The production of track-etched membranes is 5 x 104 to 1 x 108 cm–2 from an IC-100 accelerator well-known in membrane science and described in at the Flerov Laboratory of Nuclear Reactions, the literature [1-4]. Latent ion tracks are the result Joint Institute for Nuclear Research (Dubna, of the passage of swift ions through solid matter Russia). In the next step of asymmetric membrane which can be etched selectively in many materials. As a result the conical, cylindrical or other shape channels can be obtained. The increasing interest of polymer track-etched membranes with nano- -channels is connected with the development and creation of nanoporous materials with unique properties. The main directions of the research work include: (i) development of membranes with diode-like pores, highly asymmetrical nanopores for molecular sensors; highly asymmetrical nanopores for atom beam optics, etc. [3, 5]; (ii) development of high-performance asymmetrical track membranes [3]; (iii) study of propagation of X-rays and acoustic waves through track-etched membranes as model porous medium [6]; (iv) development of nano-capillary bodies for modelling the transport of molecules and ions in constrained volumes [5]. Fig.1. Scheme of track etching in an ion-irradiated polymer It has been found that conical nanopores are film in the presence of nano-sized surfactant molecules. cation selective and possess diode-like voltage-current characteristics [1, 7]. It has been also shown production one surface of the irradiated foil was that the shape of the pore tip determines the exposed to UV radiation from a source. After UV transport properties of the asymmetric narrow exposure, the samples were etched during differ- channels [8, 9]. ent times with sodium hydroxide solutions to which Asymmetric pores have been produced by the 0.05% (w/w) Dowfax 2A1 (Dow Chemicals) was surfactant-controlled etching of heavy ion tracks added at a constant temperature of 60oC. Alkaline in a polymer foil. The formation of nanopores solutions with NaOH concentrations of 4 M, 5 M, with different tip shapes is based on the interplay 6 M were used to produce membranes with gradu- between the chemical attack by alkali ions and the ally increased tapering of the pore tips. The etched protection effect of the surfactant. These two samples were examined using an LEO 1530 (Zeiss, components of the etching solution diffuse into Germany) field-emission scanning electron micro- the pore at different rates, which results in the for- scope (FESEM). Small pore density and pore di- mation of a channel with a narrow neck at the sur- ameters (tip region) were estimated by observing face. Varying the etchant component concentra- the membrane surface. The pore profiles were de- tions makes it possible to control the degree of termined via imaging of fractures of the samples. tapering. The scheme of the etching process is pre- The FESEM images of pores with highly ta- sented in Fig.1. pered tips with the “bullet-like” shape produced Polyethylene terephthalate (PET) film 12-μm by etching at three different alkali concentrations thick (Hostaphan RNK, Mitsubishi Polyester Films) are shown in Fig.2. It can be clearly seen that use was irradiated with accelerated heavy ions: 170-MeV of the lower alkali concentrations provides a less Xe-ion beam with the ion fluence in the range of pronounced bullet-like tip. 78 LABORATORY OF MATERIAL RESEARCH

ABC

Fig.2. FESEM images of typical pore tip in membranes obtained by etching in surfactant-doped alkaline solutions: A – 4 M NaOH, 7 min; B – 5 M NaOH, 6.5 min; C – 6 M NaOH, 5 min. From the images of membrane fractures, one membrane and the use of the described controlled can extract quantitative information on the pore etching method can give pore channels unique profile. The data measured for several single properties with potential practical applications, channels were averaged to obtain a profile typical for example: ultrafiltration and microfiltration of used etching conditions. Experimentally ob- processes, cation selectivity, mimicking the prop- tained tip profiles of the observed membranes are erties of biological ion channels, nanocapillary 200 bodies for modelling molecule transport in constrained volumes. (c)

), nm 150 This work has been partially supported by the x (b) cooperation programme of the Polish scientific 100 institutes with the Joint Institute for Nuclear (a) Research in 2010 according the subject number 50 04-5-1076-2009/2011. This work has been partially supported by the 0 Polish Ministry of Science and Higher Education Pore radius a( 0 1000 2000 3000 under the project with a decision 766/W-ZIBJ Depth x, nm DUBNA/2010/0. Fig.3. Experimentally obtained tip profiles for pores obtained by etching in surfactant-doped alkaline solutions: References (a) 4 M NaOH, 7 min; (b) 5 M NaOH, 6.5 min; (c) 6 M [1]. Apel P.Yu., Korchev Yu.E., Siwy Z., Spohr R., Yoshida NaOH, 5 min. M.: Nucl. Instrum. Meth. Phys. Res. B, 184, 337-346 presented in Fig.3. The pore profile a(x) was fitted (2001). using an exponential function suggested by Rami- [2]. Apel P.Yu., Blonskaya I.V., Dmitriev S.N., Orelovitch rez [9]: O.L., Presz A., Sartowska B.A.: Nanotechnology, 18, n n 305302-305308 (2007). a(x) = aR – (aR – aL) exp [-(x/d) (d/h) ] [3]. Apel P.Yu. et al.: Radiat. Meas., 43 (1), 552-555 (2008). where: aR – pore diameter at the foil side exposed [4]. Apel P.Yu., Blonskaya I.V., Orelovitch O.L., Dmitriev to UV irradiation; aL – pore diameter at the foil S.N.: Nucl. Instrum. Meth. Phys. Res. B, 267, 1023-1027 side not exposed to UV irradiation; d – pore length (2009). (thickness of used polymer foil); n and h – para- [5]. Gillespie D., Boda D., He Y., Apel P., Siwy Z.S.: meters of the pore profile (here: n = 1). Profiles Biophys. J., 95, 609-619 (2008). shown in Fig.3 were calculated using this equa- [6]. Gomez Alvarez-Arenas T.E., Apel P.Yu., Orelovitch O.L., Munoz M.: Radiat. Meas., 44, 1114-1118 (2009). tion. The fitting curves (lines) and obtained ex- et al. perimental data (points) are presented in the dia- [7]. Siwy Z. : Surf. Sci., 532-535, 1061-1066 (2003). [8]. Cervera J., Schiedt B., Neumann R., Mafe S., Ramirez gram. P.: J. Chem. Phys., 124, 104706 (2006). In conclusion: Surfactant controlled etching [9]. Ramirez P., Apel P.Yu., Cervera J., Mafe S.: Nanotech- method presented in this work allows us to control nology, 19, 315707 (2008). the shape of track-etched pores in polymeric LABORATORY OF MATERIAL RESEARCH 79 IMPROVEMENT OF TRIBOLOGICAL PROPERTIES OF STAINLESS STEEL BY ALLOYING ITS SURFACE LAYER WITH RARE EARTH ELEMENTS USING HIGH INTENSITY PULSED PLASMA BEAMS Bożena Sartowska1/, Jerzy Piekoszewski1,2/, Lech Waliś1/, Jan Senatorski3/, Marek Barlak1,2/, Wojciech Starosta1/, Cezary Pochrybniak2/, Irena Pokorska3/ 1/ Institute of Nuclear Chemistry and Technology, Warszawa, Poland 2/ The Andrzej Sołtan Institute for Nuclear Studies, Otwock-Świerk, Poland 3/ Institute of Precision Mechanics, Warszawa, Poland

Austenitic stainless steels are used in numerous tanium rods coated with mischmetal tips as elec- industrial applications, due to their very good cor- trodes and nitrogen as the working gas. The samples rosion resistance in different environments. This were characterized by: scanning electron micro- is connected with an adherent and self-healing scopy (SEM) with DSM 942 (Zeiss, Germany) for passive film on the surface and thus received grow- initial and modified surface morphology obser- ing attention in nuclear and petrochemical indus- vations, grazing angle X-ray diffraction (GXRD, o tries, pulp and paper chemical, food and chemical ω = 5 ) with CuKα radiation with a diffractometer processing and biomedical industries. However, D8 Advanced (Bruker, Germany) for material poor tribological and mechanical properties of structure determination. Wear resistance measure- austenitic stainless steels in terms of abrasion re- ments were carried out using the Amsler method sistance limited their applications in engineering with an A135 Amsler machine with the parameters: fields. sliding friction distance – 3000 m, constant load – Improvement of the wear resistance of auste- 5 daN, 41Cr4 steel counter-sample and single im- nitic stainless steels without loss of corrosion re- merse lubrication. sistance can be achieved using different surface SEM micrographs of the surface of an untreat- treatment, for example: re-solidification techniques ed sample and a sample treated with HIPPB are or enrichment of the surface layer with reactive shown in Fig.1. Grain boundaries on the untreated elements. High oxygen affinity elements such as sample are clearly visible as a result of steel pro- Y, Ce, La, Er and other rare earth elements (REE) added to steels in small amounts can improve their resistance for electrochemical corrosion [1], high temperature oxidation [1, 2] and wear [3, 4]. REE can be alloyed during the steel making process or can be added to the surface region of materials using different surface modification techniques such as: ion implantation [1, 2, 4, 5], sol-gel coating [5], metal organic chemical vapour deposition [6]. Austenitic stainless steel AISI 316L was used as the substrate for investigations. As a REE source, the mischmetal with a composition: Ce – 65.3 wt% and La – 34.0 wt% was used. REE were incorpo- rated into one surface of steel samples using high 6 8 intensity pulsed plasma beams – HIPPB (10 -10 Fig.1. SEM surface morphology of AISI 316L samples. W/cm2). The plasma pulses were generated in a rod plasma injector (RPI) described in details duction process. After the modification process, elsewhere [7]. The plasma pulses are formed at a grain boundaries almost disappeared and features low pressure, high-current discharge between two of the mixed deposit-substrate material form can concentric sets of electrodes. Two modes of RPI be seen. Craters, cracks and other morphological operation are possible: (i) pulse implantation dop- features were observed by SEM on the modified ing (PID) – when plasma contains practically ex- surfaces. They are typical for melted and rapidly clusively ions of the working gas and (ii) deposi- solidified material known from previous investi- tion by pulsed erosion (DPE) – when the beam gations [8]. XRD spectra for initial and modified contains also ions/atoms eroded from ends of the material analysis show the FCC phase presence. electrodes. The pulse energy was high enough for This is clearly recognized in the initial material – melting the surface layer of material. The melt du- austenitic stainless steel. In the case of modified ration lasts in the μs range and the rapid solidifi- material peaks characteristic of FCC structure con- cation takes place. The cooling rate was estimated firm that after remelting and alloying with REE in the range of 107-108 Ks–1. Heating and cooling austenitic phases are still present in the surface processes were of non-equilibrium type. The thick- layer of steel. This result was observed in previous ness of melting layer is about 1.5 μm. investigations and explained by a very high cool- Samples were irradiated with 3 pulses with an ing rate [8]. Two first peaks – diffraction patterns energy of density 2.0 J/cm2, in DPE mode with ti- of initial and material modified up to 1.2 and 2.01 80 LABORATORY OF MATERIAL RESEARCH at% REE are shown in Fig.2. The (200) peaks shifting towards higher angles 2θ were observed, what corresponds to a smaller lattice parameter of identified austenitic phase. Lattice parameters de-

Fig.3. Changes in linear wear of AISI 316L samples. rate and (iii) nitrogen presence in the modified layer. In conclusion: (i) alloying of AISI 316L stainless steel with REE (Ce+La), using high intensity pulsed plasma beams (HIPPB) lead to formation of the remelted and enriched steel with active ele- Fig.2. First two peaks of GXRD spectra of AISI 316L ments near the surface layer and (ii) obtained samples. modified surface layers showed improvement of termined from these shifts were: a1 = 0.3575 nm the tribological properties as compared with the (AISI 316L initial material), a2 = 0.3537 nm (AISI initial material. 316L + 1.2 at% REE) and a3 = 0.3535 nm (AISI 316L + 2.01 at% REE). It should be taken into References consideration that theoretical austenite lattice pa- [1]. Abreu C.M., Cristobal M.J., Novoa X.R., Pena G., rameter equal to a0 = 0.3582 nm [9]. It was sug- Perez M.C., Rodriguez R.J.: Surf. Coat. Technol., gested that very high cooling rate and very high 158-159, 582-587 (2002). crystallization rate lead to obtain dispersed struc- [2]. Cleugh D., Blawert C., Steinbach J., Ferkel H., Mordike B.L., Bell T.: Surf. Coat. Technol., 142-144, 392-396 ture. (2001). Figure 3 shows the dependence of linear wear [3]. Cheng X.H., Xie C.Z.: Wear, 254, 415-420 (2003). for initial and alloyed with REE materials. HIPPB [4]. Jin F., Chu P.K., Xu Z., Zhao J., Zhu M., Fu R.K.Y., modified AISI 316L steel reveals a smaller value Tong H.: Surf. Coat. Technol., 201, 4357-4360 (2006). of linear wear after each one part of wear measure- [5]. Riffard F., Buscail H., Caudron E., Cueff R., Issartel ments as compared with the initial material. Ad- C., Perrir S.: Appl. Surf. Sci., 199, 107-122 (2002). ditionally: the presented results show a bigger im- [6]. Picardo P., Chevalier S., Molins R., Viviani M., Caboche provement of tribological properties for higher G., Barbucci A., Sennour M., Amendola R.: Surf. REE concentrations. Even small REE incorpora- Coat. Technol., 201, 4471-4475 (2006). tion (0.23 at% REE) improved the tribological [7]. Werner Z., Piekoszewski J., Szymczyk W.: Vacuum, 63, 701-708 (2001). properties of AISI 316L steel by about 25%. [8]. Sartowska B., Piekoszewski J., Waliś L., Senatorski J., The present authors supposed that the improve- Stanisławski J., Nowicki L., Ratajczak R., Kopcewicz ments of tribological properties are connected with M., Szymczyk W., Nowotnik A.: Plasma Process Polym., following findings: (i) enrichment of grain bound- 4, S314-S318 (2007). aries with REE, (ii) fine grains creation in the [9]. Saker A., Leroy Ch., Michel H., Frantz C.: Mater. Sci. modified material as a result of very high cooling Eng., A 140, 702-708 (1991).

INAA AS A SOURCE OF INFORMATION FOR THE PROVENANCE OF ALABASTER SCULPTURES Tomasz Śliwa1/, Ewa Pańczyk 1/ Faculty of Geology, Geophysics and Environmental Protection, AGH University of Sciences and Technology, Kraków, Poland

For the examination, characterization and analysis jects, nuclear techniques are crucial due to their of cultural heritage artefacts or art objects and high sensitivity and reproducibility. their component materials, a conservation spe- In this paper, the basic attributes and limitations of cialist needs a palette of non-destructive and non- INAA (instrumental neutron activation analysis) -invasive techniques, in order to improve our knowl- technique for analysis of alabaster sculptures are edge concerning their elaboration, their evolution described. and degradation during time, and to a give basis There are many works of art made of alabaster for their restoration and conservation. Among vari- the authors of which as well as the centres in which ous methods used for the examination of art ob- they were created are unknown. The only criterion LABORATORY OF MATERIAL RESEARCH 81 used for dating a sculpture is the style of the epoch in the last Paleozoic-Permian period and the first or the artist. Nuclear methods, in particular neu- period of Mesozoic-Triassic period. Alabaster is a tron activation analysis (NAA) can furnish data pure substance with a very low trace element con- for estimation of the sculpture origin. By compar- centration [1]. ing the content of trace elements in alabaster form Alabaster was used, particularly in the Middle deposits and in alabaster of the examined sculp- Ages as sculptor’s material mainly in Normandy, ture, it is possible to estimate where the sculpture Westfalen, North Netherlands and England. As comes from, because the content of trace elements sculptor’s material, alabaster has excellent prop- in alabaster from different sources significantly erties: it can be readily shaped, it permits to obtain differs. For this purpose, a catalogue containing fine details, it is semitransparent, can be readily data on the content of trace elements in alabaster gold-coated or polychromed [2]. Its disadvantages originating from various mines is necessary. are: brittleness and sensitivity to atmospheric agents. Alabaster is a massive crypto-crystalline form of The purpose of this research was to identify gypsum deposited by precipitation in inland seas historical Badenian alabaster deposits from the Table 1. Description of analysed alabaster sculptures.

Desciption No. Sculpture of sample 1 The Wawel Cathedral, Potocki’s Chapel, Bishop’s Padniewski figure a_1 2 The Wawel Cathedral, Waza’s Chapel, fragment of cartouche a_2 3 The Wawel Cathedral, Lipski’s Chapel, fragment of Andrzej Lipski tombstone (1) a_3 4 The Wawel Cathedral, Lipski’s Chapel, fragment of Andrzej Lipski tombstone (2) a_4 5 The Wawel Cathedral, Lipski’s Chapel, fragment of Cardinal Jan Aleksander Lipski a_5 tombstone 6 The Basilica of Corpus Christi (Kraków), St. Stanisław Kazimierczyk Mausoleum, a_6 Madonna with Child 7 The Cathedral Basilica (Tarnów) – Ostrogski’s tombstone a_7 8 Parish church dedicated St. Cross (Zbylutowska Góra), Zbylitowski Family tombstone a_8 9 Parish church (Dobromil), epitaph of child from Herbut Family a_9 10 Parish church (Dobromil), fragment of sacrarium a_10 11 Church of the Dominican Fathers (Lvov), tombstone monuments of Władysław Dzieduszycki, a_11 Jan Swoszowski, Stanisław Włodek – figure in vestibule (pillow) 12 Church of the Dominican Fathers (Lvov), tombstone monuments of Władysław Dzieduszycki, a_12 Jan Swoszowski, Stanisław Włodek – figure in vestibule (fragment of thigh) 13 Church of the Dominican Fathers (Lvov), tombstone monuments of Władysław Dzieduszycki, a_13 Jan Swoszowski, Stanisław Włodek – figure in vestibule on the right side (pillow) 14 Church of the Dominican Fathers (Lvov), tombstone monuments of Władysław Dzieduszycki, a_14 Jan Swoszowski, Stanisław Włodek – figure in vestibule on the left side (pillow) 15 Church of the Dominican Fathers (Lvov), tombstone monuments of Władysław Dzieduszycki, a_15 Jan Swoszowski, Stanisław Włodek – figure in vestibule on the left side (pedestal) 16 Church of the Dominican Fathers (Lvov), tombstone monuments of Władysław Dzieduszycki, a_16 Jan Swoszowski, Stanisław Włodek – figure in vestibule on the right side (pedestal) 17 St. Michael Archangel Ortodox Church (Lvov), St. Cross Altar, Jan Szolc-Wolfowicz a_17 foundation 18 Latin Archbishop’s See (Lvov), Kampians Chapel, table a_18 19 Latin Archbishop’s See (Lvov), Kampians Chapel, interior decoration (base of 1st pillar) a_19 20 Latin Archbishop’s See (Lvov), High Sacristy, Altar of Family Zapała foundation a_20 21 Latin Archbishop’s See (Lvov), High Sacristy, St. Joseph Chapel, St. Joseph Altar a_21 22 Parish church (Rymanów), Jan and Sophia Sieniński tombstone (1) a_22 23 Parish church (Rymanów), Jan and Sophia Sieniński tombstone (1) a_22a 24 Parish church (Rymanów), Jan and Sophia Sieniński tombstone (2) a_23 25 Parish church (Rymanów), Jan and Sophia Sieniński tombstone (2) a_23a 26 Castle Chapel (Brzeżany), west crypt a_24 27 Castle Chapel (Brzeżany), fragment of architectural framework a_25 82 LABORATORY OF MATERIAL RESEARCH Ukrainian part of the Carpathian foredeep, which Table 2. Description of studied alabaster deposits. served as a raw material for historical sepulchral Sample and figural statues from the Renaissance era to No. Localization of alabaster deposit description the interwar period. Using the method of INAA, 24 samples of alabaster gypsum were examined 1 Kostriżiwka (1) z_1 from, among others, the chapels of the Wawel 2 Kostriżiwka (2) z_2 Cathedral, Lvov and Tarnów, as well as from the 3 Dubowce (1) z_3 parish churches of the Tarnów and Przemyśl dio- ceses. Small amounts of alabaster were collected 4 Dubowce (2) z_4 along with antique furnishings from the Roman 5 Werenczanka (1) z_5 Catholic parishes around Lvov and the Orthodox 6 Werenczanka (2) z_6 Church of St. Michael the Archangel in Lvov. Forty five alabaster samples collected from natural out- 7 Łokutki (1) z_7 crops and quarries that appear along the Dniester 8 Łokutki (2) z_8 Valley in the historic regions of Eastern Galicia, 9 Szczerzec (1) z-9 Podolia and Bukovina served as reference material. The samples are described in Tables 1 and 2. 10 Szczerzec (2) z_10 Analysis of the samples was carried out by INAA 11 Szczerzec (3) z_11 using standards of the elements to be determined. 12 Czynków z_12 Major components of alabaster (CaSO4*2H2O) have low (n,γ) reaction cross-sections which is of 13 Kriwa z_13 advantage for carrying out the analysis. By irradiat- 14 Słoboda z_14 ing alabaster with thermal neutrons, its main com- 15 Zagóreczko z_15 ponent undergoes the nuclear reaction 46Ca (n,γ) 47Ca → 47Sc 16 Mamałyga z_16 The radioisotope 47Ca has a half-life of 4.53 days 17 Podłuże z_17 and emits gamma rays of energies 1290 and 800 18 Głuszków z_18 keV. On the other hand, 47Sc with a half-life of 3.4 days emits gamma rays of an energy of 160 keV. 19 Skowiatyn z_19 The reaction cross-section is 0.250 barn and the 20 Wojniłów z_20 46 natural abundance of Ca is 0.0033% [3]. 21 Borszczów z_21 The samples were sealed in quartz ampoules and then packed together with standards of 48 22 Podkamień z_22 elements. Each packet contained also Sc and Au 23 Anadoły (1) z_23 used as monitors of the thermal neutron flux. 24 Anadoły (2) z_24 The irradiation was carried out in the MARIA reactor at Świerk (Poland), at a neutron flux of 25 Pałahicze (1) z_25 8 x 1013 ncm–2s–1. The samples were irradiated for 26 Pałahicze (2) z_26 24 h and cooled for 12 h. The radioactivity of the 27 Kudryńce (1) z_27 samples was measured by means of an HP-Ge detector (ORTEC) coupled to a CANBERRA-Sys- 28 Kudryńce (2) z_28 tem spectrometer, controlled by an IBM computer. 29 Żurawno z_29 The analysis of gamma-ray spectra of the samples 30 Bochnia z_30 was performed with the aid of the GENIE 2000 program. 31 Mielnica Podolska z_31 A multi-parameter statistical analysis was per- 32 Podillia z_32 formed to determine the degree of similarity be- 33 Oleszyw (1) z_33 tween the studied objects (analysis of principal components and cluster analysis) using the STA- 34 Oleszyw (2) z_34 TISTICA-8 program [3]. 35 Krzywcze z_35 Forty eight elements were identified and de- 36 Wasiuczyn z_36 termined in the samples examined. Out of 48 determined elements, only the elements identified 37 Łopuszka Wielka z_37 in all tested samples were selected for further 38 Pohoryłówka z_38 analysis. Elements such as Cd, Ga, Ho, Lu, Mo, 39 Kudryńce (Zamek) z_39 Ni, Rb, Se, Tb, Ta and Zr, the content of which in the majority of analysed samples, was below the 40 Jezierzany z_40 method detection threshold, were disregarded. 41 Pawlikówka z_41 The clustering analysis using STATISTICA (Stat- 42 Czerwonogród z_42 Soft) program was carried out to identify the similarity degree of analysed objects. The cluster- 43 Kreszczatyk z_43 ing analysis was carried out for standardized vari- 44 Hołowczyńce z_44 ables. 45 Kołokolin z_45 Results of this analysis are presented in Fig., which clearly shows the division into two groups in which 46 Toutry z_46 LABORATORY OF MATERIAL RESEARCH 83

Fig. Cluster analysis for 73 objects (sculptures and deposits); describes 36 features equal number analysed elements, standardized variables. the objects are very similar. Probably, the applied References alabaster was obtained from the same source. [1]. Beasley S.M.: The attribution of alabaster tomb carv- Several limitations and assumptions for the prov- ings to Medieval schools. Analytical and typographical enance studies of sculptures on the basis of ele- problems. A further study. Post-graduate thesis. Uni- mental composition have to be kept in mind: versity of Bradford, 1978, unpublished. • We assume that alabaster used for sculpture is [2]. Cheetman M.: English Medieval alabasters catalogue. homogeneous. Victoria and Albert Museum, Oxford 1984. • The samples removed from sculpture are repre- [3]. Ligęza M., Pańczyk E., Rowińska L., Waliś L., Nalepa B.: Nukleonika, 46, 2, 71-74 (2001). sentative of its stone. • Statistically a significant number of samples from deposits is taken to the elemental analysis. POLLUTION CONTROL TECHNOLOGIES LABORATORY

Research activities of the Pollution Control Technologies Laboratory concern the concepts and methods of process engineering application to the environmental area. In particular, we participate in research on the application of an electron accelerator in such environmental technologies as flue gas and water treatment, wastewater purification, processing of different industrial waste, etc. The main aims of activity of the Laboratory are: • development of new processes and technologies of environmental engineering, • development of environmental applications of radiation technologies, • promotion of nuclear methods in the field of environmental applications. The activities of our group are both basic and applicable research. Among others, the most important research fields are: • development of electron beam flue gas treatment (EBFGT) technology, • investigation of chemical reaction mechanisms and kinetics in gas phase irradiated by electron beam, • study on the mechanism of removal of volatile organic compounds (VOCs) from flue gas by electron beam excitation, • process modelling. The Laboratory is equipped with such research tools as: • laboratory installation for electron beam flue gas treatment (flow rate up to 400 m3/h), • gas chromatograph with a mass spectrometer, etc • portable gas analyser (NOX, SO2, CO, O2, .). In 2011, the research staff is involved in the following projects: • “Dissemination and fostering of plasma-based technological innovation for environment protection in Baltic Sea Region – PlasTEP” (project co-financed by ERDF).

• “Laboratory study on SO2 and NOx removal from marine diesel engines exhaust gases with use of electron beam technology”. • “Electron beam flue gas treatment pilot tests”. The Laboratory is open to any form of cooperation. The most important partners of the Laboratory are: • Faculty of Chemical and Process Engineering, Warsaw University of Technology (Poland); • International Atomic Energy Agency; • Saudi ARAMCO (Saudi Arabia); • A.P. Moeller and Maersk A/P (Denmark); • EB Tech Co., Ltd. (South Korea); • Technology Centre of Western Pomerania (Germany); • Leibniz Institute for Plasma Science and Technology (Germany); • Risø National Laboratory for Sustainble Energy, Technical University of Denmark (Den- mark); • Uppsala University, The Ångström Laboratory (Sweden); • Kaunas University of Technology (Lithuania); • Vilnius Gediminas Technical University (Lithuania); • Robert Szewalski Institute of Fluid-Flow Machinery, Polish Academy of Sciences (Poland); • West Pomeranian University of Technology (Poland); • Ukrainian Engineering Pedagogic Academy (Ukraine). 86 POLLUTION CONTROL TECHNOLOGIES LABORATORY

MODELLING STUDY OF NOx REMOVAL IN FLUE GAS IN THE PRESENCE OF C2H6 UNDER ELECTRON BEAM IRRADIATION Yongxia Sun, Volodymyr Morgunov1/, Andrzej G. Chmielewski

1/ General and Experimental Physics Department, Ukrainian Engineering Pedagogic Academy, Kharkiv, Ukraine

Electron beam flue gas treatment (EBFGT) technology has demonstrated its efficiency in purification flue gases from SOx and NOx from coal and oil fired boilers [1]. High removal efficiency of SO2 (> 95%) and NOx (> 70%) has been demonstrated and an industrial plant applying this process has been built in Poland [2]. However, SO2 removal from off-gases by using electron beam (EB) is relatively easy, but NOx removal needs higher energy consumption. It demands a new method to Concentration [ppm] remove NOx with lower energy consumption. Our previous work showed that NOx removal efficiency was improved in the presence of alcohol [3]. In Dose [kGy] this work we theoretically studied NO removal in x Fig.1. Experimental and calculation results of NO removal the presence of C H with the aid of computer x 2 6 from flue gas vs. dose under EB-irradiation. simulation. The computer simulation of NOx removal in nents of gas, nk – concentration of the k-th compo- flue gas under EB-irradiation was carried out by nent, ni0 – the initial concentration of the i-th using a self-developed computer code “ELO”, a component. Calculations were made in the follow- GEAR method was used. 883 reactions involving ing conditions: 94 species were considered for NOx + (air + CO2 • NO = 494 ppm, NO2 = 38 ppm, CO2 = 7%, + H2O) + C2H6 (0-400 ppm) system, and 998 re- H2O = 10-11% (v/v), O2 = 10%, N2 as balance, actions involving 137 species were considered for T = 70oC (no any additives); NOx + (air + CO2 + H2O) + 400 ppm C2H6 + 700 • NO = 494 ppm, NO2 = 38 ppm, CO2 = 7%, ppm SO2. Five main groups of reactions were in- H2O = 10-11% (v/v), O2 = 10%, N2 as balance, cluded, the rate constants of reactions were mostly T = 70oC (with presence of 100 and 400 ppm taken from the literatures [4-6]. The units of rate C2H6, respectively); 3 6 2 constant are 1/s, m /mole·s and m /mole ·s for the • NO = 494 ppm, NO2 = 38 ppm, CO2 = 7%, first-, second- and third-order reactions, respec- H2O = 10-11% (v/v), O2 = 10%, N2 as balance, o tively. T = 70 C (with presence of 700 ppm SO2 and When fast electrons from electron beams are ab- 400 ppm C2H6). sorbed in the carrier gas, they cause ionization Figure 1 presents the calculation and experi- vs. and excitation process of the nitrogen, oxygen, mental results of NOx removal in flue gas dose CO2 and H2O molecules in the carrier gas. Primary under EB-irradiation. Calculation results agree, species and secondary electrons are formed. to some extent, with the experimental results [3]. The generation of active species under the elec- NOx removal under the influence of additives is tron beam is described by [6]: presented in Fig.2. It is seen that NOx removal efficiency is slightly improved in the presence of dni =ρGDxni (1) C H . The key reactions are listed below: dt i 2 6 where: ni – concentration of the i-th component [mole/m3], G – radiation yield of the i-th compo- ni nent of the gas [mole/J],. xi – mole fraction of the i-th component, D – dose rate [J/(kg·s)], ρ – gas density [kg/m3]. Kinetics of chemical reactions of species formed during the gas irradiation with molecules of the gas medium and with one another is described by differential equations: n dn efficiency [%] Removal i (n) (2) = nkii∑∏ n k dt nk1= For given initial concentrations: Dose [kGy] ni(0) = ni0 (3) where: ni – concentration of the i-th component Fig.2. Experimental and calculation results of NOx removal 3 (n) vs. [mole/m ], ki – the rate constant for n-order chem- from flue gas dose under EB-irradiation in the presence ical reaction between the i-th and the k-compo- or absence of additives. POLLUTION CONTROL TECHNOLOGIES LABORATORY 87

OH + C2H6 = C2H5• + H2O (R1) • Removal efficiency of NOx is decreased by O2 + C2H5• = C2H5O2• (R2) 23.84% at a dose of 10.9 kGy in the presence of 2C2H5O2• = 2C2H5O• + O2 (R3) 400 ppm C2H6 and 700 ppm SO2. The SO2 pres- C2H5O2• + NO = C2H5O• + NO2 (R4) ence decreases the removal efficiency of NOx C2H5O2• + NO + M = C2H5ONO2 + M (R5) when ammonia is not added. C H O • + NO + M = C H O NO + M (R6) 2 5 2 2 2 5 2 2 References NO2 + OH + M = HNO3 + M (R7) et al. The oxidation-reduction cycle between NO2 and [1]. Basfar A.A. : Fuel, 87, 8-9, 1446-1452 (2008). NO is toward the oxidation path and an increase [2]. Chmielewski A.G. et al.: Radiat. Phys. Chem., 71, 1-2, in NO removal efficiency is favoured. 439-442 (2004). x et al. From calculation results, the following conclu- [3]. Chmielewski A.G. : Radiat. Phys. Chem., 65, 4-5, sions are drawn: 397-403 (2002). [4]. Albritton, D.L.: At. Data Nucl. Data, 22, 1-101 (1978). • Removal efficiency of NOx is increased by 3% [5]. http://kinetics.nist.gov/kinetics/index.jsp. at a dose of 10.9 kGy in the presence of C2H6 [6]. Mätzing H.: Advances in chemical physics. Vol. LXXX. when the concentration of C2H6 is in the range John Wiley & Sons, Inc., New Jersey 1991, pp. 315-402. of 100 to 400 ppm.

EMISSION PROCESSES IN THE BALTIC SEA REGION – PLASMA TECHNOLOGIES IN ENVIRONMENTAL PROTECTION (PlasTEP) Sylwia Witman, Andrzej Pawelec, Andrzej G. Chmielewski

Air pollution is one of the biggest environmental cesses suitable for plasma technologies application problems, because the combustion products in the is foreseen. form of volatile compounds of sulphur, nitrogen According to PlasTEP project assumptions, are often transported along with the wind towards emission in the following countries was concerned: regions distant from the place of generation. There, Finland, Estonia, Latvia, Lithuania, Poland, North reacting with the moisture contained in the atmos- Germany, Denmark and Sweden. The national phere, these compounds form acids, causing acidi- emissions of NOx and SO2 are presented in Table 1. fication of the environment affecting the resources The highest emission were reported in Poland. of water and soil. It is the biggest of all concerned countries (38.1 Transport, industry (metallurgy, cement and mln citizens). The lowest emissions were reported chemicals), energy generation, heating and waste in North Germany with 1.7 mln citizens. Therefore, incineration have the largest share in the produc- the total emission per capita will be a better indi- tion of gaseous air pollutants. Analysis of the main cator in order to compare emission in the Baltic sources of air pollution in the Baltic Sea Region Sea Region countries. The emission of main inor- was conducted within the international project – ganic pollutants per capita is presented in Table 2. PlasTEP. Table 2. Annual SO2 and NOx emissions per capita in the Mapping the specificity of NOx and SO2 emis- Baltic Sea Region countries. sion in the Baltic Sea Region is the basis for further discussions on possible implementation of plasma Emission [kg/year] Country pollution control technologies. Therefore the docu- SO NO ment presenting main sources of emission in cer- 2 x tain countries has been elaborated. As a next step Finland 13 31 of this work, an elaboration list of potential pro- Estonia 52 26

Table 1. Annual SO2 and NOx emissions in the Baltic Sea Latvia 1 17 Region countries. Lithuania 9 20 Emission [t/year] Country Poland 26 22 SO NO 2 x North Germany 0.5 3.6 Finland 70 119 165 877 Denmark 4 28 Estonia 69 333 34 393 Sweden 3 16 Latvia 2 831 38 122 Average 15.4 22.8 Lithuania 31 531 67 739 Poland 998 561 831 225 Many problems associated with environmental pollution may be solved by properly using electro- North Germany 842 6 190 magnetic phenomena. Technologies based on elec- Denmark 19 605 151 686 tricity are environmentally „clean” and therefore wasteless, in contrast to most of the chemical tech- Sweden 30 521 154 403 nologies. Many of the newly created electromag- 88 POLLUTION CONTROL TECHNOLOGIES LABORATORY netic technologies of air purification from gaseous ducted by many scientific and research centres in pollutants (processes in non-thermal plasma, laser the world. The use of non-thermal plasma in the technologies, technologies using electron beam) agricultural and food industry for disinfection, have already been applied on an industrial scale. storage products, plant growth stimulation, seems A progressive increase in demand for electricity to be a competitive solution against conventional also brings challenges for the electricity industry chemical methods and fully justified to continue to develop more efficient technologies being in the research in this area. comply with the requirements of environment. Research of plasma technologies for reducing The presented structure of emission opens new emissions in transport is also conducted in the possibilities for plasma technology for exhaust gas country and abroad. Mobile sources that use diesel purification. engines (very large emission of NOx) can use non- Nowadays the improvement of efficiency of -thermal plasma generated by electric discharges electricity generation systems are realized through which significantly reduces the negative impact on the use of combined heat and electricity genera- the environment. tion. With the proper use of various technologies, Thus, plasma technology can be used in: the emissions of harmful compounds was partially • exhaust gases purification processes on a large- decreased, but still many problems are unsolved -scale production (EB) and small boilers (plasma and application plasma technologies for environ- created in discharges), ment protection may improve this situation. • removing harmful pollutants from exhaust gases Non-thermal plasma, generated in barrier dis- from industry, charges, is used in the processes of sterilization • purification of exhausts from mobile sources. and disinfection of solid, liquid and gas media due The results of the PlasTEP project, in which the to its numerous advantages – the most important Institute of Nuclear Chemistry and Technology being the lack of side effects as harmful to the en- (INCT) is involved, are the confirmation of the vironment waste products, the ability of plasma- importance of the research in the development of -chemical treatment at atmospheric pressure and plasma technologies for the environment. ambient temperatures. Survey in this field are con- STABLE ISOTOPE LABORATORY

Basic activity of the Stable Isotope Laboratory concern the techniques and methods of stable isotope measurements by the use of an isotope ratio mass spectrometer – IRMS. Our activity area concerns also the application to the environmental area: stable isotope composition of hydrogeological, environmental, medical and food samples. The main aims of activity of the Laboratory are: • preparation and measurement of stable isotope composition of food and environmental samples; • new area of application of stable isotope composition for food authenticity control, environmental protection and origin identification. The Laboratory is equipped with the following instruments: • mass spectrometer – DELTAplus (FinniganMAT, Germany); • elemental analyser Flash 1112NCS (Thermo Finnigan, Italy); • GasBenchII (ThermoQuest, Germany); • H/Device (ThermoQuest, Germany); • gas chromatograph (Shimadzu, Japan); • gas chromatograph with a mass spectrometer (Shimadzu, Japan); • liquid scintillation counter (for 14C and tritium environmental samples) 1414-003 Guardian (Wallac-Oy, Finland);

• portable gas analyser (N2O, CO2, CH4, H2S), (Nanosens, Poland). Research staff of the Laboratory is involved in the following projects: • “Formation of the data bank on original products for the juice sector, to supply requirements of the Polish market and producers, basing on the method of stable isotopes” (Ministry of Science and High Education grant PBZ-MEiN NR12-0043-10/2010); • “Differentiation of organically and conventionally produced foodstuff by the stable isotope method”; • accreditation process (isotopic method for food authenticity control); • interlaboratory proficiency test FIT-PTS (food analysis using isotopic techniques – proficiency testing scheme). Specific activity: industrial emission control of greenhouse gases by the use of isotopic composition and food authenticity control and origin identification. The Stable Isotope Laboratory is open for any form of cooperation. We are ready to under- take any research and development task within the scope of our activity. Especially, we offer our measurement experience, precision and proficiency in the field of stable isotope composition. Besides, we are open for any service in the area of food authenticity control by stable isotope methods supported by gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS) methods. Our Laboratory cooperates with the following national partners: • Inspekcja Jakości Handlowej Artykułów Rol- no-Spożywczych, • Urząd Ochrony Konsumenta, • Krajowa Unia Producentów Soków, • customs inspections, • food export-import company, • food control laboratories, • private people – customers and foreign partners: • Eurofins Scientific Analytics (France), • International Atomic Energy Agency (IAEA), • Join Research Centre (Ispra, Italy), • AgroIsoLab (Juelich, Germany), • others isotopic laboratories. STABLE ISOTOPE LABORATORY 91 STABLE ISOTOPES METHODS FOR JUICE AUTHENTICITY CONTROL Ryszard Wierzchnicki

With the globalization of trade, quality control of ticity control. Important limitation of the applica- food products is gaining increasing importance tion of isotopic method for juice authenticity for ensuring consumer and producer protection. control is the lack of database of stable isotope Adulteration as an addition of the artificial (pro- composition in fruits and vegetables of different hibited) components to natural products, a cheaper origin. product put into a place expensive one and misla- This Laboratory since many years is carrying belling is still frequently meet fraud. The addition out a study of isotopic composition of food for the of cheaper fruits, glucose syrup, acids, aromas and elaboration and implementation of new IRMS water are typical examples of adulteration which methods and database for some food products may occur in the juice production. The Polish mar- from the Polish market. For testing of food prod- ket has started to speed with the latest challenges ucts, we need extensive knowledge of the original facing the food industry with regard to food fraud. material. Our recent studies concern the intramol- This is connected with the economic politics of ecular isotopic distribution pattern between the EC in the agriculture sector of all EU countries. juice components. The aim of the studies is the Nowadays in Europe, stable isotope composi- extraction of chemical components and investigat- tion is probably one of the most important charac- ing their intermolecular relation with δ13C compo- teristic of juice for its authenticity control. The sition. The specific natural isotopic profile method standard method applied to determine the au- (SNIP-IRMS) [5] is based on multi-isotopic finger- thenticity of juice is the measurement of δ13C of printing in which isotopic ratios are measured on sugar and pulp and δ18O of water (Table 1). The several components of the same product and their Table 1. The isotopic methods accepted as international standards for juice authenticity control.

Product Isotopic parameter Method Document Fruit juice sugar, 13C IRMS* ENV 12140 (CEN/TC174N108) [1] Fruit juice pulp, 13C IRMS ENV 12140 (CEN/TC174N108) [2] Fruit juice water, 2H IRMS ENV 12141 (CEN/TC174N109) [3] Fruit juice water, 18O IRMS ENV 12141 (CEN/TC174N109) [4] Fruit juice ethanol, (D/H)I, (D/H)II, R SNIF-NMR** AOAC method 995.17 Fruit juice ethanol, 13C IRMS AOAC method 2004.01 * IRMS – isotope ratio mass spectrometry. ** SNIF-NMR – site-specific natural isotope fractionation determined by nuclear magnetic resonance. difference between sugar and pulp isotopic com- intermolecular isotopic correlation is investigated. position is the reason to ascertain the addition of The main components of juice are presented in sugar to tested juice. The oxygen isotopic ratio in Table 2. juice is directly related to the oxygen ratio of re- Nowadays, the role of the Stable Isotope Lab- gional precipitation and groundwater which, in oratory is the implementation of the SNIP-IRMS turn, is linked to geographical origin of fruits. It is method on the basis of original Polish fruits origi- possible to discriminate between natural and syn- nated from important regions of fruit production. thetic components (aromas, pigments, etc.) using In the future our Laboratory will check the com- nitrogen and carbon isotopic composition. The use pliance of both content and labelling of fruit juice of multicomponent and multielement approach is sold in the Polish marketplace. In the last year the studied, in which isotopic profile is built up for dif- laboratory has taken part in Food Isotopic Tech- ferent food products in order to address authen- niques – Proficiency Testing Scheme organized by Table 2. Basic chemical components of fruits and vegetables.

Content Content Basic components of fruits and vegetables Minor components of fruits and vegetables [%] [mg] Water 78-95 organic acids (citric, malic, tartaric) < 100 Sugars (glucose, fructose, sucrose) 5-15 vitamins < 80 Cellulose (texture) 0.4-5 enzymes < 0.1 Starch 0.3-1 aromas < 0.001 Fats 0.1-0.6 pigments < 0.001 Proteins 0.3-1.8 Asch 0.3-1.0 92 STABLE ISOTOPE LABORATORY the Eurofins Scientific Analytics, Nantes, France of sugars from fruit juices – Method using isotope ratio and Bevabs office, JRC, Ispra, Italy. Isotopic com- mass spectrometry. [2]. PN-ENV 12141:2004 Fruit and vegetable juices – De- position of samples of wine, juice, honey and casein 18 16 were tested. Studies of this kind, using a multicom- termination of the stable oxygen isotope ratio ( O/ O) of water from fruit juices – Method using isotope ratio ponent and multielement approach, concerning iso- mass spectrometry. tope profiles for different products, are prospected [3]. PN-ENV 12142:2004 Fruit and vegetable juices – De- for future needs of authenticity control of food. termination of the stable hydrogen isotope ratio (2H/1H) This work is supported by the Polish Ministry of water from fruit juices – Method using isotope ratio of Science and Higher Education under grant No. mass spectrometry. NR12-0043-10/2010. [4]. PN-ENV 113070:2004 Fruit and vegetable juices – De- termination of the stable carbon isotope ratio (13C/12C) References in the pulp of fruit juices – Method using isotope ratio mass spectrometry. [1]. PN-ENV 12140 : 2004 Fruit and vegetable juices – De- [5]. González J., Remaud G., Jamin E., Naulet N., Martin termination of the stable carbon isotope ratio (13C/12C) G.G.: J. Agric. Food Chem., 47(6), 2316-2321 (1999).

STABLE ISOTOPE RATIO ANALYSIS TO CHARACTERIZE CHOSEN SAMPLES OF POLISH HONEY Kazimiera Malec-Czechowska, Ryszard Wierzchnicki

Since many years the activity of the Stable Isotope pernatant was clear. The precipitated protein was Laboratory has been concentrated on the applica- dried in an oven at 60oC during at least 5 h and tion of stable isotope mass spectrometry for envi- transferred to a small tube before analysis. ronmental investigation and food authenticity con- Six parallel samples between 1.0 and 2.0 mg trol. In 2011, samples of Polish honey with a dif- each of the tested materials and each of two refer- ferent floral type such as rape, linden, buckwheat, ence standards for δ15N and δ13C (B 2155 and honeydew and mixed floral (multiflorous) were USGS-40) were transferred into tin capsules us- tested. The products were purchased in a local ing our elemental analyser. Carbon and nitrogen shop in Warsaw. The investigated honeys were pro- isotope analysis (δ13C and δ15N) were performed duced in apiarian farms situated in the Masuria on a DELTAplus mass spectrometer (Finnigan geographical region of Poland. MAT, Bremen, Germany), interfaced to elemental Honey is a sweet natural product, produced by analyser (elemental analyser Flash 1112 NCS – bees from flower nectar or from honeydew. Floral Thermo Finnigan, Italy). In one measurement the honey is composed mainly of carbohydrates, fruc- value for two isotopes were simultaneously ob- tose and glucose; but these sugars can be artifi- tained. The standard deviations of the values ob- cially added to falsify honey. Stable carbon isotope tained from measurements were: 0.3‰ for δ15N ratio analysis (SCIRA) is used to demonstrate C4 and 0.2‰ for δ13C. The values of the isotopic (corn or cane) sugars in honey at a concentration ratios are expressed as δ and correspond to an > 7%. The apparent C4 sugar content of the honey international standard (V-PDB for δ13C, and Air is calculated using the following formula: for δ15N) respectively for carbon: 13 13 13 C4 sugars [%] = 100 x [δ Cp – δ Ch]/[δ Cp – (-9.7)] where: δ13C and δ13C – the δ13C values [‰] for ⎡⎤13CC ⎡⎤ 13 p h − protein and honey, respectively; -9.7‰ – the av- ⎢⎥12 ⎢⎥ 12 13 ⎣⎦CC ⎣⎦ 13 δ=CSAMPLE STANDARD ∗ 1000 0 erage δ C value for a corn syrup. vsPDB 13 00 Proteins from honey were isolated according to ⎡⎤C ⎢⎥ the AOAC Official Method 998.12 and own pro- 12 C ⎣⎦STANDARD cedure [2]. Briefly, 10-12 g of a honey sample was placed in a 50 ml centrifuge tube and 4 ml of dis- and for nitrogen: tilled water was added and mixed. In another tube about 2 ml of 10% sodium tungstate solution was ⎡⎤15NN ⎡⎤ 15 − mixed thoroughly with 2 ml of 0.7 N sulphuric ⎢⎥14 ⎢⎥ 14 15 ⎣⎦NN ⎣⎦ acid. The solution was added to the centrifuge δ=NSAMPLE STANDARD ∗ 1000 0 vsAIR 15 00 tube and mixed with the solution containing the ⎡⎤N ⎢⎥ sample of honey. The tube was heated in a water 14 N ⎣⎦STANDARD bath at 80oC until visible flocks were formed (3-4 min). If no visible flocks were formed, or if the The carbon and nitrogen stable isotopes ratios in supernatant remained cloudy 0.7 N acid in 2 ml honey and honey proteins with different floral increments was added and repeated heating be- types such as lime tree, rape, buckwheat, multi- tween additions. The sample was then centrifuged florous and honeydew are presented in Table and at 1500 x g per 5 min and the supernatant removed. in Fig. The precipitate was washed with 50 ml of distilled Multielement stable isotope ratios (H, C, N, S) water, mixed and centrifuged. The washing proce- of honey from different European regions were re- dure was repeated at least five times, until the su- ported by A. Schellenberg [3]. In the frame of this STABLE ISOTOPE LABORATORY 93

Table. The carbon and nitrogen stable isotopes ratios in honey and honey proteins for chosen Polish honey.

13 13 15 Code sample/honey type Choney Cprotein Nprotein MP1/Multiflorous -23.66 -25.14 4.26 MP2/Rape -27.16 -27.55 1.09 MP3/Linden -26.04 -26.45 4.08 MP4/Multiflorous -26.91 -26.95 3.25 MP5/Linden -23.72 -26.15 3.62 MP6/Buckwheat -27.93 -27.27 3.85 MP7/Honeydew -25.55 -26.13 3.03 MP8/Multiflorous -26.39 -26.29 2.65 study it was to test if honeys produced in regions and δ15N of the honey proteins beyond the definite with different climatic and geological character- area. These divergences resulted probably from istics could be discriminated on the basis of the the fact that the examined honeys originated only isotopic data. Honey samples from twenty Euro- from one region of Poland, while the honeys exam- pean regions including thirty samples from Poland ined by A. Schellenberg originated from different were collected. The δ13C and δ15N mean values of regions of Poland and different type of floral. the honey proteins for Poland honey were -26.2 ± Until now, not much is known as to the investiga- 0.4 and 3.9 ± 0.9, respectively. The results ob- tion of geographical origin of honey from one tained in our Laboratory show that the samples whole country. To our knowledge, there is only one coded as MP3/Linden, MP5/Linden, MP7/Honey- study where the determination of geographical dew and MP8/Multiflorous have δ13C and δ15N origin of Slovenian black locus, linden and chest- nut honey was investigated by the analysis of some 5 -15 N

15 physicochemical parameters and the stable car- δ

2.5 -17.5 bon and nitrogen isotope ratios using isotope ratio mass spectrometry [4]. On the other hand, the dif- 13 0 -20 ference in the value δ C for protein and honey for δδ13C13C honey honey δδ13C13C protein protein the samples MP1/Multiflorous and MP5/Linden is δ15N protein -2.5 δ15N protein -22.5 greater than 1‰ what is evident indication of honey manipulation with C4 plant sugars such as

-5 -25 C

13 high fructose corn syrup (HFCS). The addition of δ C4 plant sugars calculated on the basis of the for- -7.5 -27.5 mula is about 9.3% for MP1/Multiflorous honey, and about 14.7% for MP5/Linden honey. -10 -30 MP8 MP7 MP6 MP5 MP4 MP3 MP2 MP1 References Fig. The carbon and nitrogen stable isotope ratios in honey and honey proteins for chosen Polish honey. [1]. Padovan G.J., De Jong D., Rodrigues L.P., Marchini J.S.: Food Chem., 82, 633-636 (2003). values of the honey proteins within the range cal- [2]. White J.W.: J. AOAC Int., 75 (3), 543-548 (1992). et al. culated by A. Schellenberg. The samples coded as [3]. Schellenberg A. : Food Chem., 121, 770-777 MP1/Multiflorous, MP2/Rape, MP4/Multiflorous (2010) [4]. Kropf U. et al.: Food Chem., 121, 839-846 (2010). and MP6/Buckwheat have analysed values δ13C LABORATORY FOR MEASUREMENTS OF TECHNOLOGICAL DOSES

Laboratory for Measurements of Technological Doses (LMTD) was created in 1998 and accredited as testing laboratory in February 2004 (Polish Centre of Accreditation, accreditation number: AB 461). The actual accreditation range is: • gamma radiation dose measurement by means of a Fricke dosimeter (20-400 Gy), • gamma radiation dose measurement by means of a CTA film dosimeter (10-80 kGy), • electron radiation dose measurement by means of a CTA film dosimeter (15-40 kGy), • electron radiation dose measurement by means of graphite and polystyrene calorimeters, • irradiation of dosimeters or other small objects with Co-60 gamma radiation to strictly defined doses, • irradiation of dosimeters or other small objects with 10 MeV electron beams to strictly defined doses. The secondary standard of the dose rate using by the LMTD is a Co-60 gamma source “Issle- dovatel” (cylindrical geometry, actual dose rate ~0.7 kGy/h, transit dose ~3 Gy). The source was calibrated in April 2009, according to NPL (National Physical Laboratory, Teddington, UK) primary standard. The uncertainty of the dose rate was estimated to be 2.9% (U, k = 2). 96 LABORATORY FOR MEASUREMENTS OF TECHNOLOGICAL DOSES A STUDY OF FILMS: CTA, B3 AND PVC AS POTENTIAL DOSIMETERS FOR DOSIMETRY AT LOW TEMPERATURES Anna Korzeniowska-Sobczuk, Katarzyna Doner, Magdalena Karlińska

Sterilization of health care products, pharmaceu- used: CTA, B3, PCV with optical signal detection. tical and of tissue banking are important applica- The film dosimeters were irradiated: tions of radiation technology. The manufacturer • with 10-MeV electron beams from an industrial must document that the entire process is continu- 10-kW linear accelerator. The mean electron ously under control and in compliance with nation- energy measured by the wedge method was in al and international standards for radiation sterili- the range 9.6-9.8 MeV. The interrelation be- zation. Most of the dosimetry with films is based on tween the electron beam flux and the speed of optical signal measurements [1-3]. All dosimetry the conveyor delivering dosimeters under the systems commonly used in the irradiation industry beam allowed keeping the dose at a specified are temperature sensitive. Radiation of low-tempe- level. The dosimeters placed in dry ice were ir- rature samples, must therefore take these dosimeter radiated in the polystyrene phantoms. The dose temperature effects into consideration. Although measurements were performed in a polysty- some information on temperature correction fac- rene or a graphite calorimetric dosimeters ir- tors is available in the literature, the application radiated in the same experiment. Calorimetric of a single correction factor is difficult because dosimeters and phantoms were produced at there can be batch to batch differences in dosimeter the High Dose Radiation Laboratory – HDRL response and because temperature during the ir- (Risø, Denmark); radiation process itself is not constant throughout • in the gamma field of a reference 60Co source the entire process. In a book, W. McLaughlin says Issledovatel (0.650 kGy/h), having the dose rate that “Irradiation temperature is, in fact, the most traceable to a primary standard maintained by important environmental factor contributing to the National Physical Laboratory – NPL (Ted- errors in absorbed dose estimation, and in radia- dington, UK); tion processing it is sometimes poorly determined • in the gamma field of 60Co source Gamma and difficult to correct for” [4]. Chamber 5000 (7.803 kGy/h), having the dose The alanine dosimeter response has a small but rate measured using of a Fricke dosimeter. noticeable temperature dependence, and thus the Film dosimeters were placed in a glass-metal dosimeter temperature during irradiation must be thermos in the same position as during the meas- measured properly to correct this effect. The ir- urements by determining the source using the radiation temperature coefficient is 0.23% per oC Fricke dosimeter. All irradiations in the 60Co source [5], 0.185% per oC [6] or is 0.11% per oC [7]. The were performed at the same packing geometry. reasons for differing values of temperature coef- The mean temperature of irradiation was calcu- ficient reported for different studies are not fully lated as the average of temperatures before and understood, but may by due differences in meas- after the irradiation, which were measured with a urement conditions. calibrated thermocouple. The characteristics and dosimetric response of The B3 and PVC films were heated immediately thin film dosimetry after irradiation in room tem- after irradiation to accelerate the chemical reac- perature are exactly known. CTA and B3 are films tions initiated by the ionizing radiation and playing widely use in routine dosimetry and were intro- a role in the growth of the dosimetric signals. The duced into practice a few years ago [1, 2, 8, 9]. The absorbance was measured by using a JASCO-V650 technical PVC film had been used as a routine spectrophotometer UV/Vis. The wavelength and dosimeter at a sterilization plant of the Institute absorbance scales were checked before each ex- of Nuclear Chemistry and Technology (INCT) for periment by a calibrated reference standard. many years [3, 6, 10-12]. During irradiation in the gamma source, steri- In the present paper, we studied the response lization dose (35 kGy) the impact was examined of of dosimeters after irradiation at a temperature of the density of the material being filled response o -78 C (dry ice – solid CO2). Presented are the im- on the weakening of the responce of dosimetric pact of the density of dry ice and other materials film. Summary of the results obtained is shown in on the reduction of the dosimetric response films. Table. For all investigated films, calibration curves In experiments three types of foil dosimeters were were constructed for the irradiation of highly en- Table. The response of dosimeters irradiated in the Gamma Chamber 5000 to a dose of 35 kGy, at temperatures -78oC o (dry ice – solid CO2), and 25 C (room temperature) in dependence on the density fill material.

Nominal Measuring The response in dry ice The foil The response at room temperature A – Ao thickness wavelength A – Ao dosimeters [mm] [nm] d = 1.048 g/cm3 d = 0.842 g/cm3 d = 0.677 g/cm3 d = 0.07 g/cm3 CTA 0.128 280 0.1581 ± 3.4% 0.2604 ± 1.0% 0.2871 ± 1.7% 0.2492 ± 1.4% B3 0.018 556 0.1944 ± 6.0% 0.3702 ± 2.0% 0.3979 ± 2.8% 0.3994 ± 1.9% PCV 0.257 396 0.385 ± 0.8% 1.3009 ± 1.2% 1.3981 ± 0.7% 1.6247 ± 0.7% LABORATORY FOR MEASUREMENTS OF TECHNOLOGICAL DOSES 97 ergetic electrons at the temperature of dry ice and [4]. McLaughlin W.L., Boyd A.W., Chadwick K.H., McDo- for a density of 0.75 g/cm3. The largest discrep- nald J.C., Miller A.: Dosimetry for radiation process- ancies were observed for CTA films, the conver- ing. Taylor & Francis, 1989, 251 p. gence rate was 83% and the uncertainity measure- [5]. Sanchez-Mejorada G., Frias D., Negron-Mendoza A., Ramos-Bernal S.: Radiat. Meas., 43, 287-290 (2008). ment was 16.6%. Good results were obtained for [6]. Mehta K.: Appl. Radiat. Isot., 47, 11-12, 1155-1159 PVC and B3, the convergence rate was 94 and (1996). 96%, respectively. The uncertainity measurement [7]. Wieser A., Siegele R., Regulla D.F.: Appl. Radiat. for the films PCV and B3 were 9.3 and 7.8%, re- Isot., 40, 957-959 (1989). spectively. The results are shown in Fig. [8]. Peimel-Stuglik Z.: Odpowiedź dozymetryczna nie bar- wionych folii z trioctanu celulozy (CTA) na promieniowanie gamma 60Co (Dosimetric response of un- tinted, commercially available CTA foils for 60Co gamma rays). Instytut Chemii i Techniki Jądrowej, Warszawa 2001. Raporty IChTJ. Seria B nr 11/2001 (in Polish). [9]. Peimel-Stuglik Z., Fabisiak S.: Odpowiedź radiacyjna folii PCW i folii B-3 na promieniowanie elektronowe o energii 10 MeV w zakresie dawek 5-40 kGy (Dosi- metric answer of PVC and B-3 films to electron beams with energy 10 MeV in the range 5-40 kGy). Instytut Chemii i Techniki Jądrowej, Warszawa 2005. Raporty IChTJ. Seria B nr 4/2005 (in Polish). Fig. Calibration curves for irradiation with a 10 MeV elec- [10]. Peimel-Stuglik Z., Fabisiak S.: Badanie czynników tron beam from the accelerator at a temperature of dry ice wpływających na odpowiedź radiacyjną folii PCW for the dosimetric films: (□) PCV, (♦) B3, (○) CTA. napromienianej w źródle kobaltowym (A study of influence factors affected dosimetric answer of PCV Factor associated with the density (0.75-1.05 films irradiated in 60Co source). Raporty IChTJ. In- 3 g/cm , depending on the granulation of dry ice) stytut Chemii i Techniki Jądrowej, Warszawa 2005. should be taken into account during irradiation in Seria B nr 5/2005 (in Polish). dry ice. PVC and B3 are the potential dosimeters [11]. Peimel-Stuglik Z., Fabisiak S.: Rewalidacja metody that can be used for dosimetry at low tempera- pomiaru dawki pochłoniętej promieniowania elektro- tures and to process sterilization tissue. This re- nowego dozymetrem foliowym z polichlorku winylu. quires further study. Cz.1. (Revalidation of the method used for measurement of electron beam absorbed dose by means of a polyvinylchloride film dosimeter. Part 1). Insty- tut Chemii i Techniki Jądrowej, Warszawa 2007. Ra- References porty IChTJ. Seria B nr 3/2007 (in Polish). [1]. ISO/ASTM 51275:2004(E). Standard practice for use [12]. Peimel-Stuglik Z., Fabisiak S.: Rewalidacja metody of a radiochromic film dosimetry system. pomiaru dawki pochłoniętej promieniowania elektro- [2]. ISO/ASTM 51650:2005(E). Standard practice for use nowego dozymetrem foliowym z polichlorku winylu. of a cellulose triacetate system. Cz.2. Krzywe kalibracyjne i post-efekty. (Revalida- [3]. Bułhak Z.: Stosowanie dozymetrów foliowych w eks- tion of the method used for measurement of electron ploatacji wielkiego źródła promieniowania – liniowe- beam absorbed dose by means of a polyvinylchloride go akceleratora elektronów LAE 13/6 (Use of foil film dosimeter. Part 2. Calibaration curves and post- dosimeters in the exploitation of a large radiation -effects). Instytut Chemii i Techniki Jądrowej, War- source – the electron linear accelerator LAE 13/6). szawa 2007. Raporty IChTJ. Seria B nr 4/2007 (in Instytut Badań Jądrowych, Warszawa 1975. Ph.D. Polish). dissertation (in Polish). LABORATORY FOR DETECTION OF IRRADIATED FOOD

The Laboratory for Detection of Irradiated Food was created in the Institute of Nuclear Chemistry and Technology in 1994 and, after adoption of the quality assurance system, received its first accreditation certificate in 1999. From that time, it renders analytical service in the field of detection of irradiated food to domestic and foreign customers in many countries. During the last 10 years, more than 2000 food samples have been successfully examined. In 2010, the Laboratory received a new Accreditation Certificate of Testing Laboratory Nr AB 262 issued by the Polish Centre of Accreditation on 22.10.2010 valid until 24.10.2014. The integral part of accreditation documentation is the Scope of Accreditation Nr AB 262 comprising the list of detection methods which are in use. These are: • detection of irradiated food containing bone by EPR spectroscopy – analytical procedures based on PN-EN 1786:2000 standard; • detection of irradiated food containing cellulose by EPR spectroscopy – analytical procedures based on PN-EN 1787:2001 standard; • detection of irradiated food containing crystalline sugars by EPR spectroscopy – analytical procedures based on PN-EN 13708:2003 standard; • detection of irradiated food from which silicate minerals can be isolated using thermoluminescence – analytical procedures based on PN-EN 1788:2002 standard; • detection of irradiated food using PSL (photostimulated luminescence) – analytical procedures based on PN-EN 13751:2009 standard. The analytical activity of the Laboratory, to the orders of domestic and foreign customers during the last 12 months, compiles the detection of irradiation in spices, herbal pharmaceuticals, fruit and vegetable pulps, fresh fruits and vegetables, nuts, diary, mushrooms and fish. In parallel, the Laboratory develops new analytical and measuring procedures making it possible the detection of irradiation in complex food articles containing typically low content of irradiated ingredient and minerals. The attention was focused on the examination of wet samples in L-band by EPR (electron paramagnetic resonance) method and the effectiveness of different procedures for mineral separation in TL (thermoluminescence) method. In the present year, 200 samples have been L-band electron paramagnetic resonance (EPR) spectro- examined which represented very different meter in the INCT designed and constructed in the Institute groups of foodstuffs. As much as 14% of the of Telecomunication, Teleinformatics and Acoustics, Wrocław total number of the samples were found to be University of Technology. irradiated. The TL, EPR and PSL examination of foodstuffs were executed for domestic firms and food control institutions as well as for foreign customers in Germany, Italy, France, Denmark, Spain, the Untied Kingdom, Switzer- land, Russia. The Laboratory was invited in November 2011 to join the “Intercomparative exercise for quality assurance on EPR and TL irradiated food detection method. 3rd round” organized by the Food Technology Department of Spanish Agency for Food Safety and Nutrition with the participation of specialized analytical laboratories from many countries. 100 LABORATORY FOR DETECTION OF IRRADIATED FOOD INCT PARTICIPATES IN THE INTERCOMPARATIVE EXERCISE FOR QUALITY ASSURANCE ON TL, PSL AND EPR IRRADIATED FOOD DETECTION METHODS Wacław Stachowicz, Magdalena Sadowska, Grażyna Liśkiewicz, Grzegorz P. Guzik

The National Center for Food (CNA) in Spain or- Table 1. Samples prepared by the organizer to be analysed ganized in 2011 an international intercomparative in participating laboratories. Irradiation status is indicated. study (3rd round) on the detection of food pre- Origin code Sample Irradiation dose served by ionizing radiation with the use of standardized EPR (electron paramagnetic resonance), IE3-1 oregano 1 kGy TL (thermoluminescence) and PSL (photostimu- IE3-2 green tea unirradiated lated luminescence) methods and/or their own protocols. The task of the present exercise was to IE3-3 curry 1 kGy detect which of coded food samples was irradiated IE3-4 camomile 1 kGy and to distinct the samples irradiated with lower IE3-5 pepper (black) unirradiated and higher doses of radiation. The CEN (European Committee for Standard- IE3-6 rosemary unirradiated ization) standardized methods for the detection of IE3-7 chicken bone unirradiated irradiated food by EPR, TL and PSL methods [1-5] were validated with the use of model samples ir- IE3-8 pork bone 1 kGy radiated with doses equal or close to technological IE3-9 razor shell unirradiated doses recommended. Nowadays, food producers IE3-10 clam shell 1 kGy and distributors tend to decrease irradiation doses to the lowest acceptable levels assuring the intend- IE3-11 nut shell 1 kGy ed preservation effect and microbial food safety. IE3-12 cayenne unirradiated Such “optimal” doses are markedly lower than IE3-13 raisins 1 kGy those recommended earlier. It is why in the present study low dose irradiated food samples were IE3-14 raisins unirradiated examined, too. In the present exercise twenty two laboratories • camomile, were involved from EU countries (France, Ger- • rosemary, many, Italy, Poland, Romania, Spain, United King- • raizor shell, dom) and from Turkey. Participating laboratories • clam shell. are working on or are engaged in the detection of Organization of the study irradiated food for customers or for the Official The CNA Laboratory has prepared 14 test samples Food Control System. Thirteen laboratories in- irradiated and/or not irradiated to be delivered to cluding the Laboratory for Detection of Irradiated the participant by post for examination. Thus, each Food, Institute of Nuclear Chemistry and Tech- of the participating laboratories analysed the fol- nology (INCT) participated earlier (2010) in the lowing number of samples: round 2nd intercomparative exercise in 2010, while • two samples for TL method (each sample in du- nine were new. plicate); The samples • four samples for PSL method (each sample in The following products were selected to be tested duplicate); throughout the study (Table 1): • eight samples for EPR method: two samples • for TL method two samples of dried herbs, containing cellulose, two containing crystallized oregano and green tea, coded as IE 3-1 and IE sugar, two samples of bones and two of molluscs. 3-2 and weighing about 50 g each; All samples were coded with numbers. • for PSL method four samples of dried spices, Irradiation of samples curry, camomile, black pepper and rosemary, The samples analysed in the INCT for calibrated coded as IE 3-3 to IE 3-6; irradiation were irradiated with the use of a 60Co • for EPR method eight different samples as gamma source calibrated with a ferrous-ferric dosi- chicken bone, pork bone, razor shell, clam shell, meter (Fricke dosimeter). The dose rate was 0.95 walnut shell, cayenne, raisins, coded IE 3-7 to kGy/h. IE 3-14. The CNA dosimetry was done using ECB dosi- Full list of the investigated products: meters calibrated at the High Dose Reference Lab- • chicken bone, oratory of Risø National Laboratory (Denmark), • pork bone which has traceability to the National Physical Lab- • walnut (shell), oratory (UK). The dose rate was 6.94 kGy/h. • dried herbs, EPR examination • raisins (whole fruits), The samples were examined in the INCT follow- • pepper, ing the procedures adapted in the Laboratory for • curry, Detection of Irradiated Food and based on those • cayenne, recommended by the European standards: LABORATORY FOR DETECTION OF IRRADIATED FOOD 101 • EN 1786 (chicken bones, pork bones, raizor Walnut shell and cayenne contain cellulose and shell, clam shell); hence were expected to give rise to the specific • EN 1787 (walnut shell, cayenne); cellulose EPR signal. The criterion for the detec- • EN 13708 (raisins). tion of irradiation in cellulose containing products The EPR measurements have been done with the is the appearance of two satellite lines distanced use of a Bruker ESP 300 spectrometer in X-band. by 6 mT belonging to cellulose radical triplet (cen- The samples (ca. 2.5 cm high) were placed in 5 mm tral line of this triple signal is overlapped by a Table 2. EPR examination of investigated samples.

Origin number Mass of sample [mg] Name of sample INCT result Result as origin IE 3-7 104.5 chicken bone negative negative IE 3-8 75.8 pork bone positive positive IE 3-9 309.1 raizor shell negative negative IE 3-10 300.9 clam shell positive positive IE 3-11 107.7 walnut (shell) positive positive IE 3-12 75.1 cayenne negative negative IE 3-13 103.1 raisins positive positive IE 3-14 102.1 raisins negative negative

Wilmad glass sample tubes. The EPR measuring strong quinone derivative signal). EPR signal re- conditions have followed those recommended in corded with radiation treated cayenne and walnut the above-named standard documents. shell was not specific enough to be qualified defi- PSL examination nitely as belonging to irradiated stuff. Neverthe- The samples were examined with a SURRC PSL less, a very weak shoulders in the EPR signal dis- screening system installed in this Laboratory fol- tanced by 6 mT allowed to conclude that walnut lowing the procedures recommended in the Euro- shell could be irradiated. It was not the case with pean standard EN 13751. The samples (pepper, cayenne which was qualified unirradiated. Both curry, camomile, rosemary) were placed in 5 cm qualifications were consistent with organizers data diameter Petri-dishes. The PSL measuring condi- as issued in the final report of the test. tions were adjusted as those recommended in the Results of intercomparison study obtained above-named standard document. in the INCT Laboratory Detection criteria A. EPR examination (Table 2): The criteria of the detection of radiation treat- • all non-irradiated samples were classified cor- ment were: rectly, • identification of the EPR signal specific for ir- • all irradiated samples were classified correctly. radiated samples, B. PSL and TL examination (Table 3): • comparison of the PSL signal with the lower • all non-irradiated samples were classified cor- and upper threshold values (T1 and T2) esti- rectly, mated for herbs and spices, • all irradiated samples were classified correctly, • identification of the TL signal based on the glow Conclusions ratio Glow 1/Glow 2 and the shape of Glow 1 The standardized PSL and EPR methods for de- within the range of temperatures 150-250oC for tection of radiation treatment of selected groups mineral debris isolated from food samples. of food are reliable and enable the detection of Table 3. TL and PSL examination of investigated samples.

Origin Name Glow 1 Glow 2 INCT Result number of sample – for fresh sample – after control irradiation result as origin IE 3-1 oregano 2 923 366 3 893 179 positive positive IE 3-2 green tea 9 736 650 039 negative negative IE 3-3 curry 8 257 376 15 113 288 positive positive IE 3-4 camomile 88 282 119 194 positive positive IE 3-5 pepper 268 5 023 negative negative IE 3-6 rosemary 304 63 670 negative negative

All samples investigated by the EPR method, with food samples irradiated with 1 kGy. The PSL and the exception of walnut shell and cayenne, are EPR methods for the detection of radiation treat- mentioned in relevant European standards as suit- ment of selected groups of food are capable of able for EPR examination whether irradiated. distinguishing low dose (1 kGy) and high dose 102 LABORATORY FOR DETECTION OF IRRADIATED FOOD (7-10 kGy) irradiations. The investigated range of [2]. PN-EN 1788:2001: Foodstuffs – Thermoluminescence doses covers that commercially adapted for radia- detection of irradiated food from which silicate min- tion treatment of most of foodstuffs. However, at erals can be isolated. European Committee for Stand- doses lower than 1 kGy, like for example 0.5 kGy, ardization (CEN), Brussels. [3]. PN-EN 13751:2009: Foodstuffs – Detection of irradi- the sensitivity of EPR and PPSL methods was ated food using photostimulated luminescence. Euro- found not sufficient resulting in the difficulty in pean Committee for Standardization (CEN), Brussels. the qualification of samples. The best and most [4]. PN-EN 1786:2000: Foodstuffs – Detection of irradi- reliable method for the detection of irradiation of ated food containing bone – Method by ESR spec- the investigated group of products was found the troscopy. European Committee for Standardization TL method. (CEN), Brussels. [5]. PN-EN 1787:2001: Foodstuffs – Detection of irradiat- References ed food containing cellulose by ESR spectroscopy. Euro- [1]. EN 13708:2003: Foodstuffs – Detection of irradiated pean Committee for Standardization (CEN), Brussels. food containing crystalline sugar by ESR spectroscopy. European Committee for Standardization (CEN), Brussels.

EFFECTIVENESS OF DIFFERENT PROCEDURES OF MINERAL ISOLATION FROM IRRADIATED SPICES SUITABLE FOR THERMOLUMINESCENCE DETECTION METHOD Magdalena Sadowska, Wacław Stachowicz

Analytical methods suitable for the detection of chosen. These were: dried basil leafs, powdered irradiated food have been developed to assure in- onion, powdered garlic, powdered paprika and dependent control of radiation preserved food- powdered chili, all purchased in supermarkets. The stuffs and to strengthen consumers confidence to samples undergone preliminary control by apply- this relatively new method of food conservation ing a standard TL method (density separation) of [1]. At present, the method most frequently used in mineral isolation to prove whether irradiated. The practice is thermoluminescence (TL) [2-4]. Sub- control was positive – none of the investigated stantial condition assuring high reliability of the products was found irradiated. Samples were ir- method is the isolation of mineral contaminants radiated at a dose of 10 kGy (technological dose from the tested food. adapted for spices) in a 60Co Gamma Chamber Thus, sensitivity and reliability of the detection (dose rate – 7.5 kGy/h) owned by the Centre for of irradiated food by thermoluminescence depends Radiation Research and Technology, Institute of on the effectiveness of mineral isolation from the Nuclear Chemistry and Technology (INCT). The rest of food samples. Isolation procedure recom- weight of each of the samples taken for TL exami- mended by CEN (European Committee for Stan- nation was 25 g ± 2%. dardization) standard EN 1788:2002 [5] represents The following mineral isolation procedures a number of analytical steps including the main were tested and subsequently compared: one – density separation of the mineral fraction • N – density isolation method recommended by from the organic remainder in sodium polytung- EN 1788:2002 lasting at least 2 h. A sample sus- state water solution (d = 2.0 g/cm3). The product pended in mineralized water undergoes ultra- most frequently undergoing examination whether sound treatment for 10 min. Afterwards, it is irradiated in analytical laboratories specialized in sieved wet through a 125 μm nylon net, treated the detection of radiation treatment of foodstuffs with sodium polytungstate water solution of the are spices and seasonings in a pure state (leafs or density 2 g/cm3. Then, mineral debris was treat- powders) or blended, while recently quite often ed with 3 M hydrochloric acid, washed mani- food products and diet supplements containing folds with water and centrifuged. Mineral de- spices and dried vegetables as additives as souses, posit was taken from an ampoule, treated with instant soups, phyto-pharmaceuticals and flavour acetone, transferred to TL measuring cups and extracts. Usually, the content of mineral in such dried. products is extremely low and the application of • H – acid hydrolysis method lasting at least 2.5 h. most effective and universal isolation procedure, Sample suspended in water undergoes hydrolysis as that recommended in EN 1788:2002, is needed. with 6 M HCl for 2 h and is sieved wet through On the other hand, however, spices and dried veg- a 125 μm nylon net. Mineral deposit taken from etables in pure state or blended contain typically a the button of receiver bigger is centrifuged. The lot of mineral which could be isolated by a more isolated mineral debris is treated with acetone simple, less time consuming and inexpensive and subsequently taken to TL measuring cups method. In the present study the usefulness of such and dried. methods of mineral isolation from this kind of • P – wet sieving method lasting ca. 1 h. Sample product was proven. As a subject of study, five com- was stirred in demineralized water, sieved wet mercial spices commonly used in the kitchen were through a 125 μm nylon net, while decanted LABORATORY FOR DETECTION OF IRRADIATED FOOD 103 mineral deposit is taken from the button of the silicates in it. However, this factor remains not vessel after removing the excess of water, treat- controllable and everything depends on recorded ed with acetone and transferred to TL measur- data (counts of TL glow pulses/photons). Accord- ing cups. • U – ultrasound method. Sample suspended in mineralized water is for 10 min treated with ultrasounds and then sieved wet through a 125 μm nylon sieving net. Mineral debris is taken from the button of the vessel after removing of excess water, treated with acetone and transferred to TL measuring cups, as above. Minerals deposited on TL measuring cups isolated by four mineral separation procedures from each of the five investigated products (test sample weight – 25 g ± 2%) were weighed with an accuracy of 0.0001 g. According to EN 1788:2002 standard, the weight of mineral isolated from food that Fig.3. The normalized glow curves recorded with mineral fraction isolated from irradiated garlic by four isolation procedures tested: N – mineral separation, H – hydrolysis, P – sieving, U – ultrasound treatment. ingly, weighing of minerals is in practice not necess- arily needed. Nevertheless, weighing of mineral deposits in the present study is rational, indicating how efficient was isolation procedure despite of its composition.

Fig.1. The normalized glow curves recorded with mineral fraction isolated from irradiated basil by four isolation procedures tested: N – mineral separation, H – hydrolysis, P – sieving, U – ultrasound treatment. guarantee the reliable TL detection of irradiation lies between 0.1 and 5 mg. It is also recommended Fig.4. The normalized glow curves recorded with mineral fraction isolated from irradiated paprika by four isolation to divide bigger mineral volumes to parts before procedures tested: N- mineral separation, H – hydrolysis, TL measurement. Low mineral weight below 0.1 P – sieving, U – ultrasound treatment. mg is too low to proceed properly TL measure in most cases. It is pertinent to note that a lower (0.1 For each of the investigated spices, two TL mg) threshold value of mineral weight has only measurements were done in parallel. The inten- empirical origin and was established on the ground sity of thermoluminescence (the area below glow curves) was measured within the range of temperature between 150 and 250oC. It is the region where only radiation-induced thermoluminescence appears.

Fig.2. The normalized glow curves recorded with mineral fraction isolated from irradiated onion by four isolation procedures tested: N – mineral separation, H – hydrolysis, P – sieving, U – ultrasound treatment. Fig.5. The normalized glow curves recorded with mineral of a number of repeated measurements done with fraction isolated from irradiated chili by four isolation pro- selected model samples. The factor that influences cedures tested: N – mineral separation, H – hydrolysis, P – TL response of mineral deposit is the content of sieving, U – ultrasound treatment. 104 LABORATORY FOR DETECTION OF IRRADIATED FOOD In Figs. 1-5 the TL glow curves recorded with of recommended mineral separation procedure mineral debris isolated from irradiated test prod- (N) was lower although still acceptable. ucts by four mineral isolation methods are com- • Onion – positively the highest TL intensity was pared. obtained by using a density separation proce- As seen from the Table (column III), the high- dure, while the application of ultrasound deliver- est volumes of mineral were isolated from garlic, a ed also a satisfactory result. However, hydrolysis little lower, but still high from paprika and chili, was found not suitable at all. but markedly lower from powdered onion. Isola- • Garlic – the highest TL intensities were obtain- tion procedure based on sieving only result in the ed by the examination of mineral isolated with lowest yield of mineral, lower than acceptable the use of density separation and hydrolysis. threshold level (01 μg, see EN 1788:2002). Both simplified isolation methods (sieving – P This parameter, however, is different from and ultrasound treatment – U) were found also sample to sample depending on the initial state of efficient enough. product (cleaning/washing procedures). • Paprika – the most effective mineral isolation Very interesting results were obtained when was obtained by using hydrolysis (H) and simple TL intensities of Glow 1 (column IV) recorded sieving (P). The effectiveness of two other iso- with mineral debris isolated by four different pro- lation procedures was acceptable, too. cedures from seven tested products were com- • Chili – the most efficient was mineral separa- pared: tion (N) and ultrasound treatment (U), while • Basil – the highest TL intensities were recorded the other two methods were effective, too. with mineral isolated by using hydrolysis (H) From the above comparative study, it is clearly and ultrasound treatment (U). The efficiency seen that by the examination of dried spices and Table. The results of TL examination of mineral debris isolated from irradiated (10 kGy). Weight Glow 1 – Glow 2 – Sample Isolation Glow ratio TLGlow maxima of isolated mineral count number count number number procedure* Glow1/Glow2 [oC] [mg] 150-250oC 150-250oC I II III IV V VI VII BASIL 1 N 1.24 102 761 197 26 653 589 3.85 187 2 H 1.88 148 997 859 35 116 171 4.24 192 3 P 2.04 67 270 283 15 361 976 4.37 192 4 U 2.77 132 898 929 30 471 611 4.36 191 ONION 5 N 0.18 948 159 384 089 2.47 182 6 H 0.80 2 034 15 299 0.13 211 7 P 0.01 128 372 13 370 9.60 185 8 U 0.44 523 517 380 465 1.37 184 GARLIC 9 N 2.70 240 336 683 160 706 762 1.49 212 10 H 2.40 277 935 518 97 515 393 2.85 207 11 P 2.4 135 691 991 68 385 190 1.98 215 12 U 2.6 162 791 696 79 627 348 2.04 218 PAPRIKA 13 N 2.5 253 405 801 158 385 613 1.59 199 14 H 2.1 277 457 004 124 366 735 2.23 200 15 P 3.2 291 027 650 166 605 537 1.74 200 16 U 1.2 137 331 443 69 698 228 1.97 202 CHILI 17 N 1.6 238 175 443 131 728 313 1.81 198 18 H 1.3 175 049 815 58 646 969 2.98 205 19 P 1.8 161 833 118 73 704 992 2.19 206 20 U 1.9 191 628 642 92 256 991 2.07 199 * For more details see the text above. LABORATORY FOR DETECTION OF IRRADIATED FOOD 105 vegetables the recommended density separation [2]. Autio T., Pinjoja S.: Z. Lebensm. Untersuch. Forsch., procedure (N) does not dominate much over three 191, 177-180 (1990), in German. other isolation procedures tested including rela- [3]. Calderon T., Rendell H.M., Beneitez P., Townsed P.D., tively simple sieving (P) and ultrasound treatment Millan A., Wood R.: J. Food Sci., 59, 1070-1071 (1994). [4]. Lesgards G., Fakirian A., Raffi J.: Thermolumines- (U). It is advisable to use these methods in ana- cence identification of irradiated food: LARQUA re- lytical practice under the condition that for each search. In: Detection methods for irradiated foods – product the testing and validation of isolation pro- current status. Eds. C.H. McMurray, E.M. Stewat, R. cedures will be done in advance. It has to be point- Gray, J. Pearce. Royal Society of Chemistry, Cam- ed out that the recommended density separation bridge, UK 1996, pp. 158-167. is not only a complex and time consuming proce- [5]. EN 1788:2002: Foodstuffs – Thermoluminescence de- dure, but also the most expensive one. tection of irradiated food from which silicate minerals can be isolated. European Committee for Standard- References ization (CEN), Brussels. [1]. FAO/WHO Codex Alimentarius. Vol. XVI. 1984. LABORATORY OF NUCLEAR CONTROL SYSTEMS AND METHODS

The main subject of the Laboratory activity in 2011 was the development of methods and ap- paratus, based generally on the application of ionizing radiation, and process engineering for measurements and diagnostic purposes. The research programme of the Laboratory was focused on the following topics: • development, construction and manufacturing of measuring devices and systems for industry, medicine and protection of the environment; • elaboration and implementation of wireless communication systems based on GPS or the Internet for data acquisition and transmission; • construction and laboratory testing of a gamma scanner for diagnostics of industrial installation; • development of measuring equipments for other Institute laboratories and centers; • development of a new leakage control method for testing of industrial installations during their operation; • identification and optimization of industrial processes using tracers and radiotracer methods; • application of membrane processes of biogas separation and their enrichment in methane; • elaboration and implementation on an industrial scale of new methods and technology of biogas production by fermentation of agriculture substrates and by-products; • hydrogen production from the synthesis gas using membrane separation. In the field of elaboration and construction of new nuclear instrumentation the works were directed towards radioactive contaminations, measurements of concentration of radon daughters and wireless data transmission. A radiometric stand based on the application of large area thin scintillators for alpha-, beta- and gamma-radiation measurement, was constructed and tested for contamination detection in laboratory and industrial conditions. The system for attached and unattached radon 222Rn decay products in air or water was elaborated and tested in laboratory conditions. In the frame of realized R&D project, development of a new generation of mining radiometers was undertaken. The radiometer to be used in mines where methane gas can be present, must satisfy the explosion proof conditions. All realized and constructed instruments are prepared in the version with wireless transmission of results and their storage in memory of data acquisition system. The Wi-Fi (Wireless Fidelity) and GSM (Global System for Mobile Communication) are used for data transmission depending on the distance between the detector and control unit. The same type of measuring equipment is used in a gamma scanner for diagnostics of large industrial installations. 108 LABORATORY OF NUCLEAR CONTROL SYSTEMS AND METHODS THE RADIOMETRIC PROBES FOR INDUSTRIAL MEASURING SYSTEMS Adrian Jakowiuk, Ewa Kowalska, Jan Pieńkos, Paweł Filipiak, Łukasz Modzelewski, Jacek Palige, Janusz Kraś

In the frame of the development of new measur- to determined the location and type of column ing systems a wireless probe (detector) was de- damage or disturbance of the process. The meas- signed for measurements of ionizing radiation in urements is based on the simultaneous move of industrial and field conditions (Fig.1). the radiation source and scintillation probe on opposite sides of the tested column. The drive of source and detector are on the ground (level zero). Measuring diagram is shown in Fig.2 [1].

Fig.1. Probe for industrial radiometry. Scintillation probe allows for the collection, processing and storage of measurement results through a dedicated steering software. These probes have a built-in battery and are equipped with a system for wireless communication to the central unit of data acquisition. The detector consist of radiometric and electronic parts and is equipped with a microcontroller that controls operation of communications systems and proper operation of the probe. Fig.2. Functional diagram of a gamma scanner: Z – gamma- The measurement results can be sent to a unit -radiation source 137Cs, 555 MBg (15 mCi); SS – scintillation of data collection using one of two transmission probe with scintillate NaI(Tl) φ50 x 50 mm, equipped with channels in Wi-Fi for short measurement series a wireless communication system, powered from a local (up to 48 h) or through the GSM and the Internet battery; NZ – drive shift of a source with a wireless control for long-term measurements. system; NS – drive shift of the scintillation probe with a Functional parameters of detector are the fol- wireless control system; PC – portable computer, a “note- lowing: book”, and a scanner program with a system of wireless • X-rays or gamma-radiation measurements in the communication; P – fence; LP – leading rope; NL – tension of the rope leading; KZ – wheel suspension of probe and environment probes for quantum energy above container with the source. 50 keV; • possibility of continuous work with radioactive The designed system does not have a network isotopes 60Co, 137Cs, 241Am; cable (with electric contact) for data transmission • possibility of probes work in vertical and hori- from the probe (detector) to the control and data zontal positions also as hanging device in indus- processing unit, what is important for its use in the trial and field conditions; petrochemical industry. • active front surface – 20 cm2, side – 25 cm2; Test may be conducted during normal opera- • counts efficiency for isotope 137Cs: ≥ 20%; tion of installation and requires no intervention • counts efficiency for isotope 60Co: ≥ 40%; within the diagnosed column. Realization of meas- • manage of the probe work by a laptop or PDA; urements requires only location on the external • collection the measurements results of the parts of the installation, and using of lines to move probe by using wireless communication (Wi-Fi, the source and detector in selected vertical sec- GSM); tions of the installation. Typical scans obtained • power supply: built-in battery allows continu- during the experiments are shown in Fig.3. ous operation of the probe during 10-14 days. Another application of this scintillation probe Possible connection with solar panels battery; type system is used for leak testing of industrial • range of operating temperatures: -10 to +40oC; objects using a unique method developed in the • dimension and weight: diameter – 9 cm (with Institute of Nuclear Chemistry and Technology antennas φ12), length – 63 cm, weight – 7 kg. (INCT) using radioactive tracer [2]. This kit con- Scintillation probes of this type can find appli- sists of: cation in the control and measuring the operation • four scintillation probes for the measurement parameters of various object and industrial instal- of gamma and beta radiation, lations. Such probes have been used in the gamma • multichannel impulse amplitude analyser, scanner, which is used for identification of opera- • wireless system for information transmission tion parameters of rectification columns in the between the probe and the central unit, petrochemical industry. • the software that controls work of the whole The test column is screened by using radiation set. sources 60Co or 137Cs. Based on the measurements A scheme of leak testing is presented in Fig.4. recorded in combination with archival measure- In the case of studying industrial objects, the ments made on the same installation, it is possible most important statement is the presence or ab- LABORATORY OF NUCLEAR CONTROL SYSTEMS AND METHODS 109

series 1 probes S1 to S4. Based on the time elapsed from series 3 the registration of radiation on individual probes, series 4 the overall leak installation is calculated. When none of the probes register growth radiation, the

Fig.4. A scheme of leak testing of industrial object. installation is considered as a 100% air-tight. In the case of a leak detection, the order methods for leakage localization are applied [3]. References [1]. Machaj B., Jakowiuk A., Świstowski E., Palige J.: Gamma skaner GS-08. Instrukcja obsługi (Operation manual of gamma scanner GS-08). Institute of Nuc- lear Chemistry and Technology, Warszawa 2011. Opra- cowanie wewnętrzne IChTJ nr 36/LTJ/11, in Polish. [2]. Kraś J., Waliś L.: Lokalizacja nieszczelności w obiek- tach technologicznych przy użyciu metody znaczników promieniotwórczych (Localization of leakages in technological objects using the method of radioactive markers). Postępy Techniki Jądrowej, 42, 4 (1999), in Fig.3. Course of the scan test installation (distance be- Polish. tween source and detector – 120 cm; series 1 – step of dis- [3]. Kraś J., Waliś L., Myczkowski S.: Doświadczenia z izo- tance discretization – 1 cm, time per channel – 10 s; series topowej kontroli szczelności obiektów technologicz- 3 – step of distance discretization – 5 cm, time per channel nych – aspekty techniczne i ekonomiczne (Experience – 30 s; series 4 – step of distance discretization – 5 cm, time in isotope leak-proof control of engineering objects – per channel – 10 s. technical and economical aspects). In: Technika jądro- sence of leak. The applied method is based on the wa w przemyśle, medycynie, rolnictwie i ochronie śro- introduction of radioactive tracer (methyl bro- dowiska T.2. Raporty IChTJ. Seria A nr 2/2002. Insty- tut Chemii i Techniki Jądrowej, Warszawa 2002, pp. mide) to the controlled object, followed by con- 373-379, in Polish. tinuous measurement of radiation values by using

MOBILE DOSIMETRIC GATE Adrian Jakowiuk, Ewa Kowalska, Jan Pieńkos, Paweł Filipiak, Łukasz Modzelewski

Mobile dosimetric gate was constructed for the Principles of operation and construction purpose of continuous monitoring of radiation of the gate background in places involving work with radioac- The gate uses a scintillation probe containing a tive sources (possibility of contamination) and con- sensitive to X- and gamma radiation integrated stant control of places with high concentration of detector with a NaI(Tl) scintillator, φ50 x 50 mm. people (railway stations, airports, underground) in Pulses from the detector, shaped and amplified, order to detect an illegal transport of radioactive are sent to two measuring channels. In the first isotopes. When comparing to similar devices [1-3], channel, after the photomultiplier noise being cut mobile dosimetric gate is a stand-alone device, off, pulses go to the counter, where under the con- able to work either indoors or outdoors. Current trol of microcomputer are counted at specified measurements of background radiation can be re- time intervals. The second measuring channel is ceived continuously or periodically by a computer to analyse radiation registered by the probe, by through wireless communication network Wi-Fi finding and positioning peaks in the spectrum re- [4]. Several gates, placed in different locations, can corded by the analyser. As a result, it is possible to be connected to the computer forming a monitor- determine the probable isotope type which caused ing network. The gate signals dangerous exceed- the alarm. This channel runs continuously, but the ing of the surrounding radiation background us- results are analysed only when the alarm counting ing light and sound signalling. threshold is exceeded. 110 LABORATORY OF NUCLEAR CONTROL SYSTEMS AND METHODS The gate works under the control of microcomputer, which manages the operation of the probe, registers actual measurements in the memory, launches the light and sound signalling (after exceeding alarm counting threshold) and sends information to the control centre about dangerous breaches of the background. The gate (Fig.1) consists of a long tube (φ15 x 70 cm) expanded in the lower part (φ33 x 30 cm). The scintillation probe is located in the upper part. In the middle part, electronics which registers measured radiation can be found. In the expanded part there are batteries to power the electronics and a signalling system (placed in the upper part). Thanks to using the internal power, the designed gate is mobile and easy to change location. Measurement results and ways of presenting Current measurement results of radiation background around the gate can be tracked on the computer monitor, connected to the gate through Wi-Fi network. Basic program panel to support mobile dosimetric gate (Fig.2) displays digitally the current (last 15 s) average number of background Fig.1. Mobile dosimetric gate with a solar cell used to bat- counts in pulses per second and illustrates this tery charging. value graphically. There is also given a number of exceedances of background for the set time range ground radiation (Fig.4, A area), a 1 μCi 60Co of the measurement. source was placed at a distance of 30 cm from the When turning the advanced panel on, the results centre of the probe. The system responded by can be seen as graphs for a selected period of time. turning on the alarm, rapid growth of background Sample plot of background radiation measure- indications and changed to one-second measurements of four consecutive days is shown in Fig.3. ments (Fig.4, B area). After changing the distance It is also possible to individually elaborate the to 50 cm, the average measurement results are measurement results in different graphic programs shown again in five-second intervals (Fig.4, C by transferring the results from the computer’s area). memory (“Save to file” command). This is how the The average background exceeding level fol- results of an experiment carried out with a 60Co lowed by a sound and light threat signal and the source were illustrated. After establishing the back- change of sending results to computer memory

Fig.2. The main program window for mobile dosimetric gate. LABORATORY OF NUCLEAR CONTROL SYSTEMS AND METHODS 111

Fig.3. The waveform of the background radiation measured in four consecutive days. The solid line – 1 h moving average of the measured background. every 1 s was set up to be 100 Bq. This value can ring in the spectrum, their location and their per- be changed on user’s request. centage in the spectrum. It can be then a basis for Exceeding the alarm threshold of radiation determining the type of isotope which caused the around the gate, is a signal to carry out prelimi- alarm threshold crossing. The position of the nary analysis of the radiation source (energy). The peaks can be also checked manually by changing second measuring channel containing a simple the position of two cursors on the spectrum im- analyser of the pulses amplitude is used. The op- age. eration of this system can be observed on the com- The basic operational parameters of the gate puter screen when you run advanced panel and Mobile dosimetric gate is a sensitive detector of X- and gamma radiation in its surrounding from 50 keV energy. Detection area depends on the energy and intensity of the radiation, but for the most commonly used isotopes in industry and medicine with an average activity over 200 μCi, is about 2 m around the gate (if there are no natural or artificial screens between the gate and the source of radiation). Efficiency of indications of the Gate for different incident radiation energies equals: over 90% for 1200 keV, over 60% for 660 keV and about 30% for 60 keV. Current measurement results of the gate can be received and registered on a computer using Wi-Fi wireless communication. The developed system allows different ways of viewing the results from Rys.4. The measurement of dosimetric gate B_DOZ:A001 different periods of time. 60 ca. with Co source 1 μCi: A – background radiation, B – The gate turns the sound and light signalling, source at a distance of 30 cm, C – source at a distance of 50 when the radiation in surrounding area increases cm from the centre of the probe. A, C – 5 s measurements, B – 1 s measurements. by 100 Bq in relation to the fixed background. Then, the 1 s long measurements are made and the choose the option “Collect spectrum”. The image results are transmitted to the computer with the of the spectrum changes every 5 s and after 1 min same intervals. (depending on the energy and the intensity of the When the computer is disconnected from the radiation reaching the gate’s head) it shows the network, the counts exceeding the background main peaks of the radiation source. The device are stored in the gate’s local memory and send to periodically calculates, for the main peaks occur- the computer when the connection is established. 112 LABORATORY OF NUCLEAR CONTROL SYSTEMS AND METHODS Several gates placed in different locations can References be connected via Wi-Fi network with a single com- [1]. Bramka dozymetryczna typ BD-01. www.polonizot.pl/ puter creating a network monitoring bd-01.php (in Polish). It is ensured that the continuous operation of [2]. Świstowski E., Mirowicz J., Urbański P., Pieńkos J.: mobile dosimetric gate in normal conditions should Dosimetric gate DSP-15. In: INCT Annual Report 2006. be equal to about 10 to 14 days without charging Institute of Nuclear Chemistry and Technology, War- the batteries. There is a possibility of connecting szawa 2007, pp. 158-159. the gate to the solar batteries power supply. [3]. Stacjonarne monitory do kontroli pojazdów VM 250AG/VM 250AGN. www.polon-alfa.pl/produkty/ Mobile dosimetric gate was developed and made aparatura-dozymetryczna/ (in Polish). within the project “New generation of intelligent [4]. Jakowiuk A., Pieńkos P., Kowalska E.: Wireless system radiometric tools with wireless data transmission” for radiometric measurements. Nukleonika, in press. co-financed by the European Union from the Euro- pean Regional Development Found. PUBLICATIONS IN 2011 113

PUBLICATIONS IN 2011

ARTICLES

1. Abbas K., Cydzik I., Simonell F., Krajewski S., Kasperek A., Bilewicz A. Cyclotron production of 44Sc – new radionuclide for PET technique. Journal of Labelled Compounds and Radiopharmaceuticals, 54, S1, S53 (2011). 2. Apel P.Yu., Blonskaya I.V., Orelovitch O.L., Ramirez P., Sartowska B.A. Effect of nanopore geometry on ion current rectification. Nanotechnology, 22, 175302 (13 p.) (2011) (DOI: 10.1088/0957-4484/22/17/175302). 3. Barlak M., Piekoszewski J., Werner Z., Sartowska B., Pisarek M., Waliś L., Starosta W., Kolitsch A., Groetzchel R., Bocheńska K., Pochrybniak C. Modes of the use of high intensity plasma beams for ceramic surface modification. Surface & Coatings Technology, 206, 916-919 (2011). 4. Bojanowska-Czajka A., Nichipor H., Drzewicz P., Szostek B., Gałęziowska A., Męczyńska S., Kruszewski M., Zimek Z., Nałęcz-Jawecki G., Trojanowicz M. Radiolytic decomposition of pesticide carbendazim in waters and wastes for environmental protection. Journal of Radioanalytical and Nuclear Chemistry, 289, 303-314 (2011). 5. Brzóska K., Sochanowicz B., Siomek A., Oliński R., Kruszewski M. Alternations in the expression of genes related to NF-κB signaling in liver and kidney of CuZnSOD-deficient mice. Molecular and Cellular Biochemistry, 353, 151-157 (2011). 6. Brzóska K., Stępkowski T.M., Kruszewski M. Putative proto-oncogene Pir expression in significantly up-regulated in the spleen and kidney of cytosolic superoxide dismutase-deficient mice. Redox Report, 16, 3, 129-133 (2011). 7. Chatgilialoglu C., D’Angelantonio M., Kciuk G., Bobrowski K. New insights into the reaction paths of hydroxyl radicals with 2’-deoxyguanosine. Chemical Research in Toxicology, 24, 2200-2206 (2011). 8. Chmielewska D., Gryczka U., Migdał W., Ignatowicz S. Application of radiation methods to preservation of cultural heritage. Journal of Entomological and Acarological Research, Series II, 43, 2, 237-244 (2011). 9. Chmielewski A.G. Chemistry for the nuclear energy of the future. Nukleonika, 56, 3, 241-249 (2011). 10. Chmielewski A.G. Electron accelerators for environmental protection. Reviews of Accelerator Science and Technology, 4, 149-161 (2011). 11. Chmielewski A.G. Ionizing radiation as a tool to protect environment. Annales Universitatis Mariae Curie-Skłodowska, Sectio AAA Physica, 66, 117-124 (2011). 12. Chmielewski A.G. Projekt atomowy – pierwsza elektrownia jądrowa w Polsce (The atomic project – the first power station in Poland). W Pionie i na Poziomie. Aktualności ULMA Construction Polska SA, 1, [3] p. (2011). 13. Chmielewski A.G. Przyszłość energetyczna świata i Polski (The future of energy in the world and Poland). Chemia w Szkole, 4, 6-21 (2011). 114 PUBLICATIONS IN 2011

14. Chmielewski A.G. Success of flue gas cleaning by electron beam and other applications of radiation processing in Poland. Radiation & Industries, 130, 15-19 (2011), in Japanese. 15. Chmielewski A.G., Urbaniak A., Zalewski M.K., Roubinek O.K., Harasimowicz M., Krzywda R., Zalewski M. Wzbogacanie biogazu w metan w kaskadzie modułów membranowych (Biogas enrichment in methane with membrane cascade). Inżynieria i Aparatura Chemiczna, 5, 24-25 (2011). 16. Cieślik E., Walkowska I., Molina Ruiz J., Cieślik I., Migdał W. The level of selected minerals and cadmium in chicken livers in dependence of age. Annals of Nutrition & Metabolism, 58, S3, 419 (2011). 17. Danish M., Ghafoor S., Ahmad N., Starosta W., Leciejewicz J. (Dimethyl sulfoxide-κO)trimethyl(2-methyl-3,5-dinitrobenzoato-κO1)tin(IV). Acta Crystallographica Section E, 67, m923 + [7] p. (2011). 18. Danish M., Ghafoor S., Ahmad N., Starosta W., Leciejewicz J. (Methanol-κO)(2-methyl-3,5-dinitrobenzoato-κO)triphenyltin(IV). Acta Crystallographica Section E, 67, m519 + [9] p. (2011). 19. Deptuła A., Miłkowska M., Łada W., Olczak T., Wawszczak D., Smoliński T., Zaza F., Brykała M., Chmielewski A.G., Goretta K.C. Sol-gel processing of silica nuclear waste glasses. New Journal of Glass Ceramics, 1, 105-111 (2011). 20. Duchiewicz J., Dobrucki A., Francik A., Duchiewicz T., Stachowicz W., Oleś T. Two-channel EPR spectrometer for quantitative measurements in relation to reference sample. Elektronika, 11, 106-110 (2011). 21. Duchiewicz J., Dobrucki A., Francik A., Sadowski A., Duchiewicz T., Stachowicz W., Kupriya- nova G. The 2-channel EPR spectrometer Radioman SE/X-254x for relative quantitative measurements. Elektronika, 11, 101-103 (2011). 22. Dybczyński R.S., Kulisa K. Unusual elution sequence of rare earth elements (REE) in some ion chromatographic systems and the effect of temperature. Separation Science and Technology, 46, 1767-1775 (2011). 23. Głuszewski W., Zagórski Z.P., Tran Q.K., Cortella L. Maria Skłodowska-Curie – the precursor of radiation sterilization methods. Analytical & Bioanalytical Chemistry, 400, 1577-1582 (2011). 24. Gniazdowska E., Koźmiński P. Towards substance P labeling with the ‘4+1’ technetium-99m mixed-ligand complexes. Journal of Labelled Compounds and Radiopharmaceuticals, 54, S1, S327 (2011). 25. Gniazdowska E., Koźmiński P., Fuks L. Lapatinib labeled with technetium-99m complexes as molecular imaging radiopharmaceuticals. Nuklearmedizin, 6, A175 (2011). 26. Hug F., Danish M., Starosta W., Leciejewicz J. trans-Bis(3-hydroxypyridine-κN)-diiodidoplatinum(II) dimethyl sulfoxide disolvate. Acta Crystallographica Section E, 67, m721 + [7] p. 27. Kaniewski J.T. Odpady promieniotwórcze z elektrowni jądrowych (Radioactive waste from nuclear power stations). Postępy Techniki Jądrowej, 54, 4, 2-12 (2011). 28. Kapka-Skrzypczak L., Cyranka M., Kruszewski M., Turski W.A. Środki ochrony roślin a zdrowie rolników – biomarkery oraz możliwości ich wykorzystania do oceny eks- pozycji na pestycydy (Pesticides and the health of farmers – biomarkers and the possibilities of their use to evaluate pesticide exposure). Medycyna Ogólna i Nauki o Zdrowiu, 17, 1, 28-32 (2011). PUBLICATIONS IN 2011 115

29. Kapka-Skrzypczak L., Cyranka M., Skrzypczak M., Kruszewski M. Biomonitoring and biomarkers of organophosphate pesticides exposure – state of the art. Annals of Agricultural and Environmental Medicine, 18, 2, 294-303 (2011). 30. Kapka-Skrzypczak L., Kulpa P., Sawicki K., Cyranka M., Wojtyła A., Kruszewski M. Legal hight – legal aspects and legislative solutions. Annals of Agricultural and Environmental Medicine, 18, 2, 304-309 (2011). 31. Kapka-Skrzypczak L., Niedźwiecka J., Cyranka M., Kruszewski M.K., Skrzypczak M., Wojtyła A. Nutrigenetyka – perspektywy żywienia zindywidualizowanego (Nutrigenetics – perspectives of personalized nutrition). Pediatric Endocrinology, Diabetes and Metabolism, 17, 4, 222-226 (2011). 32. Kapka-Skrzypczak L., Niedźwiecka J., Cyranka M., Skrzypczak M., Kruszewski M.K. Zespół metaboliczny a stres oksydacyjny – możliwości dietoterapii (The metabolic syndrome and oxidative stress – possibilities of dietotherapy). Medycyna Środowiskowa/Environmental Medicine, 14, 2, 57-63 (2011). 33. Koźmiński P., Gniazdowska E. Ghrelin peptide labelled with mono- or trivalent technetium-99m complexes. Journal of Labelled Compounds and Radiopharmaceuticals, 54, S1, S380 (2011). 34. Koźmiński P., Gniazdowska E. Technetium-99m(I), ‘2+1’, and technetium-99m(III), ‘4+1’, mixed-ligand complexes conjugated to Ghre- lin. Nuklearmedizin, 6, A1 (2011). 35. Koźmiński P., Gniazdowska E., Fuks L., Kowalska S. ‘2+1’ Tricarbonyltechnetium(I)/tricarbonylrhenium(I) mixed-ligand complexes with methyl thiosalicylate and isocyanide ligands as potential precursors of radiopharmaceuticals. Applied Radiation and Isotopes, 69, 436-442 (2011). 36. Krajewski S.A., Bilewicz A., Łyczko K. Synthesis of 105Rh carbonyl and ferrocene complexes for targeted radionuclide therapy. Journal of Labelled Compounds and Radiopharmaceuticals, 54, S1, S362 (2011). 37. Krygowski T.M., Ozimiński W.P., Ramsden C.A. Sigma- and pi-electron structure of aza-azoles. Journal of Molecular Modeling, 17, 1427-1433 (2011). 38. Kunstler J.-U., Bergmann R., Gniazdowska E., Koźmiński P., Walther M., Pietzsch H.-J. Impact of functionalized coligands on the pharmacokinetics of 99mTc(III) ‘4+1’ mixed-ligand complexes conjugated to bombesin. Journal of Inorganic Biochemistry, 105, 1383-1390 (2011). 39. Lewandowska A., Hug G.L., Hörner G., Pogocki D., Kazmierczak F., Marciniak B. Intramolecular H-atom transfer reactions in rigid peptides – correlated solvent and structural effects. Canadian Journal of Chemistry, 89, 266-278 (2011). 40. Lewandowska H., Kalinowska M., Brzóska K., Wójciuk K., Wójciuk G., Kruszewski M. Nitrosyl iron complexes – synthesis, structure and biology. Dalton Transactions, 40, 8273-8289 (2011). 41. Machaj B., Mirowicz J., Kowalska E. Large area scintillation detector for dosimetric stand with improved light collection. Nukleonika, 56, 4, 317-321 (2011). 42. Machaj B., Mirowicz J., Kowalska E. Performance of a plastic scintillator and GM pancake tubes as alpha and beta contamination detectors in dosimetric stand. Nukleonika, 56, 1, 53-56 (2011). 43. Majkowska-Pilip A., Bilewicz A. Macrocyclic complexes of scandium radionuclides as precursors for diagnostic and therapeutic radiopharmaceuticals. Journal of Inorganic Biochemistry, 105, 313-320 (2011). 116 PUBLICATIONS IN 2011

44. Melski K., Kubera H., Głuszewski W., Zimek Z. Effect of ionizing radiation on the properties of PLA packaging materials. Nukleonika, 56, 1, 65-69 (2011). 45. Miśkiewicz A., Velizarov S. Effect of molecular mass on boron-doped diamond anodic mineralization of water-soluble organic polymers. Separation and Purification Technology, 83, 166-172 (2011). 46. Neves M., Teixeira F.C., Antunes I., Majkowska A., Gano L., Santos A.C. Chemical and biological evaluation of 153Sm and 46/47Sc complexes of indazolebisphosphonates for targeted radiotherapy. Applied Radiation and Isotopes, 69, 80-84 (2011). 47. Orlikowski L.B., Migdał W., Ptaszek M., Gryczka U. Effectiveness of electron beam irradiation in the control of some soilborne pathogens. Nukleonika, 56, 4, 357-363 (2011). 48. Owczarek M., Jakubas R., Bator G., Pawlukojć A., Baran J., Przesławski J., Medycki W. Vibrational and thermodynamic properties and molecular motions in the incommensurate crystal of morpholinium tetrafluoroborate studied by 1H NMR. Chemical Physics, 381, 11-20 (2011). 49. Ozimiński W.P., Krygowski T.M.

Aromatization of rings of fulvene and heptafulvene due to the through space interactions in [34]3,4,6,6-fulvene-4,5,8,8-heptafulvene-cyclophane. Computational and Theoretical Chemistry, 965, 240-243 (2011). 50. Ozimiński W.P., Krygowski T.M. Natural bond orbital approach to the transmission of substituent effect through the fulvene and benzene ring systems. Journal of Molecular Modeling, 17, 565-572 (2011). 51. Palige J., Majkowska A., Herdzik I., Ptaszek S. 68Ge/68Ga radioisotope generator as a source of radiotracers for water flow investigations. Nukleonika, 56, 1, 77-80 (2011). 52. Palige J., Rudniak L., Dobrowolski A., Zalewski M., Chmielewski A.G. Optymalizacja parametrów mieszania biozawiesiny w fermentorze z wykorzystaniem metody CFD (Op- timization of biomass suspention miting in fermentor with CFD method). Inżynieria i Aparatura Chemiczna, 5, 82-83 (2011). 53. Papagiannopoulou D., Tsoukalas C., Makris G., Raptopoulou C.P., Psycharis V., Leondiadis L., Gniazdowska E., Koźmiński P., Fuks L., Pelecanou M., Pirmettis I., Papadopoulos M.S. 1 99m 188 Histidine derivatives as tridentate chelators for the fac-[M (CO)3] (Re, Tc, Re) core: Synthesis, structural characterization, radiochemistry and stability. Inorganica Chimica Acta, 378, 333-337 (2011). 54. Pawlukojć A., Sawka-Dobrowolska W., Bator G., Sobczyk L., Grech E., Nowicka-Scheibe J. The structure and vibrational spectra of the 2,5-dimethylpyrazine (2,5-DMP) 1:1 adduct with 2,5-dichloro- -3,6-dihydroxy-p-benzoquinone (CLA). Chemical Physics, 380, 34-38 (2011). 55. Persson I., Łyczko K., Lundberg D., Eriksson L., Płaczek A. Coordination chemistry study of hydrated and solvated lead(II) ions in solution and solid state. Inorganic Chemistry, 50, 1058-1072 (2011). 56. Piekoszewski J., Sartowska B., Barlak M., Konarski P., Dąbrowski L., Starosta W., Waliś L., Werner Z., Pochrybniak C., Bocheńska K., Stoch P., Szymczyk W. Improvement of high temperature oxidation resistance of AISI 316L stainless steel by incorporation of Ce-La elements using intense pulses plasma beams. Surface & Coatings Technology, 206, 854-858 (2011). 57. Poboży E., Król E., Wójcik L., Wachowicz M., Trojanowicz M. HPLC determination of perfluorinated carboxylic acids with fluorescence detection. Microchimica Acta, 172, 409-417 (2011). PUBLICATIONS IN 2011 117

58. Polkowska-Motrenko H., Chajduk E., Danko B. Instrumental neutron activation analysis (INAA) for steel analysis and certification. Nukleonika, 56, 4, 311-315 (2011). 59. Przybytniak G., Kornacka E.M., Fuks L. Functionalization of polyamide surface by radiation-induced grafting of N-vinyl-pyrrolidone and acryl- amide. Journal of Polymer Research, 18, 541-547 (2011). 60. Sartowska B., Piekoszewski J., Waliś L., Barlak M., Starosta W., Pochrybniak C., Bocheńska K. Structure and composition of scales formed on AISI 316 L steel alloyed with Ce/La using high intensity plasma pulses after oxidation in 1000oC. Acta Physica Polonica A, 120, 1, 83-86 (2011). 61. Sartowska B., Piekoszewski J., Waliś L., Senatorski J., Barlak M., Starosta W., Pochrybniak C., Pokorska I. Improvement of tribological properties of stainless steel by alloying its surface layer with rare earth elements using high intensity pulsed plasma beams. Surface & Coating Technology, 205, S2, s124-s127 (2011). 62. Schlegel-Zawadzka M., Osielczak M., Migdał W., Rokitka M. Hiking in Tatra mountains and eating habits of Polish tourists. Annals of Nutrition & Metabolism, 58, S3, 169 (2011). 63. Sommer S. Informacje o 14. Międzynarodowym Kongresie Badań Radiacyjnych (ICRR 2011), Warszawa, 28.08.2011 – 1.09.2011 (Information about 14. International Congress of Radiation Reasearch in Warsaw, 28.08.2011 – 1.09.2011). Eko-atom. Kwartalnik popularnonaukowy, 3, 10-11, 99-106 (2011) 64. Starosta W., Leciejewicz J. catena-Poly[[(6-carboxypyrazine-2-carboxylato)lithium]-μ-aqua]. Acta Crystallographica Section E, 67, m1708-m1709 + [7] p. (2011). 65. Starosta W., Leciejewicz J. catena-Poly[[(aqualithium)-μ-3-carboxypyrazine-2-carboxylato-κ4O2,N1:O3:N4]monohydrate]. Acta Crystallographica Section E, 67, m1133-m1134 + [9] p. (2011). 66. Starosta W., Leciejewicz J. catena -Poly[[μ2-aqua-diaquabis(μ4-pyridazine-3,6-dicarboxylato)tetra-lithium] monohydrate]. Acta Crystallographica Section E, 67, m1455-m1456 + [10] p. (2011). 67. Starosta W., Leciejewicz J. 2O O O Poly[aqua(μ3-pyridazine-4-carboxylato-κ : : ’)lithium]. Acta Crystallographica Section E, 67, m425-m426 + [8] p. (2011). 68. Starosta W., Leciejewicz J.

Poly[di-μ-aqua-μ4-(pyrazine-2,5-dicarboxylato)-dilithium(I)]. Acta Crystallographica Section E, 67, m50-m51 + [8] p. 69. Starosta W., Leciejewicz J.

Poly[di-μ2-aqua-μ2-(5-methylpyrazine-2-carboxylato)-(5-methylpyrazine-2-carboxylato)-μ3-nitrato- trilithium]. Acta Crystallographica Section E, 67, m1000 + [11] p. (2011). 70. Starosta W., Leciejewicz J. 2O O 2O O Poly[μ2-nitrato-κ : ’)(μ2-pyrimidinium-2-carboxylato-κ : ’)-lithium(I)]. Acta Crystallographica Section E, 67, m818 + [7] p. 71. Starosta W., Leciejewicz J. trans-Diaqua(pyridazine-3-carboxylato-κ2N2,O)lithium. Acta Crystallographica Section E, 67, m202 + [7] p. 72. Starosta W., Leciejewicz J. trans-Tetraaquabis(pyridazine-4-carboxylato-κO)magnesium(II) dihydrate. Acta Crystallographica Section E, 67, m316 + [7] p. 118 PUBLICATIONS IN 2011

73. Stępkowska A., Bieliński D.M., Przybytniak G. Application of electron beam radiation to modify crosslink structure in rubber vulcanizates and its tribological consequences. Acta Physica Polonica A, 120, 1, 53-55 (2011). 74. Stępkowski T.M., Kruszewski M.K. Molecular cross-talk between the NRF2/KEAP1 signaling pathway, autophagy, and apoptosis. Free Radical Biology and Medicine, 50, 1186-1195 (2011). 75. Szumiel I. Autophagy, reactive oxygen species and the fate of mammalian cells. Free Radical Research, 45, 3, 253-265 (2011). 76. Szumiel I. Co dała światu uparta Polka, czyli od narodzin chemii radiacyjnej po współczesną biologię molekularną (What did the adamant Pole offer to the world: from the emergence of radiation chemistry to the contemporary molecular biology). Kosmos. Problemy Nauk Biologicznych, 60, 1-2, 1-3 (2011). 77. Szumiel I., Foray N. Chromatin acetylation, β-amyloid precursor protein and its binding partner FE65 in DNA double strand break repair. Acta Biochimica Polonica, 58, 1, 11-18 (2011). 78. Uzal N., Jaworska A., Miśkiewicz A., Zakrzewska-Trznadel G., Cojocaru C. Optimization of Co2+ ions removal from water solutions via polymer enhanced ultrafiltration with application of PVA and sulfonated PVA as complexing agents. Journal of Colloid and Interface Science, 362, 615-624 (2011). 79. Walo M., Przybytniak G., Nowicki A., Świeszkowski W. Radiation-induced effects in gamma-irradiated PLLA and PCL at ambient and dry ice temperatures. Journal of Applied Polymer Science, 122, 375-383 (2011). 80. Werner Z., Pochrybniak C., Barlak M., Piekoszewski J., Korman A., Heller R., Szymczyk W., Bocheńska K. Implanted manganese redistribution in Si after He+ irradiation and hydrogen pulse plasma treatment. Nukleonika, 56, 1, 5-8 (2011). 81. Witman S., Pawelec A. Technologie plazmowe w ochronie środowiska (Plasma technologies in environmental protection). Przegląd Przemysłowy i Gospodarczy, 5-6, 57 (2011). 82. Wojewódzka M., Lankoff A., Dusińska M., Brunborg G., Czerwińska J., Iwaneńko T., Stępkowski T., Szumiel I., Kruszewski M. Treatment with silver nanoparticles delays repair of X-ray induced DNA damage in HepG2 cells. Nukleonika, 56, 1, 29-33 (2011). 83. Yasodha V., Govindarajan S., Starosta W., Leciejewicz J. New metal-organic framework solids built from barium and isoelectronic chelidamic and chelidonic acids. Journal of Chemical Crystallography, 41, 1988-1997 (2011). 84. Zagórski Z. Nukleonika militarna – nieznane fakty z historii najnowszej (Military nucleonics – unknown facts from the modern history). Postępy Techniki Jądrowej, 54, 2, 22-25 (2011). 85. Zagórski Z.P. Zimna fuzja raz jeszcze. [List do Redakcji] (Cold fusion once more – A Letter to the Editors). Wiadomości Chemiczne, 1-2, 157-161 (2011). 86. Zagórski Z.P., Rajkiewicz M., Głuszewski W. Radiacyjna modyfikacja elastomerów (Radiation modification of elastomers). Przemysł Chemiczny, 6, 1191-1194 (2011). 87. Zhydachevskii Ya., Berkowski M., Warchoł S., Suchocki A.

Dosimetric properties of the 570 K thermoluminescence peak of YAlO3:Mn crystals. Radiation Measurements, 46, 494-497 (2011). PUBLICATIONS IN 2011 119 BOOKS

1. Monitoring, control and effects of air pollution. Ed. A.G. Chmielewski. InTech, Rijeka, Croatia 2011, 254 p. 2. Radiotracer applications in wastewater treatment plants. Eds. L.E.B. Brandao, P. Brisset, A. Chmielewski, S. Genders, J.M. Griffith, J.-H. Jin, I.H. Khan, R. Kjell- strand, J. Palige, A. Pandit, H.J. Pant, Sung-Hee Jung, J. Thereska. Training Course Series no. 49. IAEA, Vienna 2011, 93 p. 3. Samczyński Z., Dybczyński R.S., Polkowska-Motrenko H., Chajduk E., Pyszynska M., Danko B., Czerska E., Kulisa K., Doner K., Kalbarczyk P. Preparation and certification of the new Polish reference material: Oriental Basma Tobacco Leaves (INCT-OBTL-5) for inorganic analysis. Institute of Nuclear Chemistry and Technology, Warszawa 2011, 87 p. 4. Samczyński Z., Dybczyński R.S., Polkowska-Motrenko H., Chajduk E., Pyszynska M., Danko B., Czerska E., Kulisa K., Doner K., Kalbarczyk P. Preparation and certification of the new Polish reference material: Oriental Virginia Tobacco Leaves (INCT-PVTL-6) for inorganic analysis. Institute of Nuclear Chemistry and Technology, Warszawa 2011, 88 p. 5. Sun Y. Air organic pollutants destruction by using electron beam technology. Experimental and theoretical study. LAP Lambert Academic Publishing, 2011, 152 p.

CHAPTERS IN BOOKS

1. Bilewicz A., Bobrowski K., Chmielewski A.G., Marcinek A., Narbutt J., Przybytniak G., Szam- rej-Foryś I. Chemia radiacyjna, chemia jądrowa i radiochemia (Radiation chemistry, nuclear chemistry and radiochemistry). In: Misja nauk chemicznych. Ed. B. Marciniec. Wydawnictwo Nauka i Innowacje, Warszawa 2011, p. 83-108. 2. Bobrowski K. Radiation-induced radicals and radical ions in amino AIDS and peptides. In: Selectivity, control, and fine tuning in high-energy chemistry. Eds. D.V. Stass, V.I. Feldman. Research Signpost, Trivandrum 2011, p. 41-68. 3. Boguski J., Przybytniak G., Mirkowski K., Bojanowska-Czajka A., Nowicki A. Starzenie radiacyjne kabli w elektrowniach jądrowych – wpływ antyutleniacza Irganox 1035 (Radiation ageing of cables in nuclear power plants – influence of Irganox1035 antioxidant). In: Modyfikacja polimerów. Stan i perspektywy w roku 2011. Ed. R. Steller. Wydawnictwo TEMPO s.c., Wrocław 2011, p. 207-210. 4. Bojanowska-Czajka A. Zastosowanie promieniowania jonizującego do rozkładu wybranych zanieczyszczeń organicznych wód i ścieków (Application of ionizing radiation to the decomposition of selected organic impurities in waters and professional sources). In: Rola dokonań młodych naukowców a możliwości osiągnięcia sukcesu naukowego i zawodowego. Vol. 2. Ed. M. Kuczer. Creativetime, Kraków 2011, p. 107-111. 5. Brandenburg R., Barankova H., Bardos L., Chmielewski A.G., Dors M., Grosch H., Hołub M., Laan M., Mizeraczek J., Pawelec A., Stamate E. Plasma-based depollution of exhausts: principles, state of the art, and future prospects. In: Monitoring, control and effects of air pollution. Ed. A.G. Chmielewski. InTech, Rijeka, Croatia 2011, p. 229-254. 6. Chajduk E., Doner K., Polkowska-Motrenko H., Bilewicz A. Opracowanie układu rozdzielczego Se-As i jego wykorzystanie w generatorze radionuklidów 72Se/72As (Elaboration of a Se-As separation system and its use in a 72Se/72As generator). In: Rola dokonań młodych naukowców a możliwości osiągnięcia sukcesu naukowego i zawodowego. Vol. 2. Ed. M. Kuczer. Creativetime, Kraków 2011, p. 128-130. 120 PUBLICATIONS IN 2011

7. Dybczyński R. Neutronowa analiza aktywacyjna i jej zastosowania (Neutron activation analysis and its applications). In: Nauka i przemysł – metody spektroskopowe w praktyce, nowe wyzwania i możliwości. Ed. Z. Hubicki. Uniwersytet M. Curie-Skłodowskiej w Lublinie, Lublin 2011, p. 12-25. 8. Hęclik K., Balawejder M., Kisała J., Mazurkiewicz W., Pogocki D. Betulina i jej pochodne – triterpeny pochodzenia naturalnego o różnorodnej aktywności farmakologicz- nej (Betulin and its derivatives – triterpenes of natural origin and different pharmacological activity). In: Nowoczesne metody analizy surowców rolniczych. Eds. Cz. Puchalski, G. Bartosz. Uniwersytet Rze- szowski, Rzeszów 2011, p. 523-533. 9. Jakowiuk A. Nowa generacja inteligentnych urządzeń radiometrycznych z bezprzewodową teletransmisją informacji (New generation of inteligent radiometric facilitaties with a wireless transmission of information). In: Nowe projekty rozwojowe. Wybrane projekty realizowane w ramach poddziałania 1.3.1 programu „Innowacyjna gospodarka”. OPI, Warszawa 2011, p. 216-217. 10. Kalbarczyk P., Polkowska-Motrenko H.

Optymalizacja procesu rozpuszczania ThO2 napromienionego w reaktorze jądrowym (Optimization of the dissolution process of ThO2 irradiated in a nuclear reactor). In: Rola dokonań młodych naukowców a możliwości osiągnięcia sukcesu naukowego i zawodowego. Vol. 2. Ed. M. Kuczer. Creativetime, Kraków 2011, p. 161. 11. Kasztovszky Z., Kunicki-Goldfinger J. Applicability of prompt gamma activation analysis to glass archaeometry. In: Proceedings of the 37. International Symposium on Archaeometry. Ed. I. Turbanti-Memmi. Sprin- ger-Verlag, Berlin-Heidelberg 2011, p. 83-90. 12. Kruszewski M., Brzóska K., Brunborg G., Asare N., Dobrzyńska M., Dusińska M., Fjellsbø L.M., Georgantzopoulou A., Gromadzka-Ostrowska J., Gutleb A., Lankoff A., Magdolenová Z., Pran E.R., Rinna A., Instanes C., Sandberg W.J., Schwarze P., Stępkowski T., Wojewódzka M., Refs- nes M. Toxicity of silver nanomaterials in higher eukaryotes. In: Advances in molecular toxicology. Vol. 5. Ed. J.C. Fishbein. Elsevier B.V., Amsterdam 2011, p. 180-218. 13. Nowicki A., Przybytniak G., Mirkowski K. Opracowanie kleju termotopliwego do instalacji ciepłowniczych (Developing of hot-melt adhesive for hot-water installation). In: Modyfikacja polimerów. Stan i perspektywy w roku 2011. Ed. R. Steller. Wydawnictwo TEMPO s.c., Wrocław 2011, p. 663-666. 14. Polkowska-Motrenko H., Kalbarczyk P., Chajduk E., Dudek J. Oznaczanie uranu w torze aktywowanym neutronami w reaktorze Maria (Determination of uranium in thorium neutron-activated in the reactor Maria). In: Badania materiałowe na potrzeby elektrowni i przemysłu energetycznego. XVIII seminarium naukowo-techniczne, Zakopane, Poland, 28-30.06.2011. IAE, Otwock-Świerk 2011, p. 127-132. 15. Przybytniak G., Kornacka E.M., Fuks L., Walo M., Łyczko K., Mirkowski K. Functionalization of polymer surfaces by radiation-induced grafting for separation of heavy metal ions. In: Report of the 3. RCM on “Development of novel adsorbents and membranes by radiation-induced grafting for selective separation purposes”, Budapest, Hungary, 6-10 December 2010. IAEA, Vienna 2011, p. 212-230. 16. Wójciuk K., Lewandowska H., Lewandowski W. Zastosowanie radiolizy impulsowej oraz metod spektroskopowych w badaniach właściwości antyutlenia- jących polifenoli występujących w żywności (Use of pulse radiolysis and spectroscopic method in the studies of antioxidant properties of polyphenols). In: Nauka i przemysł. Metody spektroskopowe w praktyce, nowe wyzwania i możliwości. Uniwersytet M. Curie-Skłodowskiej w Lublinie, Lublin 2011, p. 214-222. 17. Zalewski M., Chmielewski A.G., Palige J., Roubinek O., Wawryniuk K., Usidus J., Kryłowicz A., Chrzanowski K. Zagospodarowanie odpadów roślinnych i spożywczych do produkcji biogazu (Management of vegetable and food waste for biogas production). In: Człowiek a środowisko – w poszukiwaniu możliwej symbiozy. Kraków 2011, p. 151-157. PUBLICATIONS IN 2011 121 THE INCT PUBLICATIONS

1. INCT Annual Report 2010. Institute of Nuclear Chemistry and Technology, Warszawa 2011, 161 p. 2. Lazurik V.M., Lazurik V.T., Popov G., Rogov Yu., Zimek Z. Information system and software for quality control of radiation processing. International Atomic Energy Agency/Collaborating Centre for Radiation Processing and Industrial Dosimetry (Institute of Nuclear Chemistry and Technology), Warszawa 2011, 232 p. 3. Samczyński Z., Dybczyński R.S., Polkowska-Motrenko H., Chajduk E., Pyszynska M., Danko B., Czerska E., Kulisa K., Doner K., Kalbarczyk P. Preparation and certification of the new Polish reference material: Oriental Basma Tobacco Leaves (INCT-OBTL-5) for inorganic trace analysis. Institute of Nuclear Chemistry and Technology, Warszawa 2011, 87 p. 4. Samczyński Z., Dybczyński R.S., Polkowska-Motrenko H., Chajduk E., Pyszynska M., Danko B., Czerska E., Kulisa K., Doner K., Kalbarczyk P. Preparation and certification of the new Polish reference material: Polish Virginia Tobacco Leaves (INCT-PVTL-6) for inorganic trace analysis. Institute of Nuclear Chemistry and Technology, Warszawa 2011, 88 p. 5. Polkowska-Motrenko H., Chajduk E., Dudek J., Skwara W., Pyszynska M. Badanie biegłości ROŚLINY 10 – oznaczanie zawartości As, Cd, Cr, Cu, Hg, Pb, Se i Zn w cebuli suszo- nej (Allium cepa) (Proficiency test PLANTS 10 – determination As, Cd, Cr, Cu, Hg, Pb, Se and Zn in dry onion powder). Instytut Chemii i Techniki Jądrowej, Warszawa 2011. Raporty IChTJ. Seria B nr 1/2011, 28 p. 6. Sadowska M.W., Stachowicz W. Efektywność różnych procedur izolacji minerałów w metodzie termoluminescencji stosowanej do identyfikacji napromieniowanej żywności (Effectiveness of different procedures for mineral separation in thermoluminescence method adapted for the detection of irradiated food). Instytut Chemii i Techniki Jądrowej, Warszawa 2011. Raporty IChTJ. Seria B nr 2/2011, 15 p. 7. Zimek Z., Przybytniak G., Nowicki A., Mirkowski K., Roman K., Bułka S., Skajster J., Pujdak D. Uruchomienie modelowego urządzenia do przewijania kabli i przewodów elektrycznych w procesie obrób- ki radiacyjnej w akceleratorze IŁU-6 (Testing set up for electrical cables and wires rewinding during radiation processing based on ILU-6 electron accelerator). Instytut Chemii i Techniki Jądrowej, Warszawa 2011. Raporty IChTJ. Seria B nr 3/2011, 44 p.

CONFERENCE PROCEEDINGS

1. Alaimo G., Alessi S., Enea D., Pitarresi G., Przybytniak G., Spadaro G., Tumino D. The durability of carbon fiber/epoxy composites under hydrothermal ageing. XII DBMC – International Conference on Durability of Building Materials and Components, Porto, Portugal, 12-15.04.2011, 8 p. 2. Chmielewski A.G., Berejka A.J. Electron accelerators: a powerful tool for polymer processing. Thermoset 2011: From Monomers to Components. Proceedings of the 2. International Conference on Thermosets, Berlin, Germany, 21-23.09.2011, p. 29-31. 3. Chmielewski A.G., Pawelec A., Witman S.

Technologia jednoczesnego usuwania SO2 i NOx z gazów odlotowych przy użyciu wiązki elektronów (Si- multaneous technology of SO2 and NOx removal from exhaust gases using electron beam). IX Konferencja „Dla miasta i środowiska – Problemy unieszkodliwiania odpadów”, Warszawa, Poland, 28.11.2011, p. 134-137. 4. Chmielewski A.G., Urbaniak A., Harasimowicz M., Zalewski M.K., Wawryniuk K., Roubinek O.K. Wzbogacanie biogazu w metan w kaskadzie modułów membranowych (Biogas enrichment in methane with using mobile membrane cascade). IX Konferencja „Dla miasta i środowiska – Problemy unieszkodliwiania odpadów”, Warszawa, Poland, 28.11.2011, p. 138-141. 122 PUBLICATIONS IN 2011

5. Chmielewski A.G., Urbaniak A., Zalewski M.K., Roubinek O.K., Wawryniuk K. Membranowa separacja biogazu uzyskanego podczas fermentacji i kofermentacji odpadów lignocelulozowych (Membrane separation of biogas produced in fermentation and co-fermentation of lignocellu- losic wastes). IX Konferencja „Dla miasta i środowiska – Problemy unieszkodliwiania odpadów”, Warszawa, Poland, 28.11.2011, p. 181-183. 6. Fuks L., Gniazdowska E., Koźmiński P., Mieczkowski J. Novel technetium and rhenium complexes with the N-heterocyclic aldehyde thiosemicarbazones – potential radiopharmaceuticals. 7. International Symposium on Technetium and Rhenium – Science and Utilization, July 4-8, 2011, Moscow, Russia. Book of proceedings. Eds. K.E. German, B.F. Myasoedov, G.E. Kodina, A.Ya. Maruk, I.D. Troshkina. Publishing House GRANITSA, Moscow 2011, p. 339-342. 7. Głuszewski W. Maria Skłodowska-Curie prekursorka metody radiacyjnej sterylizacji (Maria Skłodowska-Curie as precursor of the method of radiation sterilization). XI Szkoła Sterylizacji i Mikrobiologicznej Dekontaminacji Radiacyjnej, Warszawa, Poland, 20-21.10.2011, p. I(1-6). 8. Głuszewski W. Oddziaływanie promieniowania jonizującego na materię (Interaction of ionization radiation with matter). XI Szkoła Sterylizacji i Mikrobiologicznej Dekontaminacji Radiacyjnej, Warszawa, Poland, 20-21.10.2011, p. III(1-4). 9. Gniazdowska E., Koźmiński P., Bańkowski K. 99m 2 4 9 Tc-labelled vasopressin analog d(CH2)5[D-Tyr(Et ),Ile ,Eda ]AVP as a potential radiopharmaceutical for small-cell lung cancer (SCLC) imaging. 7. International Symposium on Technetium and Rhenium – Science and Utilization, July 4-8, 2011, Moscow, Russia. Book of proceedings. Eds. K.E. German, B.F. Myasoedov, G.E. Kodina, A.Ya. Maruk, I.D. Troshkina. Publishing House GRANITSA, Moscow 2011, p. 343-346. 10. Kałuska I. Czy szykują się jakieś zmiany w przepisach związanych ze sterylizacją radiacyjną? (Are the changes in rules of radiation sterilization in preparation?). XI Szkoła Sterylizacji i Mikrobiologicznej Dekontaminacji Radiacyjnej, Warszawa, Poland, 20-21.10.2011, p. XIX(1-2). 11. Kałuska I. Kwalifikacja procesowa ze szczegółowym omówieniem wyznaczania dawki sterylizacyjnej (Process qualification with particular discussion on the determination of sterilization dose). XI Szkoła Sterylizacji i Mikrobiologicznej Dekontaminacji Radiacyjnej, Warszawa, Poland, 20-21.10.2011, p. VIII(1-4). 12. Kałuska I., Bułka S. Analiza ryzyka procesu sterylizacji radiacyjnej (Analysis of the risk of radiation sterilization process). XI Szkoła Sterylizacji i Mikrobiologicznej Dekontaminacji Radiacyjnej, Warszawa, Poland, 20-21.10.2011, p. X(1-2). 13. Kornacka E.M. Rola opakowań w sterylizacji radiacyjnej (The role of package in radiation sterilization). XI Szkoła Sterylizacji i Mikrobiologicznej Dekontaminacji Radiacyjnej, Warszawa, Poland, 20-21.10.2011, p. IX(1-6). 14. Korzeniowska-Sobczuk A. Akredytowane Laboratorium Pomiarów Dawek Technologicznych (Accredited Laboratory for Measure- ments of Technological Doses). XI Szkoła Sterylizacji i Mikrobiologicznej Dekontaminacji Radiacyjnej, Warszawa, Poland, 20-21.10.2011, p. XVII(1-2). 15. Kruszewski M. Biologiczne działanie i ryzyko promieniowania jonizującego (Biological action and the risk of ionization radiation). XI Szkoła Sterylizacji i Mikrobiologicznej Dekontaminacji Radiacyjnej, Warszawa, Poland, 20-21.10.2011, p. IV(1-4). PUBLICATIONS IN 2011 123

16. Mehta K., Chmielewski A.G. Stacje sterylizacji radiacyjnej wyposażone w izotopowe źródła promieniowania gamma (Stations of radiation sterillization equipped with isotope sources of gamma radiation). XI Szkoła Sterylizacji i Mikrobiologicznej Dekontaminacji Radiacyjnej, Warszawa, Poland, 20-21.10.2011, p. XX(1-9). 17. Migdał W., Gryczka U. Mikrobiologiczna dekontaminacja radiacyjna ziół i przypraw. Przepisy Unii Europejskiej (Microbiologi- cal radiation decontamination of herbs and spices. Regulations of the European Union). XI Szkoła Sterylizacji i Mikrobiologicznej Dekontaminacji Radiacyjnej, Warszawa, Poland, 20-21.10.2011, p. XVIII(1-4). 18. Przybytniak G. Modyfikacja materiałów polimerowych pod wpływem promieniowania jonizującego (Modification of polymer materials under the influence of ionizing radiation). XI Szkoła Sterylizacji i Mikrobiologicznej Dekontaminacji Radiacyjnej, Warszawa, Poland, 20-21.10.2011, p. XIII(1-4). 19. Rafalski A. Kontrola dozymetryczna radiacyjnej sterylizacji wyrobów medycznych (Dosimetric inspection of radiation sterilization of medical appliances). XI Szkoła Sterylizacji i Mikrobiologicznej Dekontaminacji Radiacyjnej, Warszawa, Poland, 20-21.10.2011, p. VII(1-5). 20. Stachowicz W. Przegląd metod sterylizacji (A review of sterilization methods). XI Szkoła Sterylizacji i Mikrobiologicznej Dekontaminacji Radiacyjnej, Warszawa, Poland, 20-21.10.2011, p. II(1-14). 21. Stachowicz W. Samodzielne Laboratorium Identyfikacji Napromieniowanej Żywności (Laboratory for Detection of Ir- radiated Food). XI Szkoła Sterylizacji i Mikrobiologicznej Dekontaminacji Radiacyjnej, Warszawa, Poland, 20-21.10.2011, p. XVI(1-6). 22. Walo M. Nowe materiały polimerowe modyfikowane radiacyjnie (New polymeric materials modified by radiation). XI Szkoła Sterylizacji i Mikrobiologicznej Dekontaminacji Radiacyjnej, Warszawa, Poland, 20-21.10.2011, p. XIV(1-4). 23. Zakrzewska-Trznadel G., Frąckiewicz K., Miśkiewicz A., Zielińska K., Herdzik-Koniecko I., Szczygłów K., Wołkowicz S. Uranium supply from domestic resources in Poland. Nuclear 2011: 4. Annual International Conference on Sustainable Development through Nuclear Re- search and Education, Pitesti, Romania, 25-27.05.2011, Session I, p. 161-166. 24. Zakrzewska-Trznadel G., Miśkiewicz A. Membrane distillation as a method for liquid radioactive waste treatment. Nuclear 2011: 4. Annual International Conference on Sustainable Development through Nuclear Re- search and Education, Pitesti, Romania, 25-27.05.2011, Session II, p. 161-167. 25. Zalewski M., Chmielewski A.G., Palige J., Roubinek O., Wawryniuk K., Chrzanowski K., Kryłowicz A., Usidus J. Analiza pracy małej biogazowi dla przerobu traw i ich kiszonek (Analysis of operation of small biogas plant using grasses and their silage). IX Konferencja „Dla miasta i środowiska – Problemy unieszkodliwiania odpadów”, Warszawa, Poland, 28.11.2011, p. 142-144. 26. Zimek Z. Akceleratory elektronów. Zastosowania dla potrzeb sterylizacji radiacyjnej (Electron accelerators. Ap- plications for the need of radiation sterilization). XI Szkoła Sterylizacji i Mikrobiologicznej Dekontaminacji Radiacyjnej, Warszawa, Poland, 20-21.10.2011, p. VI(1-4). 124 PUBLICATIONS IN 2011 CONFERENCE ABSTRACTS

1. Abbas K., Cydzik I., Simonell F., Krajewski S., Majkowska-Pilip A., Kasperek A., Bilewicz A. Cyklotronowa produkcja 44Sc – nowego radionuklidu dla techniki PET (Cyclotron production of 44Sc – a new radionuclide for PET techniques). Ogólnopolska Konferencja Radiofarmaceutyczna, Łódź, Poland, 12-13.05.2011, p. 64. 2. Barlak M., Piekoszewski J., Werner Z., Sartowska B., Waliś L., Starosta W., Kierzek J., Bo- cheńska K., Heller R., Wilhelm R., Kolitsch A., Pochrybniak C., Kowalska E. High-temperature oxidation resistance of stainless steel doped with yttrium using ion implantation. NUTECH-2011 International Conference on Development and Applications of Nuclear Technologies, Kraków, Poland, 11-14.09.2011. Book of abstracts, p. 66. 3. Barlak M., Piekoszewski J., Werner Z., Sartowska B., Waliś L., Starosta W., Kierzek J., Bo- cheńska K., Heller R., Wilhelm R., Kolitsch A., Pochrybniak C., Kowalska E. Wettability of carbon and silicon carbide ceramics induced by their surface alloying with Ti, Zr and Cu elements using high intensity pulsed plasma beams. NUTECH-2011 International Conference on Development and Applications of Nuclear Technologies, Kraków, Poland, 11-14.09.2011. Book of abstracts, p. 82. 4. Bartłomiejczyk T., Wojewódzka M., Grądzka I., Lankoff A., Iwaneńko T., Kruszewski M., Szu- miel I. The protective effect of iron chelator on DNA base damage in HepG2 cells treated with silver nanoparticles. 2. Congress of Biochemistry and Cell Biology, Kraków, Poland, 5-9.09.2011. Abstracts, p. 255. 5. Bartosiewicz I., Chwastowska J., Chajduk E., Dudek J., Pyszynska M., Polkowska-Motrenko H. Oznaczanie uranu i toru w materiałach geologicznych za pomocą spektrometrii mas z jonizacją w plaz- mie indukcyjnie sprzężonej (Determination of uranium and thorium in geological materials by means of inductively coupled plasma – mass spectrometry). ChemSession’11: VIII Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, 13.05.2011. Streszczenia, p. 21. 6. Bayda M., Majchrzak M., Hug G.L., Burdziński G., Kciuk G., Bobrowski K., Marciniec B., Marciniak B. Reactivity of arylene-silylene-vinylene polymers and their model compounds in the excited states. Marie-Skłodowska-Curie Symposium on the Foundation of Physical Chemistry, Warszawa, Poland, 18-19.11.2011, p. 30. 7. Biełuszka P., Frąckiewicz K., Herdzik-Konecko I., Miśkiewicz A., Szczygłów K., Wołkowicz S., Zakrzewska-Trznadel G., Zielińska B. Nuclear power industry in Poland: analysis of uranium supply from low grade ores. European Nuclear Young Generation Forum 2011, Praha, Czech Republic, 17-20.05.2011. Extended abstracts, p. 65. 8. Bobrowski K. Radiation-induced oxidation processes in peptides and proteins relevant to oxidative stress. 5. European Young Investigator Conference, Frankfurt, Germany-Słubice, Poland, 22-26.06.2011. Book of abstracts, p. 29. 9. Bobrowski K., Hug G.L., Pędziński T., Kaźmierczak F., Wiśniowski P., Marciniak B. ●OH-induced oxidation of Met-Met dipeptides: influence of geometric and steric factors. 27. Miller Conference on Radiation Chemistry, Tällberg, Sweden, 20-25.05.2011, P-44. 10. Bobrowski K., Hug G.L., Pędziński T., Kaźmierczak F., Wiśniowski P., Marciniak B. ●OH-induced oxidation of Met-Met dipeptides: influence of geometric and steric factors. 14. International Congress of Radiation Research, Warszawa, Poland, 28.08.-1.09.2011, p. 243-244. 11. Bobrowski K., Mozziconacci O., Kciuk G., Rusconi F., Mirkowski J., Wiśniowski P.B., Houee- -Levin C. Methionine residue acts as a prooxidant in the ●OH-induced oxidation of enkephalins. COST Workshop CM603 Free Radicals in Chemical Biology, Zagreb, Croatia, 14-17.06.2011, p. 21. 12. Boguski J., Przybytniak G., Mirkowski K., Bojanowska-Czajka A. Lifetime prediction of cables installed in nuclear power plants based on antioxidant decomposition in insulations. PUBLICATIONS IN 2011 125

NUTECH-2011 International Conference on Development and Applications of Nuclear Technologies, Kraków, Poland, 11-14.09.2011. Book of abstracts, p. 70. 13. Bojanowska-Czajka A., Trojanowicz M., Soltan D., Kciuk G., Nałęcz-Jawecki G. Radiolytic decomposition of diclofenac in water by gamma irradiation. NUTECH-2011 International Conference on Development and Applications of Nuclear Technologies, Kraków, Poland, 11-14.09.2011. Book of abstracts, p. 79. 14. Brykała M., Deptuła A., Łada W., Olczak T., Wawszczak D., Smoliński T. Badania nad otrzymywaniem dwutlenku uranu dotowanego torem za pomocą kompleksowej metody zol-żel (CSGP) (Synthesis of uranium dioxide doped by Th by complex sol-gel process (CSGP)). ChemSession’11: VIII Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, 13.05.2011. Streszczenia, p. 25. 15. Brzóska K., Siomek A., Sochanowicz B., Oliński R., Kruszewski M. Sod1 deficiency in mice results in increased NF-κB activity and altered expression of NF-κB related genes. Current Trends in Biomedicine Workshop: Molecular and Cellular Bases of Redox Signaling and Oxi- dative Stress: Implications in Biomedicine, Baeza, Spain, 2-4.11.2011, [1] p. 16. Brzóska K., Sochanowicz B., Grądzka I. Conjugated linoleic acid sensitized human colon cancer HT-29 cells to X-radiation by impairing DNA double strand break repair. 14. International Congress of Radiation Research, Warszawa, Poland, 28.08.-1.09.2011, p. 136. 17. Buczkowski M., Sartowska B., Starosta W. Influence of ionising and UV radiation on template deposited microstructures of silver haloids. NUTECH-2011 International Conference on Development and Applications of Nuclear Technologies, Kraków, Poland, 11-14.09.2011. Book of abstracts, p. 68. 18. Chajduk E., Danko B., Polkowska-Motrenko H. Instrumental neutron activation analysis (INAA) for steel analysis and certification. NUTECH-2011 International Conference on Development and Applications of Nuclear Technologies, Kraków, Poland, 11-14.09.2011. Book of abstracts, p. 159. 19. Chajduk E., Doner K., Polkowska-Motrenko H., Bilewicz A. Badania układów rozdzielczych Se-As oraz ocena możliwości ich zastosowania do produkcji genera- torów do Pozytonowej Tomografii Emisyjnej (Studies on separation systems for Se-As and evaluation of the possibilities of their use to the production of generators for positron emission tomography (PET)). I Ogólnopolska Konferencja Radiofarmaceutyczna, Łódź, Poland, 12-13.05.2011, p. 38. 20. Chajduk E., Dudek J., Danko B., Polkowska-Motrenko H., Skłodowska A. Analiza chemiczna blaszek z welurów genueńskich (Elemental analysis of metal threads from Genoa velvets). Analiza zabytków w ochronie zabytków – Sympozjum, Warszawa, Poland, 8-9.12.2011, p. 27. 21. Chajduk E., Kalbarczyk P., Dudek J., Polkowska-Motrenko H. Oznaczanie stosunków izotopowych uranu techniką ICP-MS (Determination of uranium isotope ratio by ICP-MS). XVI Konferencja: „Zastosowanie metod AAS, ICP-OES i ICP-MS w analizie środowiskowej”, Łódź, Poland, 5-6.12.2011, p. 27. 22. Chajduk E., Kalbarczyk P., Dudek J., Polkowska-Motrenko H. Oznaczanie stosunków izotopowych uranu techniką ICP-MS (Determination of uranium isotope ratio by ICP-MS). Konferencja Naukowo-Techniczna: „Polska nauka i technika dla elektrowni jądrowych w Polsce”, Mądralin, Poland, 13-14.01.2011, [1] p. 23. Chajduk E., Kalbarczyk P., Dudek J., Polkowska-Motrenko H. Oznaczanie stosunków izotopowych uranu techniką ICP-MS (Determination of isotope ratios of uranium by ICP-MS technique). Konferencja naukowa: „Perspektywiczne cykle paliwowe energetyki jądrowej”, Mądralin, Poland, 13-14.06.2011, [1] p. 24. Chajduk E., Kalbarczyk P., Polkowska-Motrenko H. Zastosowanie techniki ICP-MS do oznaczania stosunków izotopowych uranu (Application of ICP-MS technique to the determination of isotope ratios of uranium). 54. Zjazd Naukowy Polskiego Towarzystwa Chemicznego i Stowarzyszenia Inżynierów i Techników Przemysłu Chemicznego, Lublin, Poland, 18-22.09.2011. Materiały zjazdowe, p. 371. 126 PUBLICATIONS IN 2011

25. Chajduk E., Polkowska-Motrenko H., Dybczyński R. Zastosowanie neutronowej analizy aktywacyjnej do oznaczania metali szlachetnych (Application of neutron activation analysis to the determination of noble metals). 54. Zjazd Naukowy Polskiego Towarzystwa Chemicznego i Stowarzyszenia Inżynierów i Techników Przemysłu Chemicznego, Lublin, Poland, 18-22.09.2011. Materiały zjazdowe, p. 81. 26. Chajduk E., Skwara W., Bartosiewicz I., Pyszynska M., Chwastowska J. Ocena odpadów i produktów ubocznych przemysłu miedziowego jako źródła pierwiastków rzadkich (Evaluation of wastes and by-products in the copper industry as a source of rare earth elements). Nowoczesne metody przygotowania próbek i oznaczania śladowych ilości pierwiastków. Materiały Ju- bileuszowego XX Poznańskiego Konwersatorium Analitycznego, Poznań, Poland, 27-29.04.2011, p. 63. 27. Chmielewska D., Gryczka U., Migdał W., Daszewski W., Kuberka A., Chyrczakowska M. Radiation treatment of library and archival collections for microbiological decontamination. NUTECH-2011 International Conference on Development and Applications of Nuclear Technologies, Kraków, Poland, 11-14.09.2011. Book of abstracts, p. 181. 28. Chmielewska D., Starosta W. Influence of ionizing radiation dose on size, distribution and properties of nanosilver particles embedded in different matrixes. 27. Miller Conference on Radiation Chemistry, Tällberg, Sweden, 20-25.05.2011, p. 51. 29. Chmielewska D., Starosta W. Radiation synthesis of silver micro- and nanoparticles embedded in cotton fabric. NUTECH-2011 International Conference on Development and Applications of Nuclear Technologies, Kraków, Poland, 11-14.09.2011. Book of abstracts, p. 78. 30. Chmielewska-Śmietanko D., Gryczka U., Migdał W., Daszewski W., Kuberka A. Electron beam application to microbiological decontamination of library and archival collections. International Meeting on Radiation Processing (IMRP), Montreal, Canada, 13-16.06.2011. Book of abstracts, EA-13, p. 146. 31. Chmielewska-Śmietanko D., Sartowska B., Starosta W., Walo M. Radiation synthesis of silver nanostructures in cotton matrix. International Meeting on Radiation Processing (IMRP), Montreal, Canada, 13-16.06.2011. Book of abstracts, HC-08, p. 212. 32. Chmielewski A.G. Chemistry for the nuclear energy of the future. 14. International Congress of Radiation Research, Warszawa, Poland, 28.08.-1.09.2011, p. 68-69. 33. Chmielewski A.G. Electron accelerators application for wastewater treatment. Gdańsk Workshop: “Progress in new methods of water and waste water cleaning”, Gdańsk, Poland, 4-5.07.2011, p. 6-7. 34. Chmielewski A.G. Nanotechnology and radiation chemistry. International Meeting on Radiation Processing (IMRP), Montreal, Canada, 13-16.06.2011. Book of abstracts, EA-01.02, p. 67-68. 35. Chmielewski A.G. Rola Rady ds. Atomistyki przy Prezesie Państwowej Agencji Atomistyki w przygotowaniu programu badawczo-rozwojowego energetyki jądrowej (Role of the Council of Atomics, affiliated to the National Atomic Energy Agency, in the preparation of a research – development programme for nuclear power engineering in Poland). Konferencja Naukowo-Techniczna: „Polska nauka i technika dla elektrowni jądrowych w Polsce”, Mądralin, Poland, 13-14.01.2011, [2] p. 36. Chmielewski A.G., Harasimowicz M., Palige J., Polak A., Roubinek O., Wawryniuk K., Zale- wski M. Wzbogacanie biogazu w metan przy wykorzystaniu mobilnej instalacji membranowej (Enrichment of biogas in methane with using mobile membrane installation). ChemSession’11: VIII Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, 13.05.2011. Streszczenia, P-115. 37. Chmielewski A.G., Licki J., Pawelec A., Zimek Z., Sun Y., Witman S.

Treatment of off-gases containing NOx by electron beam. PUBLICATIONS IN 2011 127

International Symposium on Nitrogen Oxides Emission Abatement NOEA 2011, Zakopane, Poland, 4-7.09.2011. Book of abstracts, p. 17. 38. Chmielewski A.G., Migdał W., Chmielewska-Śmietanko D., Gryczka U. Biogas and radiation chemistry. International Meeting on Radiation Processing (IMRP), Montreal, Canada, 13-16.06.2011. Book of abstracts, EA-20, p. 153. 39. Chmielewski A.G., Pawelec A., Licki J., Witman S., Sun Y., Zimek Z. Plasma processes including electron beam for off-gases purification. 12. Tihany Symposium on Radiation Chemistry, Zalakaros, Hungary, 27.08.-1.09.2011, p. 15. 40. Chmielewski A.G., Pawelec A., Licki J., Witman S., Zimek Z.

Electron beam treatment of high NOx concentration off-gases. International Meeting on Radiation Processing (IMRP), Montreal, Canada, 13-16.06.2011. Book of abstracts, EA-02.02, p. 69. 41. Chmielewski A.G., Polak A. Wzbogacanie biogazu w metan w celu uzyskania produktu do zasilania sieci gazowych i wykorzystania w silnikach samochodowych (Enrichment of biogas in methane to obtain a product to supply the gas grid and to apply in motor-car engines). Energia elektryczna, ciepło i gaz – perspektywą dla gminy, Minikowo, Poland, 11.03.2011. Materiały konferencyjne, p. 1-4. 42. Chwastowska J., Chajduk E., Dudek J., Pyszynska M., Bartosiewicz I., Polkowska-Motrenko H. Opracowanie optymalnych warunków roztwarzania materiałów do oznaczania U i Th metodą ICP-MS (Elaboration of optimal conditions for the disgestion of materials for the determination of U and Th by the ICP-MS method). Nowoczesne metody przygotowania próbek i oznaczania śladowych ilości pierwiastków. Materiały Ju- bileuszowego XX Poznańskiego Konwersatorium Analitycznego, Poznań, Poland, 27-29.04.2011, p. 65. 43. Chwastowska J., Skwara W., Dudek J., Pyszynska M., Sadowska-Bratek M. Badanie wpływu nanocząsteczek srebra na organizmy żywe. Problemy analityczne (The study of influence of nano amounts of silver on living systems. The analytical problems). Nowoczesne metody przygotowania próbek i oznaczania śladowych ilości pierwiastków. Materiały Ju- bileuszowego XX Poznańskiego Konwersatorium Analitycznego, Poznań, Poland, 27-29.04.2011, p. 64. 44. Cieśla K. Radiation modification of the physicochemical and functional properties of the polysaccharide films. NUTECH-2011 International Conference on Development and Applications of Nuclear Technologies, Kraków, Poland, 11-14.09.2011. Book of abstracts, p. 76. 45. Cieśla K., Sartowska B. Modification of the structure of the films prepared basing gamma irradiated starch examined by scanning electron microscopy. NUTECH-2011 International Conference on Development and Applications of Nuclear Technologies, Kraków, Poland, 11-14.09.2011. Book of abstracts, p. 204. 46. Cieśla K., Sartowska B., Królak E., Głuszewski W. Gamma irradiation influence on the structure of potato starch gels studied by SEM. NUTECH-2011 International Conference on Development and Applications of Nuclear Technologies, Kraków, Poland, 11-14.09.2011. Book of abstracts, p. 187. 47. Dispenza C., Sabatino M.A., Niconov A., Chmielewska D., Spadaro G. E-beam crosslinked, biocompatible functional hydrogels incorporating polyaniline nanoparticles. 12. Tihany Symposium on Radiation Chemistry, Zalakaros, Hungary, 27.08.-1.09.2011, p. 112. 48. Doner K., Polkowska-Motrenko H. 186 Ocena czystości chemicznej kompozytów WO3/ZrO2 wzbogaconych w izotop W wykonana metodą 188 NAA oraz ocena stopnia Lucji Re (Assessment of chemical purity WO3/zrO2 composites enriched in the isotope 186W made by NAA and assess the degree of elution 188Re). ChemSession’11: VIII Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, 13.05.2011. Streszczenia, P-16. 49. Dybczyński R.S. Aktywacyjne metody analizy i ich znaczenie w nieorganicznej analizie śladowej (Activation methods od analysis and their significance in trace analysis). Nowoczesne metody przygotowania próbek i oznaczania śladowych ilości pierwiastków. Materiały Ju- bileuszowego XX Poznańskiego Konwersatorium Analitycznego, Poznań, Poland, 27-29.04.2011, p. 26. 128 PUBLICATIONS IN 2011

50. Dybczyński R.S, Danko B., Pyszynska M., Polkowska-Motrenko H. Ilorazowa podstawowa pomiarowa procedura odniesienia (metoda definitywna) dla oznaczania żelaza w materiałach biologicznych za pomocą radiochemicznej neutronowej analizy aktywacyjnej (Ratio primary reference measurements procedure for the determination of iron in biological materials by radiochemical neutron activation analysis). 5. Ogólnopolska Konferencja Naukowa: „Jakość w chemii analitycznej”, Mory k/Warszawy, Poland, 24-25.11.2011, p. 9. 51. Dybczyński R.S., Kulisa K. Teoretyczne i praktyczne aspekty oznaczania ziem rzadkich w materiałach biologicznych i środowiskowych za pomocą chromatografii jonowej (Theoretical and practical aspects of the determination of rare earth elements in biological and environmental materials by ion chromatography). II Konferencja Naukowa: „Monitoring i analiza wody. Chromatograficzne metody oznaczania substancji i charakterze jonowym”, Toruń, Poland, 3-5.04.2011, p. 19. 52. Dybczyński R., Pyszynska M., Chajduk E. Poszukiwanie nowej metody oddzielania śladowych ilości uranu od toru i 233Pa (Search for the new method of the separation of the amounts of uranium from thorium and 233Pa). Konferencja naukowa: „Perspektywiczne cykle paliwowe energetyki jądrowej”, Mądralin, Poland, 13-14.06.2011, [1] p. 53. Filipiak P., Jakowiuk A., Bartak J., Machaj B., Pieńkos P., Kowalska E. Laboratory automatic measuring system of gamma specimens. NUTECH-2011 International Conference on Development and Applications of Nuclear Technologies, Kraków, Poland, 11-14.09.2011. Book of abstracts, p. 136. 54. Fuks L. N-heterocyclic aldehyde thiosemicarbazones – ligands for the technetium and rhenium complexes, potential radiopharmaceuticals. 5. EuCheMS Conference on Nitrogen Ligands in Coordination Chemistry, Metal-Organic Chemistry, Materials & Catalysis, Granada, Spain, 4-8.09.2011. Conference book, p. 147. 55. Fuks L., Gniazdowska E., Koźmiński P. Novel technetium and rhenium complexes with the n-heterocyclic aldehyde thiosemicarbazones – potential radiopharmaceuticals. 7. International Symposium on Technetium and Rhenium – Science and Utilization, Moscow, Russia, 4-8.07.2011. Book of abstracts. Eds. K.E. German, B.F. Mysoedov, G.E. Kodina, I.D. Troshkina, T. Sekine. Publishing House Granitsa, Moscow 2011, p. 148. 56. Fuks L., Gniazdowska E., Koźmiński P. Technetium-99m complexed with n-heterocyclic aldehyde thiosemicarbazones – potential precursors of the radiopharmaceuticals. 11. International Symposium on Applied Bioinorganic Chemistry, Barcelona, Spain, 2-5.12.2011, [1] p. 57. Głuszewski W. Application of GC to study radiolysis of cultural heritage artefacts. NUTECH-2011 International Conference on Development and Applications of Nuclear Technologies, Kraków, Poland, 11-14.09.2011. Book of abstracts, p. 176. 58. Głuszewski W. Rok 2011 rokiem Marii Skłodowskiej-Curie (The year 2011 – the year of Maria Skłodowska-Curie). Konferencja Naukowo-Techniczna: „Polska nauka i technika dla elektrowni jądrowych w Polsce”, Mądralin, Poland, 13-14.01.2011, [1] p. 59. Głuszewski W., Zagórski Z.P., Rajkiewicz M. Modification of elastomers by ionizing radiation. 14. International Congress of Radiation Research, Warszawa, Poland, 28.08.-1.09.2011, p. 171-172. 60. Głuszewski W., Zagórski Z.P., Rajkiewicz M. Radiation modification of elastomers. NUTECH-2011 International Conference on Development and Applications of Nuclear Technologies, Kraków, Poland, 11-14.09.2011. Book of abstracts, p. 75. 61. Głuszewski W., Zagórski Z.P., Rajkiewicz M. Radiation modification of elastomers/Radiacyjna modyfikacja elastomerów. XIV Międzynarodowa Konferencja Naukowo-Techniczna ELASTOMERY 2011: „Elastomery – inno- wacja i zrównoważony rozwój”, Warszawa, Poland, 23-25.11.2011, p. 118-119. PUBLICATIONS IN 2011 129

62. Gniazdowska E., Koźmiński P., Bańkowski K. 99m 2 4 9 Tc-labelled vasopressin analog d(CH2)5[D-Tyr(Et ),Ile ,Eda ]AVP as a potential radiopharmaceutical for small-cell lung cancer (SCLC) imaging. 7. International Symposium on Technetium and Rhenium – Science and Utilization, Moscow, Russia, 4-8.07.2011. Book of abstracts. Eds. K.E. German, B.F. Mysoedov, G.E. Kodina, I.D. Troshkina, T. Sekine. Publishing House Granitsa, Moscow 2011, p. 149. 63. Grądzka I., Sochanowicz B., Brzóska K., Wojewódzka M., Sommer S., Wójciuk G., Gasińska A., Degen C., Jahreis G., Szumiel I. Mechanism of HT-29 cells radiosensitization by conjugated linoleic acid: changes in lipid raft properties. 14. International Congress of Radiation Research, Warszawa, Poland, 28.08.-1.09.2011, p. 139-140. 64. Grądzka I., Sochanowicz B., Brzóska K., Wojewódzka M., Sommer S., Wójciuk G., Gasińska A., Degen C., Jahreis G., Szumiel I. Mechanism of HT-29 cells radiosensitization by conjugated linoleic acid: influence on double-strand DNA break repair and lipid rafts properties. 2. Congress of Biochemistry and Cell Biology, Kraków, Poland, 5-9.09.2011. Abstracts, p. 80. 65. Guzik G.P. Rozdzielanie i unieszkodliwianie odpadów promieniotwórczych z elektrowni jądrowych (Separation and neutralisation of radioactive waste from nuclear power stations). Konferencja naukowa: „Perspektywiczne cykle paliwowe energetyki jądrowej”, Mądralin, Poland, 13-14.06.2011, [1] p. 66. Guzik G.P., Stachowicz W., Michalik J. Study on radiation induced radicals giving rise to EPR signals employed for the detection of radiation treatment in sugar containing food. NUTECH-2011 International Conference on Development and Applications of Nuclear Technologies, Kraków, Poland, 11-14.09.2011. Book of abstracts, p. 190. 67. Ignasiak M., Pędziński T., Scuderi D., Filipiak P., Kciuk G., Houee-Levin Ch., Marciniak B. Oxidation studies of methionine-containing peptides. 5. European Young Investigator Conference, Frankfurt, Germany-Słubice, Poland, 22-26.06.2011. Book of abstracts, p. 35. 68. Jakowiuk A., Bartak J., Machaj B., Kowalska E., Filipiak P. System pomiaru stężenia radonu w powietrzu i wodzie (System for measuring the concentration of radon in air and water). III Pomorska Konferencja z cyklu „Jakość powietrza”, Gdańsk, Poland, 7-8.04.2011, p. 45. 69. Jakowiuk A., Machaj B., Pieńkos P., Kowalska E., Filipiak P., Świstowski E. Wireless system for radiometric measurements. NUTECH-2011 International Conference on Development and Applications of Nuclear Technologies, Kraków, Poland, 11-14.09.2011. Book of abstracts, p. 216. 70. Jaworska A., Romm H., Oestreicher U., Thierens H., Vral A., Rothkamm K., Ainsbury E., Bendertitter H., Voisin P., Fattibene P., Lindholm C., Barquinero F., Sommer S., Woda K., Scherthan H., Beinke C., Vojnovic B., Trompier F., Bajinskis A., Wójcik A. MULTIBIODOSE: multi-disciplinary biodosimetric tools to manage high scale radiological casualties. 14. International Congress of Radiation Research, Warszawa, Poland, 28.08.-1.09.2011, p. 64. 71. Kalbarczyk P., Polkowska-Motrenko H., Chajduk E. Study of thorium-uranium fuel cycle. NUTECH-2011 International Conference on Development and Applications of Nuclear Technologies, Kraków, Poland, 11-14.09.2011. Book of abstracts, p. 51. 72. Kalbarczyk P., Polkowska-Motrenko H., Chajduk E. Wydzielanie uranu z dwutlenku toru napromieniowanego w reaktorze jądrowym (Separation of uranium from thorium dioxide irradiated in a nuclear reactor). ChemSession’11: VIII Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, 13.05.2011. Streszczenia, p. 58. 73. Kalbarczyk P., Polkowska-Motrenko H., Chajduk E. Wydzielanie uranu z dwutlenku toru napromieniowanego w reaktorze jądrowym (Separation of uranium from thorium dioxide irradiated in a nuclear reactor). Sympozjum: „Bezpieczeństwo i ochrona radiologiczna w aspekcie budowy elektrowni jądrowej w Pol- sce”, Warszawa, Poland, 6.06.2011, [1] p. 130 PUBLICATIONS IN 2011

74. Kałuska I., Zimek Z., Sadło J. Comparison trials in dosimetry. International Meeting on Radiation Processing (IMRP), Montreal, Canada, 13-16.06.2011. Book of abstracts, TE-06, p. 219. 75. Kaźmierczak U., Banaś D., Bogowicz M., Braziewicz J., Buraczewska I., Choiński J., Czerwiński M., Czub J., Jaskóła M., Korman A., Kruszewski M., Lankoff A., Szefliński Z., Wojewódzka M., Wójcik A., Wrzesień M. Investigation of bystander responses in CHO-K1 cells irradiated by 12C ions. 14. International Congress of Radiation Research, Warszawa, Poland, 28.08.-1.09.2011, p. 89-90. 76. Kciuk G. Electron transfer in dipeptides containing methionine and tyrosine. 5. European Young Investigator Conference, Frankfurt, Germany-Słubice, Poland, 22-26.06.2011. Book of abstracts, p. 44. 77. Kciuk G., Bobrowski K., Mirkowski K., De la Fuente J.R., Aliaga C. Spectral and kinetic properties of transient species derived from 2-methyl-3-azaoxoisoaporphine in organic solvents. 5. European Young Investigator Conference, Frankfurt, Germany-Słubice, Poland, 22-26.06.2011. Book of abstracts, p. 68. 78. Kciuk G., Bobrowski K., Mirkowski K., De la Fuente J.R., Aliaga C. Spectral and kinetic properties of transient species derived from quinoxaline-derivatives in irradiated organic solvents. 14. International Congress of Radiation Research, Warszawa, Poland, 28.08.-1.09.2011, p. 113. 79. Kisała J., Kumięga P., Balawejder M., Hęclik K., Pogocki D. Linuron contaminated water detoxification by ozonolysis and Fenton reaction. Risk Factors of Food Chain – 11. International Conference, Iwonicz, Poland, 5-6.09.2011, p. 44. 80. Kocia R., Grodkowski J., Mirkowski J. Excited states of p-terphenyl in selected ionic liquid under electron pulses irradiation. 14. International Congress of Radiation Research, Warszawa, Poland, 28.08.-1.09.2011, p. 313. 81. Kocia R., Grodkowski J., Mirkowski J., Szreder T., Nyga M., Sulich A.

Inicjowana radiacyjnie redukcja CO2 w środowisku wybranej cieczy jonowej (Radiation-induced reduction of CO2 in a medium of a selected ionic liquid). ChemSession’11: VIII Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, 13.05.2011. Streszczenia, p. 69. 82. Kornacka E.M., Zagórski Z.P. Ionizing radiation assisted, abiotic formation of methane. ESF-COST High-Level Research Conference on Systems Chemistry III, 23-28.10.2011 and Systems Chemistry, COST Action CM0703 Meeting – Chembiogenesis 2011, 27-30.10.2011, Heraklion-Crete, Greece. Abstracts, p. 37. 83. Kornacka E.M., Zagórski Z.P. Radiation chemistry of DNA as origins of life connection. Origins 2011: ISSOL and Bioastronomy Joint International Conference, Montpellier, France, 3-8.07.2011. Program and abstracts, [1] p. 84. Korzeniowska-Sobczuk A., Doner K., Karlińska M. Accredited Laboratory for Measurement of Technological Doses (LMTD). NUTECH-2011 International Conference on Development and Applications of Nuclear Technologies, Kraków, Poland, 11-14.09.2011. Book of abstracts, p. 193. 85. Kosno K., Celuch M., Mirkowski J., Pogocki D. Dwa oblicza nikotyny (Two faces of nicotine). ChemSession’11: VIII Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, 13.05.2011. Streszczenia, p. 72. 86. Krajewski S., Kasperek A., Bilewicz A., Abbas K., Cydzik I., Simonell F. Cyclotron production of 44Sc – new radionuclide for PET technique. EU COST Action D38 Final Meeting, Oxford, Great Britain, 13-15.09.2011, [1] p. 87. Kruszewski M., Brzóska K., Stępkowski T., Wojewódzka M., Wójciuk G., Wójciuk K., Lankoff A., Dusińska M., Dobrzyńska M., Gromadzka-Ostrowska J., Brunborg G. PUBLICATIONS IN 2011 131

Nanosilver induced changes in cellular signal transduction in HEPG2 cells. EEMS – European Environmental Mutagen Society Annual Meeting, Barcelona, Spain, 4-7.07.2011, p. 100. 88. Kruszewski M., Buraczewska I., Lankoff A., Sommer S., Wojewódzka M. Radiobiologia w służbie energetyki jądrowej (Radiobiology for nuclear industry). Konferencja Naukowo-Techniczna: „Polska nauka i technika dla elektrowni jądrowych w Polsce”, Mądralin, Poland, 13-14.01.2011, [1] p. 89. Kruszewski M., Grądzka I., Bartłomiejczyk T., Iwaneńko T., Lankoff A., Dusińska M., Brun- borg G., Dobrzyńska M., Gromadzka-Ostrowska J., Wojewódzka M. In vitro and in vivo toxicity of silver nanoparticles. 9. International Comet Assay Workshop, Kusadasi, Turkey, 13-16.09.2011, p. 42. 90. Kubera H., Melski K., Assman K., Głuszewski W., Zimek Z., Czaja-Jagielska N. Changes in properties of hydrobiodegradable film based on aliphatic-aromatic copolymers treated by ionizing radiation. NUTECH-2011 International Conference on Development and Applications of Nuclear Technologies, Kraków, Poland, 11-14.09.2011. Book of abstracts, p. 60. 91. Łyczko K., Łyczko M., Herdzik-Koniecko I., Zielińska B. Nowa metoda rozpuszczania tlenku toru (New dissolution method of thorium oxide). Konferencja Naukowo-Techniczna: „Polska nauka i technika dla elektrowni jądrowych w Polsce”, Mądralin, Poland, 13-14.01.2011, [1] p. 92. Migdał W., Chmielewska-Śmietanko D., Dubiel M. Możliwości wykorzystania materiałów lignocelulozowych do produkcji biogazu (Possibilities of application lignocellulose materials for biogas production). Energia elektryczna, ciepło i gaz – perspektywą dla gminy, Minikowo, Poland, 11.03.2011. Materiały konferencyjne, p. 5-6. 93. Migdał W., Ptaszek M., Gryczka U., Orlikowski L.B. Możliwość wykorzystania technologii radiacyjnych w ochronie roślin przed chorobami (Possibility of application radiation technologies in protection of plants against diseases). 51. Sesja Naukowa Instytutu Ochrony Roślin Państwowego Instytutu Badawczego, Poznań, Poland, 17-18.02.2011. Streszczenia, [2] p. 94. Migdał W., Ptaszek M., Orlikowski L., Gryczka U. Influence of electron beam irradiation on the growth of Phytophthora cinnamoni and its control in substrates. International Meeting on Radiation Processing (IMRP), Montreal, Canada, 13-16.06.2011. Book of abstracts, EA-21, p. 153-154. 95. Miśkiewicz A., Zakrzewska-Trznadel G. Radiotracers as an effective tool for membrane processes investigation. NUTECH-2011 International Conference on Development and Applications of Nuclear Technologies, Kraków, Poland, 11-14.09.2011. Book of abstracts, p. 137. 96. Miśkiewicz A., Zakrzewska-Trznadel G. Using of isotopes produced from radionuclide generators as tracer for membrane installation investigation. 6. International Conference on Tracers and Tracing Methods, TRACER 6, Oslo, Norway, 6-8.06.2011. Abstracts, [1] p. 97. Narbutt J. Ekstrakcyjne wydzielanie pierwiastków transuranowych z wypalonego paliwa jądrowego (Solvent extraction separation of transuranium elements from spent nuclear fuel). Konferencja Naukowo-Techniczna: „Polska nauka i technika dla elektrowni jądrowych w Polsce”, Mądralin, Poland, 13-14.01.2011, [1] p. 98. Nichipor H., Yacko S., Sun Y., Chmielewski A.G., Zimek Z., Bułka S. Degradation mechanism of benzene in air under electron beam irradiation. 4. Central European Symposium on Plasma Chemistry, Zlatibor, Serbia, 21-25.08.2011. Book of abstracts. Eds. M.M. Kuraica, B.M. Obradović, p. 107-108. 99. Nyga M., Grodkowski J., Kocia R., Mirkowski J. Różnice wartości stałej równowagi w cieczach jonowych w porównaniu do klasycznych rozpuszczalników (Differences in the values of equillibrium constant in ionic liquids compared to classical solvents). 132 PUBLICATIONS IN 2011

ChemSession’11: VIII Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, 13.05.2011. Streszczenia, p. 109. 100. Nyga M., Hug G.L., Mirkowski J., Szreder T., Grodkowski J. Equilibrium reactions in ionic liquids. 27. Miller Conference on Radiation Chemistry, Tällberg, Sweden, 20-25.05.2011, p. 63. 101. Nyga M., Hug G.L., Mirkowski J., Szreder T., Grodkowski J. Generation of oxidizing radicals and their reactivity in ionic liquids with the same anion. 14. International Congress of Radiation Research, Warszawa, Poland, 28.08.-1.09.2011, p. 313-314. 102. Orlikowski L.B., Gryczka U., Ptaszek M., Migdał W. Activity of e-beam irradiation in the control of Rhizoctonia solani. NUTECH-2011 International Conference on Development and Applications of Nuclear Technologies, Kraków, Poland, 11-14.09.2011. Book of abstracts, p. 186. 103. Pitarević Svedružić L., Rončević S., Chajduk E. Spectrometric analysis of lanthanides in archeological ceramics. IX International Congress of Young Chemists ‘YoungChem 2011’, Cracow, Poland, 12-16.10.2011, [1] p. 104. Polkowska-Motrenko H. Jądrowe metody analizy. Znaczenie dla metrologii chemicznej (Nuclear analytical techniques – importance for chemical metrology). Nowoczesne metody przygotowania próbek i oznaczania śladowych ilości pierwiastków. Materiały Ju- bileuszowego XX Poznańskiego Konwersatorium Analitycznego, Poznań, Poland, 27-29.04.2011, p. 27-28. 105. Polkowska-Motrenko H., Chajduk E. Przypisanie wartości właściwościom materiałów do badań w programie Rośliny (Assigment of property values in the procifiency test scheme Plants). 5. Ogólnopolska Konferencja Naukowa: „Jakość w chemii analitycznej”, Mory k/Warszawy, Poland, 24-25.11.2011, p. 19. 106. Polkowska-Motrenko H., Fuks L., Kalbarczyk P., Pyszynska M. Przygotowanie materiałów do badań biegłości laboratoriów oznaczających pierwiastki radioaktywne w środowisku i żywności (Preparation of materials for proficiency tests of laboratories determining radioactive elements in the environment and food). Nowoczesne metody przygotowania próbek i oznaczania śladowych ilości pierwiastków. Materiały Ju- bileuszowego XX Poznańskiego Konwersatorium Analitycznego, Poznań, Poland, 27-29.04.2011, p. 47. 107. Polkowska-Motrenko H., Fuks L., Kalbarczyk P., Skotniczna M. Program badań biegłości dla placówek specjalistycznych prowadzących pomiary skażeń promienio- twórczych w ramach monitoringu radiacyjnego kraju (Proficiency test scheme for radiochemical laboratories forming the radiation monitoring network in Poland). Sympozjum: „Bezpieczeństwo i ochrona radiologiczna w aspekcie budowy elektrowni jądrowej w Pol- sce”, Warszawa, Poland, 6.06.2011, [1] p. 108. Polkowska-Motrenko H., Fuks L., Kalbarczyk P., Skotniczna M. Program badań biegłości dla placówek specjalistycznych prowadzących pomiary skażeń promienio- twórczych w ramach monitoringu radiacyjnego kraju (Proficiency test scheme for radiochemical laboratories forming the radiation monitoring network in Poland). 5. Ogólnopolska Konferencja Naukowa: „Jakość w chemii analitycznej”, Mory k/Warszawy, Poland, 24-25.11.2011, p. 19. 109. Polkowska-Motrenko H., Kalbarczyk P., Chajduk E., Łyczko K.

Badania produktów napromieniania ThO2 (Studies on the irradiation products of ThO2). Konferencja naukowa: „Perspektywiczne cykle paliwowe energetyki jądrowej”, Mądralin, Poland, 13-14.06.2011, [1] p. 110. Przybytniak G. Degradacja kabli i przewodów niskiego napięcia wykorzystywanych w elektrowniach jądrowych (Degra- dation of low-voltage cables and wires applied in nuclear power plants). Konferencja Naukowo-Techniczna: „Polska nauka i technika dla elektrowni jądrowych w Polsce”, Mądralin, Poland, 13-14.01.2011, [1] p. 111. Przybytniak G. Radiation-induced effects in polyesters – influence of chemical structure and morphology. 27. Miller Conference on Radiation Chemistry, Tällberg, Sweden, 20-25.05.2011, p. 43. PUBLICATIONS IN 2011 133

112. Przybytniak G., Nowicki A., Boguski J. Starzenie polimerów stosowanych jako warstwy izolacyjne i osłony w kablach (Ageing of polymers applied as insulating layers and shields in cables). Konferencja Naukowo-Techniczna: „Polska nauka i technika dla elektrowni jądrowych w Polsce”, Mądralin, Poland, 13-14.01.2011, [1] p. 113. Przybytniak G., Zimek Z., Nowicki A., Mirkowski K., Boguski J. Selection of the materials for radiation cross-linked cables. NUTECH-2011 International Conference on Development and Applications of Nuclear Technologies, Kraków, Poland, 11-14.09.2011. Book of abstracts, p. 80. 114. Ritter S., Pignalosa D., Lee R., Hartel C., Durante M., Sommer S., Nikoghosyan A., Debus J. mBAND analysis of aberrations reveals marked differences between cells exposed in vitro and in vivo to X-rays or C-ions. 14. International Congress of Radiation Research, Warszawa, Poland, 28.08.-1.09.2011, p. 195-196. 115. Sadło J., Michalik J., Strzelczak G., Lewandowska-Szumieł M., Sterniczuk M. Carbon-centered radicals in γ-irradiated bone substituting biomaterials based on hydroxyapatite. III Spotkanie Użytkowników Systemów Firmy Bruker w Polsce, Poznań, Poland, 27-28.09.2011, p. 70. 116. Samczyński Z. Determination of uranium(VI) and thorium(IV) in technological phosphoric acid solutions. NUTECH-2011 International Conference on Development and Applications of Nuclear Technologies, Kraków, Poland, 11-14.09.2011. Book of abstracts, p. 156. 117. Samczyński Z., Dybczyński R.S., Polkowska-Motrenko H., Chajduk E., Pyszynska M., Danko B., Czerska E., Kulisa K., Kalbarczyk P., Doner K. Nowe polskie materiały odniesienia dla nieorganicznej analizy śladowej (New Polish reference materials for inorganic trace analysis). 5. Ogólnopolska Konferencja Naukowa: „Jakość w chemii analitycznej”, Mory k/Warszawy, 24-25.11.2011, p. 21. 118. Sartowska B., Orelovitch O.L., Presz A., Apel P.Yu., Blonskaya I.V. Nanopores with controlled profiles in track-etched membranes. NUTECH-2011 International Conference on Development and Applications of Nuclear Technologies, Kraków, Poland, 11-14.09.2011. Book of abstracts, p. 205. 119. Sartowska B., Piekoszewski J., Waliś L., Barlak M., Starosta W., Pochrybniak C. Poprawa odporności na wysokotemperaturowe utlenianie stali AISI 316L przez stopowanie pierwiast- kami ziem rzadkich przy wykorzystaniu intensywnych impulsów plazmowych (Improvement of high temperature oxidation resistance of AISI 316L steel by alloying with rare earth elements using intense pulses). Konferencja Naukowo-Techniczna: „Polska nauka i technika dla elektrowni jądrowych w Polsce”, Mądralin, Poland, 13-14.01.2011, [1] p. 120. Sartowska B., Piekoszewski J., Waliś L., Starosta W., Barlak M., Ratajczak R., Kopcewicz M. Application of nuclear techniques for materials surface characterisation: own investigations examples. NUTECH-2011 International Conference on Development and Applications of Nuclear Technologies, Kraków, Poland, 11-14.09.2011. Book of abstracts, p. 154. 121. Skłodowska A., Polkowska-Motrenko H., Danko B., Dudek J., Chajduk E. INAA and other analytical techniques in cultural heritage – elemental analysis of metal threads from silk velvet in Wilanów Museum-Palace. NUTECH-2011 International Conference on Development and Applications of Nuclear Technologies, Kraków, Poland, 11-14.09.2011. Book of abstracts, p. 178. 122. Smoliński T., Deptuła A., Chmielewski A.G. Methods of immobilization of radioactive elements in Synroc materials. NUTECH-2011 International Conference on Development and Applications of Nuclear Technologies, Kraków, Poland, 11-14.09.2011. Book of abstracts, [1] p. 123. Smoliński T., Deptuła A., Chmielewski A.G. Nowoczesne metody neutralizacji odpadów radioaktywnych w materiałach typu SYNROC (Modern neutralization methods of radioactive wastes immobilized in SYNROC materials). ChemSession’11: VIII Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, 13.05.2011. Streszczenia, p. 126. 134 PUBLICATIONS IN 2011

124. Sommer S., Buraczewska I., Grądzka I., Szumiel I., Kruszewski M. On the role of biological dosimetry in nuclear power industry safety assurance. 1. International Nuclear Energy Congress, Warszawa, Poland, 23-24.05.2011, [2] p. 125. Sommer S., Kowalska M., Szymańska M., Buraczewska I., Kruszewski M. Inter-laboratory comparison of ionising radiation dose reconstruction by the dicentric assay in Poland. 19. Nuclear Medical Defence Conference, Munich, Germany, 16-19.05.2011. Supplement to MCIF 2/4, p. 20-21. 126. Sommer S., Lankoff A., Wojewódzka M., Buraczewska I., Szumiel I., Kruszewski M. Development of multiparameter biodosimetry test for triage of casualties in a large scale radiological event. 19. Nuclear Medical Defence Conference, Munich, Germany, 16-19.05.2011. Supplement to MCIF 2/4, p. 20. 127. Sommer S., Nasonova E., Kruszewski M., Ritter S. Aneuploidy of individual human chromosomes in m-FISH assay. 19. Nuclear Medical Defence Conference, Munich, Germany, 16-19.05.2011. Supplement to MCIF 2/4, p. 20. 128. Starosta W., Sartowska B., Pawlukojć A., Waliś L., Buczkowski M. Metal-organic framework materials (MOF) and their applications. NUTECH-2011 International Conference on Development and Applications of Nuclear Technologies, Kraków, Poland, 11-14.09.2011. Book of abstracts, p. 203. 129. Steczek Ł., Kiegel K., Zakrzewska-Trznadel G. Application of Calix[6]arene for extraction of uranium(VI) from water solution. 1. International Conference on Methods and Materials for Separation Processes: Separation Science – Theory and Practice 2011, Kudowa Zdrój, Poland, 5-9.06.2011, [1] p. 130. Steczek Ł., Zakrzewska-Trznadel G. Design of liquid membranes with calixarenes as carriers for separation of uranium from aqueous solutions. XXVIII Membrane Summer School, Smardzewice, Poland, 11-15.09.2011, p. 78. 131. Steczek Ł., Zakrzewska-Trznadel G., Kiegiel K. Synthesis of Calix[6]arenes as carriers for separation of uranium from aqueous solutions. ChemSession’11: VIII Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, 13.05.2011. Streszczenia, P-115. 132. Sterniczuk M., Michalik J., Sadło J., Strzelczak G. Paramagnetic centers generated radiolytically in molecular sieves exposed to carbon monoxide. III Spotkanie Użytkowników Systemów Firmy Bruker w Polsce, Poznań, Poland, 27-28.09.2011, p. 69. 133. Sterniczuk M., Michalik J., Sadło J., Strzelczak G. Paramagnetyczne produkty radiolizy tlenku węgla stabilizowane w sitach molekularnych (Paramagnetic products of carbon monoxide radiolysis in molecular sieves). ChemSession’11: VIII Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, 13.05.2011. Streszczenia, p. 134. 134. Sterniczuk M., Michalik J., Sadło J., Strzelczak G. Radiolitically generated paramagnetic centers in molecular sieves with adsorbed carbon monixide. EUROMAR 2011 - Magnetic Resonance Conference, Frankfurt am Main, Germany, 21-25.08.2011, p. 85. 135. Sterniczuk M., Michalik J., Sadło J., Strzelczak G. Radiolitically generated paramagnetic centers in molecular sieves with adsorbed carbon monoxide. 14. International Congress of Radiation Research, Warszawa, Poland, 28.08.-1.09.2011, p. 172. 136. Stępkowski T., Bartłomiejczyk T., Grądzka I., Iwaneńko T., Męczyńska-Wielgosz S., Krusze- wski M. Oxidative stress related effects in HepG2 and A549 cells treated with silver nanoparticles. Current Trends in Biomedicine Workshop: Molecular and Cellular Bases of Redox Signaling and Oxi- dative Stress: Implications in Biomedicine, Baeza, Spain, 2-4.11.2011, [1] p. 137. Strzelczak G., Pogocki D., Bobrowski K. EPR study of dipeptides containing tyrosine. 27. Miller Conference on Radiation Chemistry, Tällberg, Sweden, 20-25.05.2011, p. 54. PUBLICATIONS IN 2011 135

138. Sulich A., Grodkowski J., Mirkowski J., Kocia R., Foreman M. Benzophenone as a probe in the pulse radiolysis of cyclohexanone and 1-octanol, diluents for procedures in minor actinides extraction. 5. European Young Investigator Conference, Frankfurt, Germany-Słubice, Poland, 22-26.06.2011. Book of abstracts, p. 57. 139. Sulich A., Grodkowski J., Mirkowski J., Kocia R., Foreman M. Radioliza impulsowa wybranych ligandów i rozpuszczalników, proponowanych do procesu SANEX w przetwórstwie zużytego paliwa jądrowego (Pulse radiolysis of selected ligands and solvents proposed for the SANEX process in reprocessing of spent nuclear fuels). ChemSession’11: VIII Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, 13.05.2011. Streszczenia, p. 135. 140. Sulich A., Grodkowski J., Mirkowski J., Kocia R., Foreman M. Studies on improving radiation stability of substances applied in the recycling of a spent nuclear fuel. 14. International Congress of Radiation Research, Warszawa, Poland, 28.08.-1.09.2011, p. 178. 141. Sun Y., Chmielewski A.G. Overview of multiple pollutants treatment by using electron beam technology. 4. Central European Symposium on Plasma Chemistry, Zlatibor, Serbia, 21-25.08.2011. Book of abstracts. Eds. M.M. Kuraica, B.M. Obradović, p. 27-28. 142. Szczygłów K., Zakrzewska-Trznadel G., Frąckiewicz K. Metody pozyskiwania uranu ze złóż występujących w Polsce (Methods of recovery uranium from low grade ores in Poland). ChemSession’11: VIII Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, 13.05.2011. Streszczenia, P-120. 143. Śmietanko-Chmielewska D.K., Chmielewski A.G. Application of ionizing radiation for metal nanoclusters synthesis. 12. Tihany Symposium on Radiation Chemistry, Zalakaros, Hungary, 27.08.-1.09.2011, p. 39. 144. Thierens H., Vral A., Romm H., Oestreicher U., Barnard S., Rothkamm K., Ainsbury E., Som- mer S., Beinke C., Wójcik A. The automated micronucleus assay as a reliable biodosimetric tool for population triage in large scale radiation accidents. 14. International Congress of Radiation Research, Warszawa, Poland, 28.08.-1.09.2011, p. 64. 145. Trojanowicz M., Bojanowska-Czajka A., Gumiela M., Męczyńska S., Kruszewski M., Nałęcz-Ja- wecki G. Hyphenated ionizing radiation based AOP methods for decomposition of toxic pollutants in waters. International Meeting on Radiation Processing (IMRP), Montreal, Canada, 13-16.06.2011. Book of abstracts, EA-02.04, p. 70. 146. Walo M., Przybytniak G. Polyurethane biomaterial modified with electron beam radiation. 27. Miller Conference on Radiation Chemistry, Tällberg, Sweden, 20-25.05.2011, p. 22. 147. Walo M., Przybytniak G., Akkas Kavakli P., Barsbay M., Güven O. Functionalization of polyurethane surface by radiation-induced graft polymerization. 14. International Congress of Radiation Research, Warszawa, Poland, 28.08.-1.09.2011, p. 172-173. 148. Walo M., Przybytniak G., Mirkowski K. Radiacyjna modyfikacja poli(estrouretanów) (Radiation modification of poly(estrourethanes)). ChemSession’11: VIII Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, 13.05.2011. Streszczenia, p. 144. 149. Wawryniuk K., Chmielewski A.G., Palige J., Roubinek O., Zalewski M. Procesy membranowe oczyszczania gazu syntezowego (Membrane processes of the synthesis gas purification). ChemSession’11: VIII Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, 13.05.2011. Streszczenia, P-129. 150. Węgierek-Ciuk A., Arabski M., Lisowska H., Banasik-Nowak A., Kędzierawski P., Florek A., Gozdz S., Wójcik A., Lankoff A. Relationship between acute reactions to radiotherapy, micronucleous yields in lymphocytes and SNP polymorphisms in XRCC1, XRCC3, OGG1 genes in cervix cancer patients treated by external beam radiotherapy. 136 PUBLICATIONS IN 2011

14. International Congress of Radiation Research, Warszawa, Poland, 28.08.-1.09.2011, p. 165. 151. Witman S., Pawelec A., Chmielewski A.G. Technologie plazmowe w ochronie środowiska (Plasma technology for environment protection). ChemSession’11: VIII Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, 13.05.2011. Streszczenia, P-133. 152. Wojewódzka M., Iwaneńko T., Bartłomiejczyk T., Lankoff A., Kruszewski M. The gamma-H2AX assay – an effective alternative for the comet assay in biodosimetry? 9. International Comet Assay Workshop, Kusadasi, Turkey, 13-16.09.2011, p. 73. 153. Wojewódzka M., Lankoff A., Kruszewski M. The optimisation of a finger-prick blood collection method for the gamma-H2AX assay: potential application in population triage. 14. International Congress of Radiation Research, Warszawa, Poland, 28.08.-1.09.2011, p. 83-84. 154. Wójcik A., Bajinskis A., Romm H., Oestreier U., Thierens H., Vral A., Rothkamm K., Ainsbury E., Bendertitter M., Fattibene P., Jaworska A., Lindholm C., Barquinero F., Sommer S., Woda K., Scherthan H., Vojnovic B., Trompier F. Multi-disciplinary biodosimetric tools to manage high scale radiological casualties – MULTIBIODOSE. 1. International Nuclear Energy Congress, Warszawa, Poland, 23-24.05.2011, [2] p. 155. Wójcik A., Bajinskis A., Romm H., Oestreier U., Thierens H., Vral A., Rothkamm K., Ainsbury E., Bendertitter M., Fattibene P., Jaworska A., Lindholm C., Whitehouse C., Barquinero F., Som- mer S., Woda K., Scherthan H., Vojnovic B., Trompier F. MULTIBIODOSE: multi-disciplinary biodosimetric tools to manage high scale radiological casualties. 19. Nuclear Medical Defence Conference, Munich, Germany, 16-19.05.2011. Supplement to MCIF 2/4, p. 15. 156. Wójciuk G., Wójciuk K., Kruszewski M. Biokoniugaty des-acyl greliny z wybranymi radionuklidami jako potencjalne radiofarmaceutyki (Bio- conjugates des-acyl ghrelin analogs with chosen radionuclides as potential radiopharmaceuticals). ChemSession’11: VIII Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, 13.05.2011. Streszczenia, P-135. 157. Zagórski Z.P., Kornacka E.M. Connections of radiation research to origins of life. 14. International Congress of Radiation Research, Warszawa, Poland, 28.08.-1.09.2011, p. 134. 158. Zagórski Z.P., Kornacka E.M. Critical analysis of attempts leading to the experimental confirmation of Panspermia hypothesis. ESF-COST High-Level Research Conference on Systems Chemistry III, 23-28.10.2011 and Systems Chemistry, COST Action CM0703 Meeting – Chembiogenesis 2011, 27-30.10.2011, Heraklion-Crete, Greece. Abstracts, p. 49. 159. Zagórski Z.P., Kornacka E.M. Ionizing radiation assisted, abiotic formation of methane. Origins 2011: ISSOL and Bioastronomy Joint International Conference, Montpellier, France, 3-8.07.2011. Program and abstracts, [1] p. 160. Zagórski Z.P., Kornacka E.M. Składowisko odpadów w kopalni soli w USA – wizja lokalna (Waste storage in a salt mine in the USA – a local visit). Konferencja Naukowo-Techniczna: „Polska nauka i technika dla elektrowni jądrowych w Polsce”, Mądralin, Poland, 13-14.01.2011, [1] p. 161. Zakrzewska-Trznadel G. Implementing public participation approaches in radioactive waste disposal. NUTECH-2011 International Conference on Development and Applications of Nuclear Technologies, Kraków, Poland, 11-14.09.2011. Book of abstracts, p. 45. 162. Zakrzewska-Trznadel G. Projekty badawcze wsparciem energetyki jądrowej w kraju (Research projects as support for nuclear energy in the country). Konferencja Naukowo-Techniczna: „Polska nauka i technika dla elektrowni jądrowych w Polsce”, Mądralin, Poland, 13-14.01.2011, [1] p. PUBLICATIONS IN 2011 137

163. Zakrzewska-Trznadel G., Frąckiewicz K., Zielińska B., Herdzik-Koniecko I., Biełuszka P., Miśkiewicz A., Szczygłów K., Wołkowicz S., Strzelecki R., Kiegel K. Analysis of uranium supply from domestic resources. NUTECH-2011 International Conference on Development and Applications of Nuclear Technologies, Kraków, Poland, 11-14.09.2011. Book of abstracts, [1] p. 164. Zakrzewska-Trznadel G., Frąckiewicz K., Zielińska K., Herdzik-Koniecko I., Miśkiewicz A., Szczygłów K., Biełuszka P., Chajduk E., Oszczak A. Metody pozyskiwania uranu z rud występujących w Polsce (Methods for obtaining uranium from ores occurring in Poland). Konferencja Naukowo-Techniczna: „Polska nauka i technika dla elektrowni jądrowych w Polsce”, Mądralin, Poland, 13-14.01.2011, [1] p. 165. Zakrzewska-Trznadel G., Harasimowicz M., Miśkiewicz A., Jaworska A. The hybrid system for liquid low-level radioactive waste treatment with application of membrane processes. NUTECH-2011 International Conference on Development and Applications of Nuclear Technologies, Kraków, Poland, 11-14.09.2011. Book of abstracts, p. 54. 166. Zakrzewska-Trznadel G., Miśkiewicz A., Fuks L., Kulisa K. Concentration of liquid radioactive waste using biopolymer-enhanced ultrafiltration. NUTECH-2011 International Conference on Development and Applications of Nuclear Technologies, Kraków, Poland, 11-14.09.2011. Book of abstracts, p. 42. 167. Zalewski M., Chmielewski A.G., Palige J., Roubinek O., Wawryniuk K., Chrzanowski K., Kry- łowicz A., Usidus J. Instalacja do wytwarzania biogazu z odpadów rolniczo-spożywczych (Installation for production of biogas from agricultural and food waste). ChemSession’11: VIII Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, 13.05.2011. Streszczenia, P-142. 168. Zimek Z., Przybytniak G., Nowicki A. Optimization of electron beam crosslinking of wire and cable insulation. 12. Tihany Symposium on Radiation Chemistry, Zalakaros, Hungary, 27.08.-1.09.2011, p. 78.

SUPPLEMENT LIST OF THE PUBLICATIONS IN 2010

1. Biełuszka P., Zakrzewska-Trznadel G. Zagęszczanie i oczyszczanie roztworów uranu za pomocą metod membranowych (Concentration and purification of uranium solutions by means of membrane methods). ChemSession’10: VII Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, 14.05.2010. Streszczenia, p. 36. 2. Deptuła A., Brykała M., Łada W., Olczak T., Wawszczak D., Modolo G., Daniels H., Chmiele- wski A.G. Synthesis of uranium and thorium dioxides by Complex Sol-Gel Processes (CSGP). Proceedings of the First ACSEPT International Workshop, Lisbon, Portugal, 31.03.-2.04.2010, [10] p. 3. Harasimowicz M., Chmielewski A.G., Palige J., Roubinek O., Zalewski M., Urbaniak A. Zastosowanie kaskady membranowych modułów separacyjnych do wzbogacania biogazu w metan (Ap- plication of separation membrane module cascade for biogas enrichment in methane). VIII Konferencja „Dla miasta i środowiska – problemy unieszkodliwiania odpadów”, Warszawa, Poland, 29.11.2010. Materiały konferencyjne, p. 66-68. 4. Koss U., Bilewicz A., Czerwiński A. 186 Otrzymywanie beznośnikowego Re z naświetlonych neutronami tarcz Re2(CO)10 i Re(CO)5Cl z wykorzystaniem efektu Szilarda-Chalmersa (Obtaining of carrier-free 186Re from neutron-irradiated Re2(CO)10 and Re(CO)5Cl targets, using the effect of Szilard-Chalmers). ChemSession’10: VII Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, 14.05.2010. Streszczenia, p. 87. 5. Krygowski T.M., Oziminski W.P., Palusiak M., Fowler P.W., McKenzie A.D. Aromaticity of substituted fulvene derivatives: substituent-dependent ring currents. Physical Chemistry Chemical Physics, 12, 10740-10745 (2010). 138 PUBLICATIONS IN 2011

6. Kubera H., Melski K., Ziajka A., Głuszewski W., Zimek Z. Influence of ionizing irradiation on polymers sleeves using for sterilization of medical utensils. Zeszyty Naukowe Uniwersytetu Ekonomicznego w Poznaniu, 160, 43-49 (2010). 7. Majkowska A., Bilewicz A. Macrocyclic complexes of scandium radionuclides as precursors for diagnostic and therapeutic radiopharmaceuticals. In: Application of radiotracers in chemical, environmental and biological sciences. Vol. 3. Eds. S. Lahiri, M. Maiti, S.K. Das. Saha Institute of Nuclear Physics, Kolkata 2010, p. 324-326. 8. Majkowska-Pilip A., Pruszyński M., Bilewicz A., Loktionova N., Rösch F. Labeling and stability of 46Sc-DOTATATE and 44Sc-DOTATATE radiobioconjugates. COST D38 Action: Metal-based systems for molecular imaging applications. Annual Meeting, Thessalo- niki, Greece, 20-22.06.2010, [1] p. 9. Musijowski J., Szostek B., Koc M., Trojanowicz M. Determination of fluoride as fluorosilane derivative using reversed-phase HPLC with UV detection for determination of total organic fluorine. Journal of Separation Science, 33, 2636-2644 (2010). 10. Oszczak A. Paliwo jądrowe. Przerób wypalonego paliwa (Nuclear fuel and reprocessing). Materiały Krakowskiej Konferencji Młodych Uczonych, Kraków, Poland, 23-25.09.2010. Sympozja i Kon- ferencje KKMU no. 5, p. 131-136. 11. Oziminski W.P., Garnuszek P., Mazurek A.P. Theroretical modeling of Pt-histamine complex hydrolysis and interactions with guanine and adenine. 5. Central European Conference “Chemistry towards biology”, Primošten, Croatia, 8-11.09.2010. Book of abstracts, p. 108. 12. Oziminski W.P., Krygowski T.M. Substituent effects in exocyclically substituted fulvene derivatives. Central European School on Physical Organic Chemistry, Przesieka, Poland, 8-12.06.2010, p. 39. 13. Oziminski W.P., Krygowski T.M., Fowler P.W., Soncini A. Aromatization of fulvene by complexation with lithium. Organic Letters, 12, 21, 4880-4883 (2010). 14. Trojanowicz M. Chromatographic and capillary electrophoretic determination of microcystins. Journal of Separation Science, 33, 359-371 (2010). 15. Trojanowicz M., Latoszek A., Poboży E. Analysis of genetically modified food using high-performance separation methods. Analytical Letters, 43, 1633-1679 (2010). NUKLEONIKA 139

NUKLEONIKA THE INTERNATIONAL JOURNAL OF NUCLEAR RESEARCH

EDITORIAL BOARD Andrzej G. Chmielewski (Editor-in-Chief, Poland), Krzysztof Andrzejewski (Poland), Janusz Z. Beer (USA), Jacqueline Belloni (France), Grażyna Bystrzejewska-Piotrowska (Poland), Gregory R. Choppin (USA), Hilmar Förstel (Germany), Andrei Gagarinsky (Russia), Andrzej Gałkowski (Poland), Evgeni A. Krasavin (Russia), Marek Lankosz (Poland), Stanisław Latek (Poland), Sueo Machi (Japan), Dan Meisel (USA), Jacek Michalik (Poland), Heino Nitsche (USA), Robert H. Schuler (USA), Christian Streffer (Germany), Irena Szumiel (Poland), Alexander Van Hook (USA)

CONTENTS OF No. 1/2011 1. Editorial – 2011 – the Year of Maria Skłodowska-Curie 2. Implanted manganese redistribution in Si after He+ irradiation and hydrogen pulse plasma treatment Z. Werner, C. Pochrybniak, M. Barlak, J. Piekoszewski, A. Korman, R. Heller, W. Szymczyk, K. Bocheńska 3. Targetry and radiochemistry for no-carrier-added production of 117,118m,119,120m,122Sb M. Sadeghi, M.R. Aboudzadeh Rovais, M. Enferadi, P. Sarabadani 4. Application of a neuro-fuzzy model for neutron activation analysis (NAA) H. Khalafi, M.S. Terman, F. Rahmani 5. Self-absorption correction and efficiency calibration for radioactivity measurement of environmental samples by gamma-ray spectrometry R. Misiak, R. Hajduk, M. Stobiński, M. Bartyzel, K. Szarłowicz, B. Kubica 6. Treatment with silver nanoparticles delays repair of X-ray induced DNA damage in HepG2 cells M. Wojewódzka, A. Lankoff, M. Dusińska, G. Brunborg, J. Czerwińska, T. Iwaneńko, T. Stępkowski, I. Szumiel, M. Kruszewski 7. Preparation and evaluation of a [66Ga]gallium chitosan complex in fibrosarcoma bearing animal models A. Pourjavadi, M. Akhlaghi, A.R. Jalilian 8. Preparation and primary evaluation of 66Ga-DTPA-chitosan in fibrosarcoma bearing mice M. Akhlaghi, A. Pourjavadi 9. The effect of external wedge on the photoneutron dose equivalent at a high energy medical linac S.M. Hashemi, G. Raisali, M. Taheri, A. Majdabadi, M. Ghafoori 10. Performance of a plastic scintillator and GM pancake tubes as alpha and beta contamination detectors in dosimetric stand B. Machaj, J. Mirowicz, E. Kowalska 11. Seasonal variation of the elemental composition of particulate matter collected in a small town near Warszawa, Poland L. Samek, M. Lankosz 12. Effect of ionizing radiation on the properties of PLA packaging materials K. Melski, H. Kubera, W. Głuszewski, Z. Zimek 13. Evaluation and benchmarking of gamma dose rate employing different nuclear data libraries for MCNP code at the decommissioning stage of Ignalina NPP G. Stankunas, A. Tonkunas, R. Pabarcius 14. 68Ge/68Ga radioisotope generator as a source of radiotracers for water flow investigations J. Palige, A. Majkowska, I. Herdzik, S. Ptaszek 140 NUKLEONIKA CONTENTS OF No. 2/2011 Proceedings of the 9th Kudowa Summer School “Towards Fusion Energy”, 8-12 June 2010, Kudowa Zdrój, Poland 1. Editorial – 9th Kudowa Summer School “Towards Fusion Energy” 2. Generation and diagnostics of fast electrons within tokamak plasmas M.J. Sadowski 3. Studies on fast electron transport in the context of fast ignition D. Batani 4. Diagnostics and scaling of fusion-produced neutrons in PF experiments H. Schmidt 5. Laser-induced ablation: physics and diagnostics of ion emission L. Torrisi 6. Measurements of electron and ion beams emitted from the PF-1000 device in the upstream and down- stream direction R. Kwiatkowski, E. Skladnik-Sadowska, K. Malinowski, M.J. Sadowski, K. Czaus, J. Zebrowski, L. Karpinski, M. Paduch, M. Scholz, I.E. Garkusha, P. Kubeš 7. Optical emission spectroscopy of plasma streams in PF-1000 experiments K. Jakubowska, M. Kubkowska, E. Skladnik-Sadowska, K. Malinowski, A.K. Marchenko, M. Paduch, M.J. Sadowski, M. Scholz 8. Creation of linear DC plasma generator for pyrolysis/gasification of organic materials A. Tamošiūnas, V. Grigaitienė, P. Valatkevičius 9. Real-time diagnostics of fast light ion beams accelerated by a sub-nanosecond laser D. Margarone, J. Krása, A. Picciotto, J. Prokupek 10. CVD diamond detectors for fast alpha particles escaping from the tokamak D-T plasma I. Wodniak, K. Drozdowicz, J. Dankowski, B. Gabańska, A. Igielski, A. Kurowski, B. Marczewska, T. Nowak, U. Woźnicka 11. Ponderomotive self-focusing of a short laser pulse under a plasma density ramp N. Kant, S. Saralch, H. Singh 12. Conceptual design of Light Impurity Monitor for Wendelstein 7-X I. Książek, R. Burhenn, J. Musielok 13. Post-acceleration of ions from the laser-generated plasma L. Giuffrida, L. Torrisi 14. Carbon equation of state at high pressure: the role of the radiative transport in the impedance mismatch diagnostics A.A. Aliverdiev, D. Batani, R. Dezulian, T. Vinci 15. Localized plasma polarimetry based on the phenomenon of normal mode conversion Yu.A. Kravtsov, B. Bieg 16. Possible accuracy of the Cotton-Mouton polarimetry in a sheared toroidal plasma Yu.A. Kravtsov, J. Chrzanowski 17. On the study of ion cyclotron waves in a cylindrical magnetized plasma N.G. Zaki 18. Post-recoil thermal annealing study of 177Lu, 169Yb, 175Yb, 166Ho and 153Sm in different organometallic compounds L. Nassan, B. Achkar, T. Yassine

CONTENTS OF No. 3/2011 Special Issue on the 100th Anniversary of the Nobel Prize in Chemistry to Maria Skłodowska- -Curie 1. Marie Skłodowska-Curie: teacher, mentor, research center founder, and “la Patronne” D.C. Hoffman NUKLEONIKA 141

2. Historic landmarks in radiation chemistry since early observations by Marie Skłodowska-Curie and Pierre Curie J. Belloni 3. Synthesis of heaviest nuclei and heaviest chemical elements A. Sobiczewski 4. Isotope effects in chemistry W.A. Van Hook 5. Chemistry for the nuclear energy of the future A.G. Chmielewski

CONTENTS OF No. 4/2011 1. Clastogenic effects in human lymphocytes exposed to low and high dose rate X-ray irradiation and vita- min C M. Konopacka, J. Rogoliński 2. Routine simultaneous production of no-carrier-added high purity 64Cu and 67Ga A.H. Al Rayyes, Y. Ailouti 3. Production of 166Ho and 153Sm using hot atom reactions in neutron irradiated tris(cyclopentadienyl) compounds L. Nassan, B. Achkar, T. Yassine

18 4. Production of F by proton irradiation of C6H6NF and C6H5NF2 E. Běták, R. Mikołajczak, J. Staniszewska, S. Mikołajewski, E. Rurarz, J. Wojtkowska 5. Preparation, quality control and biodistribution studies of 165Dy-chitosan for radiosynovectomy S. Shirvani-Arani, A. Mahmoodabadi, A. Bahrami-Samani, A.R. Jalilian, M. Mazidi, H. Afarideh, M. Ghannadi-Maragheh 6. Computer simulation of temperature distribution on a solid target for 201Tl production M.R. Aboudzadeh Rovais, K. Yousefi, K. Ardaneh, M. Mirzaii 7. Monte Carlo study on a new concept of a scanning photon beam system for IMRT A.M. Wysocka-Rabin, G.H. Hartmann 8. Simulation of computed tomography (CT) images using a Monte Carlo approach A.M. Wysocka-Rabin, S. Qamhiyeh, O. Jäkel 9. Effects of warmness and spatial nonuniformity of plasma waveguide on periodic absolute parametric instability N.G. Zaki, A.H. Bekheit 10. Instrumental neutron activation analysis (INAA) for steel analysis and certification H. Polkowska-Motrenko, E. Chajduk, B. Danko 11. Large area scintillation detector for dosimetric stand with improved light collection B. Machaj, J. Mirowicz, E. Kowalska 12. A real-valued genetic algorithm to optimize the parameters of support vector machine for classification of multiple faults in NPP F.Z. Amer, A.M. El-Garhy, M.H. Awadalla, S.M. Rashad, A.K. Abdien 13. Radiation-heterogenic processes of hydrogen accumulation in water-cooled nuclear reactors A. Garibov 14. Experimental research on the effects of radioactive waste repository upon groundwaters A. Zagorskis, V. Verikaitė 15. Electron beam decomposition of pollutant model compounds in aqueous systems T.-M. Ting, K.Z.M. Dahlan 16. Effectiveness of electron beam irradiation in the control of some soilborne pathogens L.B. Orlikowski, W. Migdał, M. Ptaszek, U. Gryczka 17. Natural radioactivity in building materials in Iran S. Mehdizadeh, R. Faghihi, S. Sina 142 NUKLEONIKA

18. Development of an automation system for iodine-125 brachytherapy seed encapsulated by Nd:YAG laser welding S.L. Somessari, A. Feher, F.E. Sprenger, M.E.C.M. Rostelato, F.E. da Costa, W.A.P. Calvo 19. Leakage test evaluation used for qualification of iodine-125 seeds sealing A. Feher, M.E.C.M. Rostelato, C.A. Zeituni, W.A.P. Calvo, S.L. Somessari, J.A. Moura, E.S. Moura, C.D. Souza, P.R. Rela 20. An intraoral cone system for a Neptun 10PC linear accelerator P. Shokrani, M. Soltani 21. Effect of magnetic field on the corrosion of iron as studied by positron annihilation R. Pietrzak, R. Szatanik 22. In memoriam – Professor Antoni M. Dancewicz

Information INSTITUTE OF NUCLEAR CHEMISTRY AND TECHNOLOGY NUKLEONIKA Dorodna 16, 03-195 Warszawa, Poland phone: +48 22 504 11 32; fax: +48 22 811 15 32; e-mail: [email protected] Abstracts and full texts are available on-line at http://www.nukleonika.pl INTERVIEWS IN 2011 143

INTERVIEWS IN 2011

1. Chmielewski A.G. Projekt atomowy – pierwsza elektrownia jądrowa w Polsce (The atomic project – the first power station in Poland). W Pionie i na Poziomie. Aktualności ULMA Construccion Polska SA, 1(9), 8-10 (2011). 2. Chmielewski A.G. Indeks cen uranu wzrósł o 75 proc. w ciągu roku (The index of uranium prices increased by 75% within one year). Puls Biznesu, www.pb.pl, 20.02.2011. 3. Chmielewski A.G. Sytuacja reaktora Fukushima (Situation in the Fukushima nuclear reactor). TVN, 15.03.2011. 4. Chmielewski A.G. Truszczak D.: Sytuacja reaktora Fukushima (Situation in Fukushima reactor). Program I Polskiego Radia, 16.03.2011. 5. Chmielewski A.G. Feder A.: Program “Era Wynalazków”, TVP Info, 20.11.2011. 6. Chmielewski A.G. Truszczak D.: Atomowa czy zielona? (Nuclear or green?). Wieczór z Jedynką. Program I Polskiego Radia, 07.12.2011. 7. Kruszewski M. Szmidt B.: Wiadomości. Program IV Polskiego Radia (TOK FM), 16.03.2011. 8. Lankoff A. Truszczyńska B.: Katastrofa w elektrowni jądrowej Fukushima w Japonii (The catastrophe in the nuclear power plant Fukushima). Wieczór Naukowy. Program I Polskiego Radia, 16.03.2011. 9. Lankoff A. Husberg Å.: Maria Skłodowska-Curie – woman of science. www.nobelmuseum.se/en/marie-sklodowska- -madame-curie, 16.09.2011. 144 THE INCT PATENTS AND PATENT APPLICATIONS IN 2011

THE INCT PATENTS AND PATENT APPLICATIONS IN 2011

PATENTS

1. Sposób otrzymywania terapeutycznych ilości radionuklidu 177Lu (Method for obtaining therapeutic quantities of the 177Lu radionuclide) A. Bilewicz, E. Iller Polish Patent 209169 2. Sposób otrzymywania dwuwolframianu itrowo-potasowego oraz nanokompozytu tego dwuwolframianu dotowanego iterbem (Method for obtaining yttrium-potassium ditungstate and nanocomposite of this compound doped with ytterbium) A. Deptuła, W. Łada, T. Olczak, D. Wawszczak, M. Borowiec, H. Szymczak, W. Diakonow, M. Barański Polish Patent 209170 (with the Institute of Physics, Polish Academy of Sciences)

3. Sposób otrzymywania warstw ochronnych z dwutlenku tytanu (TiO2) albo tytanu litu (Li2TiO2) na kato- dach niklowych (Method of production protective coatings made of titanium dioxide (TiO2) or lithium titanate (Li2TiO2) on nickel cathodes) W. Łada, A. Deptuła, D. Wawszczak, E. Simonetti, A. Sabazia, M. Brocco Polish Patent 209414 4. Sposób otrzymywania napełniaczy o strukturze montmorylonitu (Method for obtaining fillers of montmorillonite structure) Z. Zimek, I. Legocka, K. Mirkowski, A. Nowicki, G. Przybytniak Polish Patent 5. Sposób modyfikowania srebrem pigmentów mineralnych i tkanin (Method for modification of mineral pigments and fabrics with silver) A. Łukasiewicz, D. Chmielewska, L. Waliś, J. Michalik Polish Patent 6. Method and equipment for simultaneous removal of acidic inorganic pollutants and volatile organic compounds from stream of flue gases A.G. Chmielewski, A. Pawelec, B. Tymiński, J. Licki, A.A. Basfar Saudi Arabia Patent No. 2810 (with King Abdulaziz City for Science and Technology)

PATENT APPLICATIONS

1. Radiofarmaceutyk terapeutyczny znakowany radionuklidami radu oraz sposób jego wytwarzania (Thera- peutic radiopharmaceutical labelled with radionuclides of radium and method for its obtaining) A. Bilewicz, A. Kasperek P-394340 2. Sposób otrzymywania sferycznych ziaren trójtlenku itru (Method for obtaining spherical grains of yttrium trioxide) A. Deptuła, W. Łada, D. Wawszczak, E. Iller, L. Królicki, J. Ostyk-Narbutt P-394645 3. Sposób i układ transportu i mieszania zawiesiny biomasy w hydrolizerze i fermentorze (Method and system of transport and mixing of biomass suspension in a hydrolyser and fermenter) A. Kryłowicz, J. Usidus, K. Chrzanowski, A.G. Chmielewski P-395860 4. Sposób selektywnego wydzielania uranu i protaktynu z materiału zawierającego tor (A selective extraction of uranium and protactinium from material containing thorium) P. Kalbarczyk, H. Polkowska-Motrenko, E. Chajduk P-396564 THE INCT PATENTS AND PATENT APPLICATIONS IN 2011 145

5. Sposób pozyskiwania i separacji cennych pierwiastków metali, zwłaszcza z ubogich rud uranowych oraz ścieków radioaktywnych (Method for separation and obtaining of valuable metals particularly from low- -grade uranium ores and radioactive effluents) G. Zakrzewska-Trznadel, A. Jaworska-Sobczak, A. Miśkiewicz, W. Łada, E. Dłuska, S. Wroński P-397379 6. Sorbent for receiving radionuclide arsenic-72, production of this sorbent and its use H. Polkowska-Motrenko, A. Bilewicz, K. Doner, E. Chajduk European Patent Application No. EP12152024.1 7. A selective extraction of uranium and protactinium from material containing thorium P. Kalbarczyk, H. Polkowska-Motrenko, E. Chajduk European Patent Application No. EP12152025.8 8. Method of dissolution of thorium oxide K. Łyczko, M. Łyczko, I Herdzik, B. Zielińska European Patent Application 9. Method of dissolution of thorium oxide K. Łyczko, M. Łyczko, I. Herdzik, B. Zielińska Indian Patent Application 146 CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2011

CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2011

1. SPOTKANIE POLSKIEJ GRUPY ROBOCZEJ PROJEKTU IPPA FP7 EU (POLISH NA- TIONAL GROUP MEETING IN THE FRAME OF IPPA FP7 EU PROJECT), 5 APRIL 2011, WARSZAWA, POLAND Organized by the Institute of Nuclear Chemistry and Technology, Institute of Atomic Energy Organizing Committee: Grażyna Zakrzewska-Trznadel, Ph.D., D.Sc., professor in INCT, Barbara Zielińska, Ph.D., Agnieszka Miśkiewicz, M.Sc., Bogumiła Mysłek-Laurikainen, Ph.D., Ewelina Miśta, M.Sc.

2. SEMINAR ON THE EXCHANGE OF INFORMATION ON NUCLEAR SAFETY AND RADIOLOGICAL PROTECTION WITH PARTICIPATION OF GOVERNMENT DELE- GATIONS OF AUSTRIA AND POLAND, 25-26 MAY 2011, WARSZAWA, POLAND Organized by the Institute of Nuclear Chemistry and Technology

3. SPOTKANIE POLSKIEJ GRUPY ROBOCZEJ PROJEKTU IPPA FP7 EU (POLISH NA- TIONAL GROUP MEETING IN THE FRAME OF IPPA FP7 EU PROJECT), 1 JULY 2011, WARSZAWA, POLAND Organized by the Institute of Nuclear Chemistry and Technology, Institute of Atomic Energy Organizing Committee: Grażyna Zakrzewska-Trznadel, Ph.D., D.Sc., professor in INCT, Barbara Zielińska, Ph.D., Agnieszka Miśkiewicz, M.Sc., Bogumiła Mysłek-Laurikainen, Ph.D., Ewelina Miśta, M.Sc.

4. PlasTEP SUMMER SCHOOL AND TRAINING COURSE IN WARSAW/SZCZECIN, 25 JULY-5 AUGUST 2011, WARSZAWA/SZCZECIN, POLAND Organized by the Institute of Nuclear Chemistry and Technology; Faculty of Electrical Engineering, West Pomeranian University of Technology Organizing Committee: Andrzej Pawelec, Ph.D., Sylwia Witman, M.Sc., Marcin Hołub, Ph.D.

5. WORKSHOP “CURRENT TRENDS IN RADIATION CHEMISTRY RESEARCH”, 26 AUGUST 2011, WARSZAWA, POLAND Organized by the Institute of Nuclear Chemistry and Technology Organizer: Prof. Krzysztof Bobrowski, Ph.D., D.Sc.

6. INTERNATIONAL CONFERENCE ON DEVELOPMENT AND APPLICATIONS OF NU- CLEAR TECHNOLOGIES NUTECH-2011, 11-14 SEPTEMBER 2011, KRAKÓW, POLAND Organized by the Institute of Nuclear Chemistry and Technology; Faculty of Physics and Applied Computer Science, AGH University of Science and Technology Organizing Committee: Prof. Marek Lankosz, Ph.D., D.Sc., Dariusz Węgrzynek, Ph.D., D.Sc., Marek Ciechanowski, Ph.D., Zdzisław Stęgowski, Ph.D., Joanna Chwiej, Ph.D., Joanna Dudała, Ph.D., Grażyna Zakrzewska-Trznadel, Ph.D., D.Sc., Wojciech Migdał, Ph.D., D.Sc., Wojciech Głuszewski, Ph.D., Piotr Urbański, Ph.D., D.Sc.

7. SPOTKANIE POLSKIEJ GRUPY REFERENCYJNEJ PROJEKTU IPPA FP7 EU (POLISH REFERENCE GROUP MEETING IN THE FRAME OF IPPA FP7 EU PROJECT), 20 SEPTEMBER 2011, WARSZAWA, POLAND CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2011 147

Organized by the Institute of Nuclear Chemistry and Technology, National Centre for Nuclear Re- search Organizing Committee: Grażyna Zakrzewska-Trznadel, Ph.D., D.Sc., professor in INCT, Barbara Zielińska, Ph.D., Agnieszka Miśkiewicz, M.Sc., Bogumiła Mysłek-Laurikainen, Ph.D., Ewelina Miśta, M.Sc.

8. XI SZKOŁA STERYLIZACJI I MIKROBIOLOGICZNEJ DEKONTAMINACJI RADIA- CYJNEJ (XI TRAINING COURSE ON RADIATION STERILIZATION AND HYGENIZA- TION), 20-21 OCTOBER 2011, WARSZAWA, POLAND Organized by the Institute of Nuclear Chemistry and Technology Organizing Committee: Zbigniew Zimek, Ph.D., Iwona Kałuska, M.Sc., Andrzej Rafalski, Ph.D., Wojciech Głuszewski, Ph.D.

9. RER/8/014 COORDINATION MEETING ON RADIATION ENGINEERED NANOSTRUC- TURES – SUPPORTING RADIATION SYNTHESIS AND THE CHARACTERIZATION OF NANOMATERIALS FOR HEALTH CARE, ENVIRONMENTAL PROTECTION AND CLEAN ENERGY APPLICATIONS, 16-18 NOVEMBER 2011, WARSZAWA, POLAND Organized by the International Atomic Energy Agency, Institute of Nuclear Chemistry and Tech- nology Organizing Committee: Andrei Chupov, Agnes Sáfrány, Prof. Andrzej G. Chmielewski, Ph.D., D.Sc., Wojciech Starosta, Ph.D., Marek Buczkowski, Ph.D.

10. PIERWSZE WARSZTATY W RAMACH PROJEKTU IPPA FP7 EU (1st WORKSHOP IN THE FRAME OF IPPA FP7 EU PROJECT), 24 NOVEMBER 2011, WARSZAWA, POLAND Organized by the Institute of Nuclear Chemistry and Technology, National Centre for Nuclear Re- search Organizing Committee: Grażyna Zakrzewska-Trznadel, Ph.D., D.Sc., professor in INCT, Barbara Zielińska, Ph.D., Agnieszka Miśkiewicz, M.Sc., Bogumiła Mysłek-Laurikainen, Ph.D., Ewelina Miśta, M.Sc.

11. IX KONFERENCJA “DLA MIASTA I ŚRODOWISKA – PROBLEMY UNIESZKODLI- WIANIA ODPADÓW” (IX CONFERENCE ON “FOR THE CITY AND ENVIRONMENT – PROBLEMS OF WASTE DISPOSAL), 28 NOVEMBER 2011, WARSZAWA, POLAND Organized by the Warsaw University of Technology, Institute of Nuclear Chemistry and Technology (PlasTEP project), Solid Communal Waste Utilization Plant (Warszawa), Gdańsk University of Technology Organizing Committee: Maria Obrębska, Ph.D., Michał Kalita, Ph.D., Agata Urbaniak, M.Sc., Syl- wia Witman, M.Sc. 148 Ph.D./D.Sc. THESES IN 2011

Ph.D./D.Sc. THESES IN 2011

Ph.D. THESES

1. Maroor Raghavan Ambikalmajan Pillai, Ph.D. Studies on radioimmunoassays for thyroid and related hormones University of Mumbai, India, 1986 Nostrification: Institute of Nuclear Chemistry and Technology, 25.02.2011 2. Kamil Brzóska, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Aktywność szlaku NF-κB w warunkach permanentnego stresu oksydacyjnego: wnioski z badań na modelu myszy pozbawionych cytozolowej dysmutazy ponadtlenkowej (SOD1) (NF-κB signalling pathway activity under conditions of chronic oxidative stress: lessons from cytosolic superoxide dismutase (SOD1) deficient mice) supervisor: Prof. Marcin Kruszewski, Ph.D., D.Sc. Institute of Biochemistry and Biophysics, Polish Academy of Sciences, 10.05.2011 3. Sylwia Męczyńska-Wielgosz, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Wpływ tlenku azotu i nadtlenoazotynu na konformację i aktywność białek zawierających żelazo (The influence of nitric oxide and peroxynitrite on conformation and activity of iron containing proteins) supervisor: Prof. Marcin Kruszewski, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology, 30.06.2011 4. Karolina Ewa Wójciuk, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Rola wysokocząsteczkowych ligandów w powstawaniu dinitrozylowych kompleksów żelaza (Role of high- -molecular ligands in the formation of dinitrosyl complexes of iron) supervisor: Prof. Marcin Kruszewski, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology, 30.06.2011 5. Gabriel Kciuk, M.Sc. (Industrial Chemistry Research Institute, Warszawa, Poland) Wpływ grup funkcyjnych aminokwasów na mechanizmy reakcji rodnikowych w peptydach zawierających tyrozynę (Influence of functional groups of neighbouring amino acids on the mechanism of radical reactions occurring in peptides containing tyrosine) supervisor: Prof. Krzysztof Bobrowski, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology, 30.06.2011 6. Danuta Wawszczak, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

Synteza kompleksową metodą zol-żel kompozytów ZrO2, TiO2, SiO2 na bazie tlenków wolframu, ich badania strukturalne, przykładowe zastosowania (A complex method for the synthesis of sol-gel composites ZrO2, TiO2, SiO2 on the basis of tungsten oxides) supervisor: Edward Iller, Ph.D., D.Sc., professor in NCBJ Institute of Nuclear Chemistry and Technology, 16.12.2011

D.Sc. THESES

1. Maroor Raghavan Ambikalmajan Pillai, Ph.D. (Bhabha Atomic Research Centre, Trombay, Mumbai, India) Metallic radionuclides and therapeutic radiopharmaceuticals Institute of Nuclear Chemistry and Technology, 15.12.2011 EDUCATION 149

EDUCATION

Ph.D. PROGRAMME IN CHEMISTRY

The Institute of Nuclear Chemistry and Technology holds a four-year Ph.D. degree programme for graduates of chemical, physical and biological departments of universities, for graduates of medical universities and to engineers in chemical technology and material science. The main areas of the studies are: • chemical aspects of nuclear energy, • radiation chemistry and biochemistry, • chemistry of radioelements, • isotopic effects, • radiopharmaceutical chemistry, • analytical methods, • chemistry of radicals, • application of nuclear methods in chemical and environmental research, material science and protection of historical heritage. The candidates accepted for the mentioned programme will be employed in the Institute. The candidates can apply for a doctoral scholarship. The INCT offers accommodation in 10 rooms in the guest- house for Ph.D. students not living in Warsaw. During the four-year Ph.D. programme, the students participate in lectures given by senior staff from the INCT, University of Warsaw and the Polish Academy of Sciences. In the third year, the Ph.D. students are obliged to prepare a seminar related to the various aspects of nuclear energy. Each year the Ph.D. students are obliged to deliver a lecture on topic of his/her dissertation at a seminar. The final requirements for the Ph.D. programme graduates, consistent with the regulation of the Ministry of Science and Higher Education, are: • submission of a formal dissertation, summarizing original research contributions suitable for publica- tion; • final examination and public defense of the dissertation thesis. In 2011, the following lecture series were organized: • “The physical foundations of nuclear energy. Radioactivity, its application and elements of radiation protection” – Prof. Ludwik Dobrzyński, Ph.D., D.Sc. (National Centre for Nuclear Research, Świerk, Poland); • “Adsorbents and their part in environmental protection, in industry and in analytical chemistry: classical approach and the trends of the current studies” – Krystyna Cieśla, Ph.D., D.Sc., professor in INCT (Institute of Nuclear Chemistry and Technology, Warszawa, Poland); • “Automatization and miniaturization of instrumentation in chemical analysis” – Prof. Marek Tro- janowicz, Ph.D., D.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland). The qualification interview for the Ph.D. programme takes place in the mid of September. Detailed information can be obtained from: • head: Prof. Aleksander Bilewicz, Ph.D., D.Sc. (phone: +48 22 504 13 57, e-mail: [email protected]); • secretary: Dr. Ewa Gniazdowska (phone: +48 22 504 11 78, e-mail: [email protected]).

TRAINING OF STUDENTS

Number Institution Country Period of participants Adam Mickiewicz University Poland 1 2 weeks Faculty of Law and Administration Korea Nuclear Energy Foundation Korea 4 one-day course 150 EDUCATION

Number Institution Country Period of participants Philippine Nuclear Research Institute Philippines 1 2 weeks University of Warsaw Poland 3 3 weeks Faculty of Chemistry Warsaw University of Life Sciences Poland 42 one-day course Faculty of Human Nutrition and Consumer Sciences Warsaw University of Technology Poland 8 one-day practice Faculty of Chemical and Process Engineering

Warsaw University of Technology 2 1 month Poland Faculty of Chemistry 2 1.5 month

Warsaw University of Technology 15 one-day course Poland Faculty of Materials Science and Engineering 2 1 month

Warsaw University of Technology 15 one-day course Poland Faculty of Physics 20 one-day practice WAT Military University of Technology Poland 4 1.5 month Zespół Szkół Samochodowych i Licealnych nr 3 Poland 16 one-day course im. I.J. Paderewskiego RESEARCH PROJECTS AND CONTRACTS 151

RESEARCH PROJECTS AND CONTRACTS

RESEARCH PROJECTS GRANTED BY THE NATIONAL SCIENCE CENTRE IN 2011

1. The influence of nitric oxide and peroxynitrite on conformation and activity of iron containing proteins. supervisor: Prof. Marcin Kruszewski, Ph.D., D.Sc. 2. Novel technetium and rhenium complexes with the N-heterocyclic aldehyde thiosemicarbazones – the potential radiopharmaceuticals. supervisor: Leon Fuks, Ph.D. 3. Provenance and chronology studies of selected silver coins minted in the Polish and Central Europe coinages by means of chemical composition, sources of raw materials and technology. supervisor: Lech Waliś, Ph.D. 4. Synthesis and physicochemical properties of conjugates technetium-99m complexes with n-oc- tanoyl-[Ser3]-ghrelin(1-6) peptide as potential diagnostic radiopharmaceuticals. supervisor: Przemysław Koźmiński, M.Sc. 5. Radiochemical separation of arsenic from selenium and its potential usage in generator 72Se/72As construction. supervisor: Ewelina Chajduk, Ph.D. 6. Glass in Central Europe from the late-medieval times to the end of the pre-industrial era. Chemical composition. supervisor: Jerzy Jakub Kunicki-Goldfinger, Ph.D. 7. Complexes of 44Sc as precursors of radiopharmaceuticals for molecular imaging. supervisor: Prof. Aleksander Bilewicz, Ph.D., D.Sc. 8. Participation of radiation chemistry in systems chemistry, especially in prebiotic chemistry. supervisor: Prof. Zbigniew P. Zagórski, Ph.D., D.Sc. 9. Radiosensitizing effect of conjugated linoleic acid (CLA) on the colon adenocarcinoma cells HT-29 investigation of the mechanism of double-strand DNA break (DSB) repair delay. supervisor: Iwona Grądzka, Ph.D. 10. Radiation-induced radical processes in model amino acid and polypeptide molecules. supervisor: Prof. Krzysztof Bobrowski, Ph.D., D.Sc.

DEVELOPMENT PROJECTS GRANTED BY THE NATIONAL CENTRE FOR RESEARCH AND DEVELOPMENT IN 2011

1. New detection systems for the control of dosimetric stands. supervisor: Bronisław Machaj, Ph.D. 2. A new generation of mining radiometers for the measurement of radon decay products. supervisor: Jakub Bartak, Eng. 3. A plant for the liquid radioactive waste treatment in research institutes and organizations using radioactive substances. supervisor: Grażyna Zakrzewska-Trznadel, Ph.D., D.Sc., professor in INCT 4. Obtaining of carrier-free-scandium-47 – a radionuclide for therapeutic radiopharmaceuticals. supervisor: Prof. Aleksander Bilewicz, Ph.D., D.Sc. 152 RESEARCH PROJECTS AND CONTRACTS

5. Labelling of biomolecules with At-211 –- obtaining of therapeutic radiopharmaceuticals for nuclear medicine. supervisor: Monika Łyczko, Ph.D. 6. Preparation of a hot-melt adhesive for the insulation of joints in preinsulation pipes used in heating installations. supervisor: Grażyna Przybytniak, Ph.D., D.Sc., professor in INCT 7. Radiation sterilized substrata for plant cultivation inoculated with selected microorganisms. supervisor: Wojciech Migdał, Ph.D., D.Sc., professor in INCT 8. Formation of the data bank on original products for the juice sector, to supply requirements of the Polish market and producers, basing on the method of stable isotopes. supervisor: Ryszard Wierzchnicki, Ph.D. 9. Elaboration of the synthesis procedure of a receptor diagnostic radiopharmaceutical for breast cancer, of the type Her-2, imaging lapatinib labelled with technetium-99m. supervisor: Ewa Gniazdowska, Ph.D. 10. A mobile membrane installation for the enrichment of gas in methane (project INITECH). supervisor: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc. 11. Technical project of high-performance installation for obtaining and management of biogas (project INITECH). supervisor: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc.

INTERNATIONAL PROJECTS CO-FUNDED BY THE MINISTRY OF SCIENCE AND HIGHER EDUCATION IN 2011

1. Functionalization of polymer surfaces by radiation grafting for the separation of heavy metals including radioactive lanthanides. supervisor: Grażyna Przybytniak, Ph.D., D.Sc., professor in INCT 2. Developing of an advanced industrial gamma scanning system with wireless data acquisition. supervisor: Jacek Palige, Ph.D. 3. Supporting radiation synthesis and the characterization of nanomaterials for health care, environmental protection and clean energy applications. supervisor: Dagmara Chmielewska-Śmietanko, M.Sc. 4. Enhancing quality control methods and procedures for radiation technology. supervisor: Iwona Kałuska, M.Sc. 5. Radiation supporting synthesis and curing of nanocomposites suitable for practical applications. supervisor: Grażyna Przybytniak, Ph.D., D.Sc., professor in INCT 6. Ageing diagnostic and prognostic of low voltage C and I cables. supervisor: Grażyna Przybytniak, Ph.D., D.Sc., professor in INCT 7. Multi-disciplinary biodosimetric tools to manage high scale radiological casualties. supervisor: Sylwester Sommer, Ph.D. 8. Implementing public participation approaches in radioactive waste disposal. supervisor: Grażyna Zakrzewska-Trznadel, Ph.D., D.Sc., professor in INCT 9. Synthesis and research on new metal-organic framework coordination compounds of light s- block metal ions with heterocyclic ligands. supervisor: Wojciech Starosta, Ph.D. 10. Formation, investigations and characterization of new nanostructured porous and composite materials. supervisor: Bożena Sartowska, Ph.D. RESEARCH PROJECTS AND CONTRACTS 153 STRATEGIC PROJECT “NEW TECHNOLOGIES SUPPORTING DEVELOPMENT OF SAFE NUCLEAR ENERGY”

1. Scientific problem no. 3: Principles to secure fuel needs for the Polish nuclear energy supervisor: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc. 2. Scientific problem no. 4: Development of techniques and technologies aiding the management of spent nuclear fuel and radioactive wastes supervisor: Leon Fuks, Ph.D. 3. Scientific problem no. 5: Participation criteria of the Polish industry in the development of nuclear energy. Study of the case supervisor: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc. 4. Scientific problem no. 6: Development of methods securing nuclear safety and radiological protection for the current and future needs of nuclear energy supervisor: Prof. Marcin Kruszewski, Ph.D., D.Sc.

STRATEGIC PROJECT “ADVANCED TECHNOLOGIES FOR GAINING ENERGY”

1. Scientific problem no. 3: Elaboration of a technology of coal gasification for highly efficient production of fuel and electric energy (coordinated by the Institute for Chemical Processing of Coal) • Studies on the processes of membrane purification of synthesis gas supervisor: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc. 2. Scientific problem no. 4: Elaboration of integrated technologies for production of fuels and energy from biomass, agriculture waste and others (coordinated, in part, by the University of Warmia and Mazury in Olsztyn) • Concentration of methane in biogas formed during fermentation and co-fermentation of lignocellulose (4.2.1.C) supervisor: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc. • Studies on the degradation efficiency of lignocellulose materials under the influence of ionizing radiation (4.4.A) supervisor: Wojciech Migdał, Ph.D., D.Sc., professor in INCT • Design work on a biogas-plant (2.1.B) supervisor: Jacek Palige, Ph.D.

IAEA RESEARCH CONTRACTS IN 2011

1. Functionalization of polymer surfaces by radiation grafting for separation of heavy metals including radioactive lanthanides. No. 14431 principal investigator: Grażyna Przybytniak, Ph.D., D.Sc., professor in INCT 2. Radiation supporting synthesis and curing of nanocomposites suitable for practical applications. No. 16666 principal investigator: Grażyna Przybytniak, Ph.D., D.Sc., professor in INCT 3. Laboratory and feasibility study for industrial waster wate effluent treatment by radiation. No. 16454 principal investigator: Zbigniew Zimek, Ph.D. 154 RESEARCH PROJECTS AND CONTRACTS IAEA TECHNICAL AND REGIONAL CONTRACTS IN 2011

1. Developing of an advanced industrial gamma scanning system with wireless data acquisition. POL/0/010 2. Supporting radiation synthesis and the characterization of nanomaterials for health care, environmental protection and clean energy applications. RER/8/014 3. Enhancing quality control methods and procedures for radiation technology. RER/8/017 4. Using nuclear techniques for the characterization and preservation of cultural heritage artefacts in the European Region. RER/8/015

PROJECTS WITHIN THE FRAME OF EUROPEAN UNION FRAME PROGRAMMES IN 2011

1. FP7 Integrated Project: Actinide recycling by separation and transmutation (ACSEPT). principal investigator: Prof. Jerzy Narbutt, Ph.D., D.Sc. 2. FP7 Collaborative Project: Multidisciplinary biodosimetric tools to manage high scale radiological casulaties (MULTIBIODOSE). principal investigator: Sylwester Sommer, Ph.D. 3. FP7 – EURATOM, FUSSION: Ageing diagnostic and prognostic of low voltage C and I cables (ADVANCE). principal investigator: Grażyna Przybytniak, Ph.D., D.Sc., professor in INCT 4. FP7 – EURATOM, FUSSION: Implementing public participation approaches in radioactive waste disposal (IPPA). principal investigator: Grażyna Zakrzewska-Trznadel, Ph.D., D.Sc., professor in INCT 5. FP7 – EURATOM, FUSSION: New MS linking for an advanced cohesion in Euratom research (NEWLANCER). principal investigator: Grażyna Zakrzewska-Trznadel, Ph.D., D.Sc., professor in INCT

EUROPEAN REGIONAL DEVELOPMENT FUND: BALTIC SEA REGION PROGRAMME

1. Dissemination and fostering of plasma based technological innovation environment protection in BSR PlasTEP. supervisor: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc.

INTERNATIONAL RESEARCH PROGRAMMES IN 2011

1. European cooperation in the field of scientific and technical research. COST CM0703 Systems chemistry – Chemistry and molecular sciences and technologies. Participation of radiation chemistry in systems chemistry, especially in prebiotic chemistry. supervisor: Prof. Zbigniew Zagórski, Ph.D., D.Sc. 2. European cooperation in the field of scientific and technical research. COST ACTION CM 0603 – Free radicals in chemical biology. supervisor: Prof. Krzysztof Bobrowski, Ph.D., D.Sc. 3. European cooperation in the field of scientific and technical research. COST D38 – Metal based probes for imaging applications. Complexes of 44Sc as precursors of radiopharmaceuticals for molecular imaging. supervisor: Prof. Aleksander Bilewicz, Ph.D., D.Sc. RESEARCH PROJECTS AND CONTRACTS 155

4. Polish-Norwegian Research Fund – Impact of nanomaterials on human health: lessons from in vitro and animal models. supervisor: Prof. Marcin Kruszewski, Ph.D., D.Sc. 5. European cooperation in the field of scientific and technical research. COST Action BM 0607 Targeted radionuclide therapy. supervisor: Prof. Aleksander Bilewicz, Ph.D., D.Sc.

STRUCTURAL FUNDS: OPERATIONAL PROGRAMME INNOVATIVE ECONOMY

1. Centre of Radiochemistry and Nuclear Chemistry – meeting the needs for nuclear power and nuclear medicine. supervisor: Roman Janusz, M.Sc. 2. Analysis of the possibilities of uranium supply from indigenous resources in Poland supervisor: Grażyna Zakrzewska-Trznadel, Ph.D., D.Sc. 3. Analysis of the effects of utilization of thorium in a power reactor supervisor: Prof. Jacek Michalik, Ph.D., D.Sc. 4. New generation of electrical wires modified by radiation. supervisor: Zbigniew Zimek, Ph.D. 5. A multiparameter “Triage” test for assessment of radiation exposure to the general population. supervisor: Prof. Marcin Kruszewski, Ph.D., D.Sc. 6. A new generation of radiometric devices with wireless transmission of information. supervisor: Adrian Jakowiuk, M.Sc. 156 LIST OF VISITORS TO THE INCT IN 2011

LIST OF VISITORS TO THE INCT IN 2011

1. Adliene Diana, Department of Physics, Kaunas University of Technology, Lithuania, 16-18.11.2011. 2. Alessis Sabina, University of Palermo, Italia, 14-18.02.2011. 3. Alkin Ahmet, TUPRAS, Turkey, 05.04.2011. 4. Amilcar Antonio, Polytechnic Institute of Bragança, Portugal, 29.11.-02.12.2011. 5. Benea Vasile, Institute of Applied Physics, Academy of Sciences of Moldova, Republic of Moldova, 16-18.11.2011. 6. Brisut Patrick, International Atomic Energy Agency, Austria, 12-15.12.2011. 7. Cantser Valeriu, National Council for Accreditation and Attestation, Republic of Moldova, 16-18.11.2011. 8. Chitho Pavayno Feliciano, Philippine Nuclear Research Institute, Philippines, 01.09.-30.11.2011. 9. Chupor Andrey, International Atomic Energy Agency, Austria, 15.11.2011. 10. De la Fuente Julia, University of Chile, Chile, 25.10.-14.11.2011. 11. Dogan Alisan, TUPRAS, Turkey, 05.04.2011. 12. Gabulov Ibrahim, Institute of Radiation Problems, Azerbaijan National Academy of Sciences, Azer- baijan, 16-18.11.2011. 13. Garibov Adil, Institute of Radiation Problems, Azerbaijan National Academy of Sciences, Azerbaijan, 15.11.2011. 14. Guidez Joel, Atomic Energy and Alternative Energies Commission (CEA), France, 13.03.2011. 15. Guven Olgun, Department of Chemistry Hacettepe University, Turkey, 16-18.11.2011. 16. Hoveé-Levin Chantal, University of Paris-Sud 11, Orsay, France, 25-31.08.2011. 17. Hyun Jin Kim, Embassy of the Republic of Korea, 26.05.2011. 18. Jaksic Milko, Division of Experimental Physics, Ruđer Bošković Institute, Croatia, 16-18.11.2011. 19. Kalugin Oleg N., Kharkiv National University, Ukraine, 20-26.02.2011. 20. Kovac Peter, BIONT a.s., Slovakia, 16-18.11.2011. 21. Krkljes Aleksandra, Vinča Institute of Nuclear Sciences, Serbia, 16-18.11.2011. 22. Letournol Eric, VIVIRAD, France, 05.04.2011. 23. Lyssukhin Sergey, National Nuclear Center of the Republic of Kazakhstan (NNC), Kazakhstan, 16-18.11.2011. 24. Maningas Aurelio, Philippine Nuclear Research Institute, Philippines, 01.09.-30.11.2011. 25. Morgunov Volodymir, Kharkiv National University, Ukraine, 05-15.12.2011. 26. Ristova Mimoza, Faculty of Natural Sciences and Mathematics, Ss. Cyril and Methodius University in Skopje, Republic of Macedonia, 16-18.11.2011. 27. Sabatino Maria Antonella, University of Palermo, Italy, 14-18.02.2011. 28. Schay Zoltan, Institute of Isotopes Co., Ltd., Hungarian Academy of Sciences, Hungary, 16-18.11.2011. 29. Seanh Wan Baek, Embassy of the Republic of Korea, 26.05.2011. 30. Spadaro Giuseppe, University of Palermo, Italy, 14-18.02.2011. 31. Sueo Machi, Japan, 14-17.09.2011. 32. Tan Erdal, Turkish Atomic Energy Commission (TAEK), Turkey, 05.04.2011. 33. Tchelidze Tamar, Tbilisi State University, Georgia, 16-18.11.2011. 34. Tetsuro Majimy, Osaka University, Japan, 27-31.08.2011. 35. Tulsi Mukherjee, Bhabha Atomic Research Centre, India, 25.08.-02.09.2011. 36. Vnul Suat, Turkish Atomic Energy Commission (TAEK), Turkey, 05.04.2011. LIST OF VISITORS TO THE INCT IN 2011 157

37. Wischart James F., Brookhaven National Laboratory, USA, 25.08.-02.09.2011. 38. Yeunje Oh, Embassy of the Republic of Korea, 26.05.2011. 39. Ylli Fatos, Centre of Applied Nuclear Physics, Albania, 16-18.11.2011. 40. Young Mi Nam, Korean Atomic Energy Research Institute, Republic of Korea, 09.03.2011. 158 THE INCT SEMINARS IN 2011

THE INCT SEMINARS IN 2011

1. Tomasz Białopiotrowicz, Ph.D., D.Sc. (Maria Curie-Skłodowska University, Lublin, Poland) Swobodna energia powierzchniowa i kąt zwilżania jako parametry określające stan energetyczny po- wierzchni (The surface free energy and contact angle as parameters determining energetic state of a surface) 2. Krystyna Cieśla, Ph.D., D.Sc., professor in INCT (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Chemia w żywności: zagrożenia czy ulepszenie. Rola dodatków funkcjonalnych w kształtowaniu cech współczesnej żywności (Chemical substances in food: impendence or improvement. The weight of functional additives as the agents modifying the properties of the contemporary food) 3. Izabela Cydzik, M.Sc. (Joint Research Centre, European Commission, IHCP Nanobioscience Unit, Ispra, Italy) Production of radioactive nanoparticles for biological studies 4. Nasir Hamodi, M.Sc. (Nuclear Fuel Group, University of Manchester, United Kingdom) Manufacturing TRISO particles from kernel to a nuclear fuel element used in high temperature reactor (HTR) 5. Prof. Oleg N. Kalugin (V.N. Karazin Kharkiv National University, Ukraine) Computer modelling nanomaterials: possibilities and perspectives 6. Prof. Zbigniew Karpiński, Ph.D., D.Sc. (Institute of Physical Chemistry, Polish Academy of Sciences, Warszawa, Poland) Katalityczne wodoroodchlorowanie tetrachlorometanu na katalizatorach platynowych (Catalytic hydrogen-dechlorination of tetrachloromethane on platinum catalysts) 7. Robert Kołos, Ph.D., D.Sc. (Institute of Physical Chemistry, Polish Academy of Sciences, War- szawa, Poland) Kilka nienasyconych cząsteczek łańcuchowych o znaczeniu astrochemicznym: teoria, eksperyment, ob- serwacje (A few unsaturated chain molecules of astrochemical importance: theory, experiment, observations) 8. Seweryn Krajewski, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Metaloorganiczne i chelatowe kompleksy 105Rh i 103mRh jako potencjalne prekursory radiofarmaceuty- ków terapeutycznych (Organometallic and chelate compexes of 105Rh and 103mRh as potential precursors of therapeutic radiopharmaceuticals) 9. Prof. Doron Lancet (Weizmann Institute of Science, Rehovot, Israel) Life’s origin: complex networks right from day one 10. Małgorzata Nyga, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Generowanie rodników utleniających i ich reaktywność w wytypowanej grupie cieczy jonowych (Genera- tion of oxidizing radicals and their reactivity in selected group of ionic liquids) 11. Prof. Jerzy Ostyk-Narbutt, Ph.D., D.Sc. (Institute of Nuclear Chemistry and Technology, War- szawa, Poland) Chemia dla energetyki jądrowej przyszłości (Chemistry for the nuclear energy of the future) 12. Marcin Sterniczuk, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Centra paramagnetyczne generowane radiacyjnie w sitach molekularnych z zaadsorbowanym tlenkiem węgla (Radiation generated paramagnetic centres in molecular sieves with adsorbed carbon oxide) 13. Prof. Ion Tiginyanu (Academy of Sciences of Moldova) Novel nanomaterials based on inorganic nanostructured membranes 14. Marta Walo. M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Rola segmentów giętkich w radiacyjnej modyfikacji poli(estrouretanów) (The role of soft segments in radiation modification of poly(ester-urethanes)) LECTURES AND SEMINARS DELIVERED OUT OF THE INCT IN 2011 159

LECTURES AND SEMINARS DELIVERED OUT OF THE INCT IN 2011

LECTURES

1. Bilewicz A. Wyzwania stojące przed kształceniem w zakresie chemii dla enegetyki jądrowej w Polsce (Challenges of education and training in chemistry for nuclear energy in Poland). Francusko-Polska Konferencja „Chemia dla energetyki jądrowej przyszłości” (French-Polish Sympo- sium “Chemistry for the nuclear energy of the future”), Montpellier, France, 05.04.2011. 2. Bobrowski K. Chemia radiacyjna w Polsce: 100 lat po odkryciu Marii Skłodowskiej-Curie (Radiation chemistry in Poland: 100 years after Maria Skłodowska-Curie’s discovery). Seminarium „Maria Skłodowska-Curie: naukowe dziedzictwo i współczesne polskie badania” (Seminar “Maria Skłodowska-Curie: scientific heritage and contemporary Polish research”), Brussels, Belgium, 09-11.06.2011. 3. Bobrowski K. Radiation-induced electron transfer in enkephalins. ESF Conference in partnership with LFUI “Charge transfer in biosystems”, Obergugl, Austria, 17-22.07.2011. 4. Bobrowski K. Radiation chemistry in Poland: 100 years after Maria Skłodowska-Curie’s discovery. Workshop “Current trends in radiation chemistry research”, Warszawa, Poland, 26.08.2011. 5. Bobrowski K. From retinal polyenes to peptides and proteins: radiation chemistry approach. Colloque Chimie sous Rayonnement: l’Heritage de Marie Curie, Paris, France, 14-17.11.2011. 6. Buczkowski M. Influence of ionising and UV radiation on template deposited nano-/microstructures of silver haloids. RER/8/014 Coordination Meeting on Radiation Engineered Nanostructures – Supporting Radiation Synthesis and the Characterization of Nanomaterials for Health Care, Environmental Protection and Clean Energy Applications, Warszawa, Poland, 16-18.11.2011. 7. Chmielewski A.G., Polak A., Palige J., Harasimowicz M., Zalewski M., Wawryniuk K., Roubi- nek O. Nowe rozwiązania technologiczne biogazowni – współpraca polskiej nauki z przemysłem (New technologic solution of biogas-works – cooperation of the Polish science and industry). Konferencja „Energia elektryczna, ciepło i gaz – perspektywą dla Gminy”, Minikowo, Poland, 11.03.2011. 8. Chmielewski A.G. Przyszłość energetyczna świata (The future of energy of the world). Mazowieckie Forum Nauczycieli Przedmiotów Przyrodniczych „Poznać chemię. Zrozumieć przyrodę”, Warszawa, Poland, 16.03.2011. 9. Chmielewski A.G. Chemia dla energetyki jądrowej przyszłości (Chemistry for nuclear energy of the future). Francusko-Polska Konferencja „Chemia dla energetyki jądrowej przyszłości” (French-Polish Sympo- sium “Chemistry for the nuclear energy of the future”), Montpellier, France, 05.04.2011. 10. Chmielewski A.G. Role of the Polish R&D institutions, academic organizations and industry in the development of nuclear energy in Poland. 1st International Nuclear Energy Congress, Warszawa, Poland, 23-24.05.2011. 11. Chmielewski A.G. Chemia dla energetyki jądrowej przyszłości (Chemistry for nuclear energy of the future). 160 LECTURES AND SEMINARS DELIVERED OUT OF THE INCT IN 2011

Chemia w rozwoju i postępie cywilizacji – Konferencja w Senacie Rzeczpospolitej Polskiej z okazji Mię- dzynarodowego Roku Chemii IYC 2011 i Roku Marii Skłodowskiej-Curie MSC-100, Warszawa, Poland, 07.06.2011. 12. Chmielewski A.G. Fossil, fissile and renewable energy sources, they role in sustainable country development. Conference “Scientific support to a competitive European carbon economy: energy, transport and emerg- ing technologies”, Warszawa, Poland, 07.06.2011. 13. Chmielewski A.G. Electron beam generated plasma flue gas treatment. 17th Romanian International Conference on Chemistry and Chemical Engineering, Sinaia, Romania, 07-10.09.2011. 14. Chmielewski A.G. Chemia radiacyjna i radiochemia w Polsce – sto lat później (Radiation chemistry and radiochemistry in Poland – 100 years later). Konferencja „Historia badań radiacyjnych w Polsce”, Warszawa, Poland, 14.11.2011. 15. Cieśla K. Application of ionizing radiation for preparation of edible and biodegradable nanostructured packaging materials based on polysaccharides. RER/8/014 Coordination Meeting on Radiation Engineered Nanostructures – Supporting Radiation Synthesis and the Characterization of Nanomaterials for Health Care, Environmental Protection and Clean Energy Applications, Warszawa, Poland, 16-18.11.2011. 16. Deptuła A., Brykała M., Łada W., Olczak T., Wawszczak D., Modolo G., Daniels H. Badania na syntezą tlenków uranowych za pomocą kompleksowej metody zol-żel (CSGP) (Synthesis of uranium oxides by complex sol-gel processes (CSGP)). Konferencja Naukowo-Techniczna „Polska nauka i technika dla elektrowni jądrowych w Polsce”, Mądralin, Poland, 13-14.01.2011. 17. Deptuła A., Brykała M., Łada W., Wawszczak D., Olczak T. Synthesis of uranium oxides doped by Th by complex sol-gel processes (CSGP). ACSEPT 3rd Annual Meeting, Manchester, Great Britain, 04-07.04.2011. 18. Głuszewski W. Radiacyjne metody modyfikacji elastomerów (Radiation methods for modification of elastomers). Seminarium poświęcone tematyce tworzyw sztucznych, Poznań, Poland, 22.03.2011. 19. Głuszewski Wojciech Wpływ prac Marii Skłodowskiej-Curie na rozwój technik radiacyjnych (Impact of the work of Maria Skłodowska-Curie on the development of radiation techniques). Konferencja „Maria Skłodowska-Curie. Dwukrotna noblistka i jej wkład w powstanie nowych dziedzin nauki”, Warszawa, Poland, 24.03.2011. 20. Głuszewski W. Maria Skłodowska-Curie prekursorką radiacyjnych metod konserwacji dzieł sztuki (Maria Skłodowska- -Curie precursor radiation method of preservation art work). XII Beskidzki Festiwal Nauki i Sztuki, Bielsko-Biała, Poland, 27-28.05.2011. 21. Głuszewski Wojciech Od Marii Skłodowskiej-Curie do radiacyjnych metod konserwacji obiektów o znaczeniu historycznym (From Maria Skłodowska-Curie to radiation methods of conservation of historical objects). Konferencja „Wybitne odkrycia źródłem inspiracji dla wynalazców – w 100-lecie II nagrody Nobla Marii Skłodowskiej-Curie”, Warszawa, Poland, 17.06.2011. 22. Głuszewski W. Prezentacja wystawy poświęconej 100. rocznicy nagrody Nobla przyznanej Marii Skłodowskiej-Curie (Presentation of the exibition, devoted to the anniversary of the Noble Prize for Maria Skłodowska- -Curie). 3rd International Nuclear Energy Forum, Warszawa, Poland, 18-19.10.2011. 23. Głuszewski W. Od Marii Skłodowskiej-Curie do radiacyjnej modyfikacji polimerów dla energetyki jądrowej (From Maria Skłodowska-Curie to radiation modification of polymers for nuclear power). 3rd International Nuclear Energy Forum, Warszawa, Poland, 18-19.10.2011. LECTURES AND SEMINARS DELIVERED OUT OF THE INCT IN 2011 161

24. Kalbarczyk P., Polkowska-Motrenko H., Chajduk E. Wydzielanie uranu z dwutlenku toru napromieniowanego w reaktorze jądrowym (Separation of uranium from thorium dioxide irradiated in nuclear reaction). Sympozjum „Bezpieczeństwo i ochrona radiologiczna w aspekcie budowy elektrowni jądrowej w Polsce”, Warszawa, Poland, 06.06.2011. 25. Kałuska I. Radiation sterilization – operational experience. IAEA Technical Cooperation Regional Project – RER/8/017 “Enhancing quality control methods and procedures for radiation technology” – IAEA Regional Training Course on Feasibility Studies for the Establishment of Radiation Processing Facilities, Zalakaros, Hungary, 28.08.-02.09.2011. 26. Kałuska I. Radiation sterilization – QA/QC requirements and programs. IAEA Technical Cooperation Regional Project – RER/8/017 “Enhancing quality control methods and procedures for radiation technology” – IAEA Regional Training Course on Feasibility Studies for the Establishment of Radiation Processing Facilities, Zalakaros, Hungary, 28.08.-02.09.2011. 27. Kałuska I. Inter-comparison trials in dosimetry. IAEA Technical Cooperation Regional Project – RER/8/017 “Enhancing quality control methods and procedures for radiation technology” – IAEA Regional Training Course on Feasibility Studies for the Establishment of Radiation Processing Facilities, Zalakaros, Hungary, 28.08.-02.09.2011. 28. Kciuk G. Electron transfer in dipeptides containing methionine and tyrosine. Workshop “Current trends in radiation chemistry research”, Warszawa, Poland, 26.08.2011. 29. Krajewski S., Bilewicz A., Łyczko K. Dicarbonyl and cyclopentadienyl 105Rh complexes as precursors for therapeutic radiopharmaceuticals. Working Group and MC Meeting of COST Action BM0607 “Targeted radionuclide therapy”, Inns- bruck/Igls, Austria, 08-09.04.2011. 30. Kruszewski M., Buraczewska I., Lankoff A., Wojewódzka M., Sommer S. Dozymetria biologiczna w Centrum Radiobiologii i Dozymetrii Biologicznej Instytutu Chemii i Techniki Jądrowej (Biological dosimetry in the Centre of Radiobiology and Biological Dosimetry, Institute of Nuclear Chemistry and Technology). Sympozjum „Bezpieczeństwo i ochrona radiologiczna w aspekcie budowy elektrowni jądrowej w Polsce”, Warszawa, Poland, 06.06.2011. 31. Kruszewski M. Nanosilver panaceum or Pandora box? RER/8/014 Coordination Meeting on Radiation Engineered Nanostructures – Supporting Radiation Synthesis and the Characterization of Nanomaterials for Health Care, Environmental Protection and Clean Energy Applications, Warszawa, Poland, 16-18.11.2011. 32. Lankoff A. Mechanizmy popromiennej śmierci komórkowej (Mechanisms of radiation-induced cell death). Kurs specjalistyczny z radiobiologii, Kielce, Poland, 07-10.11.2011. 33. Lankoff A. Mechanizmy powstawania popromiennych uszkodzeń DNA i ich naprawa (Mechanisms of radiation-induced DNA damage and repair). Kurs specjalistyczny z radiobiologii, Kielce, Poland, 07-10.11.2011. 34. Nyga M. Generation of oxidizing radicals and their reactivity in a selected group of ionic liquids. Workshop “Current trends in radiation chemistry research”, Warszawa, Poland, 26.08.2011. 35. Ostyk-Narbutt J. Co może wnieść Polska do współpracy międzynarodowej w zakresie chemii dla energetyki jądrowej? (What can Poland contribute into international collaboration on chemistry for nuclear power?). Francusko-Polska Konferencja „Chemia dla energetyki jądrowej przyszłości” (French-Polish Sympo- sium “Chemistry for the nuclear energy of the future”), Montpellier, France, 05.04.2011. 36. Polkowska-Motrenko H., Fuks L., Kalbarczyk P., Skotniczna M. Program badań biegłości dla placówek specjalistycznych prowadzących pomiary skażeń promienio- twórczych w ramach monitoringu radiacyjnego kraju (Proficiency testing scheme for laboratories forming radiation monitoring network). 162 LECTURES AND SEMINARS DELIVERED OUT OF THE INCT IN 2011

Sympozjum „Bezpieczeństwo i ochrona radiologiczna w aspekcie budowy elektrowni jądrowej w Polsce”, Warszawa, Poland, 06.06.2011. 37. Przybytniak G. Radiation chemistry of polymers. Top-down and bottom-up apporaches. Workshop “Current trends in radiation chemistry research”, Warszawa, Poland, 26.08.2011. 38. Przybytniak G. Effect of ionizing radiation on epoxy resin based composites. RER/8/014 Coordination Meeting on Radiation Engineered Nanostructures – Supporting Radiation Synthesis and the Characterization of Nanomaterials for Health Care, Environmental Protection and Clean Energy Applications, Warszawa, Poland, 16-18.11.2011. 39. Sartowska B., Piekoszewski J., Waliś L., Barlak M., Brunelli K., Starosta W., Senatorski J. Alloying the near surface layer of stainless steel with rare earth elements (REE) using intensity pulsed plasma beams (HIPPB). XIV International Conference on Electron Microscopy, Wisła, Poland, 26-30.06.2011. 40. Sommer Sylwester Biologiczne skutki promieniowania jonizującego (Biological effects of ionizing radiation). Konferencja „PoRa na Marię. Promieniotwórczośc wokół nas”, Warszawa, Poland, 09.11.2011. 41. Sommer Sylwester Biologiczne skutki promieniowania jonizującego (Biological effects of ionizing radiation). II Forum Nauczycieli Przedmiotów Przyrodniczych „PoRa na Marię. Promieniotwórczość wokół nas”, Ciechanów, Poland, 23.11.2011. 42. Starosta W. Metal-organic framework materials as templates for nanomaterials synthesis. Synthesis and characterization methods. RER/8/014 Coordination Meeting on Radiation Engineered Nanostructures – Supporting Radiation Synthesis and the Characterization of Nanomaterials for Health Care, Environmental Protection and Clean Energy Applications, Warszawa, Poland, 16-18.11.2011. 43. Sterniczuk M., Michalik J. Silownie jądrowe oparte na reaktorach PWR i BWR (Types of nuclear reactors – PWR and BWR systems). Konferencja Naukowo-Techniczna „Polska nauka i technika dla elektrowni jądrowych w Polsce”, Mądralin, Poland, 13-14.01.2011. 44. Walo M. Radiation modification of polyurethane biomaterials. Workshop “Current trends in radiation chemistry research”, Warszawa, Poland, 26.08.2011. 45. Wołkowicz S., Miecznik J., Strzelecki R., Zakrzewska-Trznadel G., Polkowska-Motrenko H. Uranium resources of Poland. IAEA Technical Meeting on Uranium Provinces and Mineral Potential Modeling, Vienna, Austria, 20-22.06.2011. 46. Zagórski Z.P.., Kornacka E.M. Historia badań radiacyjnych w Polsce po II wojnie światowej (The history of radiation research in Poland after the World War II). Konferencja „Historia badań radiacyjnych w Polsce”, Warszawa, Poland, 14.11.2011. 47. Zakrzewska-Trznadel G., Frąckiewicz K., Herdzik-Koniecko I., Kiegiel K., Gajda D., Chajduk E. Leaching of uranium ores from Polish deposits. Third General Assembly of the Sustainable Nuclear Energy Technology Platform, Warszawa, Poland, 29-30.11.2011. 48. Zakrzewska-Trznadel G., Biełuszka P., Zielińska B., Oszczak A., Chajduk E. Membrane processes for the uranium recovery from aqueous solutions. Third General Assembly of the Sustainable Nuclear Energy Technology Platform, Warszawa, Poland, 29-30.11.2011. LECTURES AND SEMINARS DELIVERED OUT OF THE INCT IN 2011 163 SEMINARS

1. Brykała Marcin Chemia paliw jądrowych (Nuclear fuel chemistry). Warsaw University of Technology, Faculty of Power and Aeronautical Engineering, Warszawa, Poland, 30.03.2011. 2. Chmielewski Andrzej G. Chemia i inżynieria chemiczna w energetyce jądrowej (Chemistry and chemical engineering in nuclear technologies). Łódź University of Technology, Łódź, Poland, 07.03.2011. 3. Chmielewski Andrzej G. Plazma generowana wiązką elektronów w technologiach ochrony środowiska (Electron-beam-generated plasma in technologies for the protection of environment). Rzeszów University of Technology, Rzeszów, Poland, 09.12.2011. 4. Chmielewski Andrzej G. Inżynieria chemiczna i procesowa w energetyce jądrowej (Chemical and process engineering in nuclear technologies). Rzeszów University of Technology, Rzeszów, Poland, 09.12.2011. 5. Chmielewski Andrzej G. Chemia w energetyce jądrowej (Chemistry for nuclear power). Jerzy Haber Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences, Kraków, Poland, 14.12.2011. 6. Doner Katarzyna Promieniowanie w nas i wokół nas (Radiation in us and around us). Maria Skłodowska-Curie Museum, Warszawa, Poland, 18.09.2011. 7. Głuszewski Wojciech Od Marii Skłodowskiej-Curie do współczesnych zastosowań chemii radiacyjnej (From Maria Skłodo- wska-Curie to modern applications of radiation chemistry). Maria Skłodowska-Curie Museum, Warszawa, Poland, 20.09.2011. 8. Krajewski Seweryn Przyroda sama tworzy reaktor? Reaktor w Oklo – stworzony w naturalnych warunkach (Does nature create reactor by itself? Reactor in Oklo – created in natural conditions). Maria Skłodowska-Curie Museum, Warszawa, Poland, 21.09.2011. 9. Lankoff Anna Maria Skłodowska-Curie – woman of science. Noble Museum, Stockholm, Sweden, 16.09.2011-31.01.2012. 10. Smoliński Tomasz, Chmielewski Andrzej G. A jednak, mimo wszystko, energetyka jądrowa? (In spite of everything, nuclear power?). Warsaw University of Technology, Faculty of Chemical and Process Engineering, Warszawa, Poland, 19.09.2011. 164 AWARDS IN 2011

AWARDS IN 2011

1. Preparation of nanocomposite tungsten-zirconium, potential material for radionuclide generators W-188/Re-188 Special award of the Croatian Association of Inventors at the XIV Moscow International Salon of In- ventions and Innovation Technologies “Archimedes-2011”, Moscow, Russia, 05-08.04.2011 Edward Iller, Danuta Wawszczak, Andrzej Deptuła, Marcin Konior, Wiesława Łada, Tadeusz Olczak 2. Diploma of the Ministry of Science and Higher Education for the project “Method of bioceramic material production” Wiesława Łada, Andrzej Ignaciuk, Andrzej Deptuła, Michał Kozłowski, Tadeusz Olczak 3. Diploma of the Ministry of Science and Higher Education for the project “Method for obtaining uranium dioxide in the form of spherical and irregular grains” Andrzej Deptuła, Marcin Brykała, Andrzej G. Chmielewski, Danuta Wawszczak, Wiesława Łada, Tadeusz Olczak 4. Application of GC to study radiolysis of cultural heritage artefacts The Best Poster Presentation Award at the International Conference on Development and Applications of Nuclear Technologies NUTECH-2011, Kraków, Poland, 11-14.09.2011 Wojciech Głuszewski

5. Method of production protective coatings made of titanium dioxide (TiO2) or lithium titanate (Li2TiO2) on nickel cathodes Gold Medal at the V International Warsaw Invention Show IWIS 2011, Warszawa, Poland, 03-05.11.2011 Wiesława Łada, Andrzej Deptuła, Danuta Wawszczak, Elisabetta Simonetti, Marco Brocco

6. Method of production protective coatings made of titanium dioxide (TiO2) or lithium titanate (Li2TiO2) on nickel cathodes Special Prize of Scientific School of Causality at the International Trade Fair “Ideas – Inventions – New Products” IENA-2011, Nuremberg, Germany, 27-30.10.2011 Wiesława Łada, Andrzej Deptuła, Danuta Wawszczak, Elisabetta Simonetti, Marco Brocco 7. Officer’s Cross of Order of Polonia Restituta conferred by the President of Poland for outstanding achievements in the scientific, didactic and social work and for the popularization of science in Poland and in the world Irena Szumiel 8. First degree award of Director of the Institute of Nuclear Chemistry and Technology for the chapter “Chemistry of sulfur-centered radicals” in the book “Recent trends in radiation chemistry” Krzysztof Bobrowski 9. Second degree award of Director of the Institute of Nuclear Chemistry and Technology for five publications on the structure and dynamics of charge transfer (CT) complexes published in international journals with high IF Andrzej Pawlukojć 10. Third degree award of Director of the Institute of Nuclear Chemistry and Technology for five publications on the properties of new complexes of uranium, lead, zinc and lithium with a pyridazine-carboxylic ligand published in “Acta Crystallographica” Janusz Leciejewicz, Wojciech Starosta 11. Distinction of the first degree of Director of the Institute of Nuclear Chemistry and Technology for the achieved progress in the preparation of thesis and professional activity Marcin Sterniczuk 12. Distinction of the second degree of Director of the Institute of Nuclear Chemistry and Technology for the achieved progress in the preparation of thesis and professional activity and participation in the preparation and realization of research projects Paweł Kalbarczyk AWARDS IN 2011 165 13. Distinction of the second degree of Director of the Institute of Nuclear Chemistry and Technology for the achieved progress in the preparation of thesis and professional activity and participation in the preparation and realization of research projects Przemysław Koźmiński 166 INDEX OF THE AUTHORS

INDEX OF THE AUTHORS

A J Abbas Kamel 42 Jahreis Gerhard 60 Apel Pavel 77 Jakowiuk Adrian 108, 109 Janik Ireneusz 20 B Jaworska-Sobczak Agnieszka 45 Banasik-Nowak Anna 59 Bańkowski Krzysztof 43 K Barlak Marek 79 Karlińska Magdalena 96 Barsbay Murat 28 Kavaklı Pınar Akkas 28 Bartłomiejczyk Teresa 58, 59 Kciuk Gabriel 64 Bartosiewicz Iwona 47, 68 Kiegiel Katarzyna 47 Bilewicz Aleksander 42 Kisała Joanna 23 Blonskaya Irina 77 Kocia Rafał 19 Bobrowski Krzysztof 64 Kornacka Ewa Maria 30 Bojanowska-Czajka Anna 23, 64 Korzeniowska-Sobczuk Anna 96 Brunborg Gunnar 58 Kosno Katarzyna 20, 23 Brykała Marcin 48, 51 Kowalska Ewa 108, 109 Brzóska Kamil 60 Koźmiński Przemysław 43 Bulgheroni Antonio 42 Krajewski Seweryn 42 Buraczewska Iwona 59 Kraś Janusz 108 Kruszewski Marcin 57, 58 C Kulisa Krzysztof 23 Celuch Monika 20, 23 L Chajduk Ewelina 47, 68 57, 58, 59 Chmielewski Andrzej G. 51, 86, 87 Lankoff Anna 73 Chwastowska Jadwiga 47, 68 Leciejewicz Janusz 26 Cieśla Krystyna 31 Lewandowska-Szumieł Małgorzata 59 Cydzik Izabela 42 Lisowska Halina Liśkiewicz Grażyna 100 D Ł Degen Christian 60 Łada Wiesława 48, 51 Deptuła Andrzej 48, 51 Łyczko Krzysztof 41 Doner Katarzyna 96 Łyczko Monika 41 Dusinska Maria 58 M F Majkowska-Pilip Agnieszka 42 Filipiak Paweł 108, 109 Malec-Czechowska Kazimiera 92 Frąckiewicz Kinga 47 Michalik Jacek 25, 26 G Miecznik Jerzy B. 47 19, 20 Gajda Dorota 47 Mirkowski Jacek 45 Głuszewski Wojciech 31 Miśkiewicz Agnieszka 108, 109 Gniazdowska Ewa 43 Modzelewski Łukasz 86 Grądzka Iwona 58, 60 Morgunov Volodymyr Grodkowski Jan 19 N 64 Gumiela Magdalena Nałęcz-Jawecki Grzegorz 64 28 Guven Olgun Narbutt Jerzy 39 100 Guzik Grzegorz P. Nyga Małgotrzata 19 H O Harasimowicz Marian 45 Olczak Tadeusz 48, 51 Herdzik-Koniecko Irena 39, 41 Orelovitch Oleg 77 I P Iwaneńko Teresa 58, 59 Palige Jacek 108 INDEX OF THE AUTHORS 167

Pańczyk Ewa 80 Sulich Agnieszka 19 Pawelec Andrzej 87 Sun Yongxia 86 Piekoszewski Jerzy 79 Szreder Tomasz 19 Pieńkos Jan 108, 109 Szumiel Irena 58, 59, 60 79 Pochrybniak Cezary Ś Pogocki Dariusz 20, 23 Śliwa Tomasz 80 Pokorska Irena 79 Polkowska-Motrenko Halina 68 T 77 Presz Adam Trojanowicz Marek 64 Przybytniak Grażyna 28 Pyszynska Marta 68 W Waliś Lech 79 S Walo Marta 28 25, 26 Sadło Jarosław Wawszczak Danuta 48, 51 100, 102 Sadowska Magdalena Wewiór Iwona 59 77, 79 Sartowska Bożena Węgierek-Ciuk Aneta 59 79 Senatorski Jan Wierzchnicki Ryszard 91, 92 39 Siekierski Sławomir Witman Sylwia 87 42 Simonell Federica Wojewódzka Maria 57, 58 48, 51 Smoliński Tomasz Wołkowicz Stanisław 47 60 Sochanowicz Barbara Wójciuk Grzegorz 60 Sommer Sylwester 59 Stachowicz Wacław 100, 102 Z Starosta Wojciech 73, 79 Zagórski Zbigniew Paweł 30 Sterniczuk Marcin 25, 26 Zakrzewska-Trznadel Grażyna 45, 47 Strzelczak Grażyna 25, 26 Zaza Fabio 51 Strzelecki Ryszard 47 Zielińska Barbara 41